Computational Techniques for

Process Simulation and Analysis

Using MATLAB®
 Computational Techniques for
Process Simulation and Analysis
Using MATLAB®

Niket S. Kaisare
MATLAB ® is a trademark of The MathWorks, Inc. and is used with permission. The MathWorks does not warrant the accuracy
of the text or exercises in this book. This book’s use or discussion of MATLAB ® software or related products does not constitute
endorsement or sponsorship by The MathWorks of a particular pedagogical approach or particular use of the MATLAB ® software.

CRC Press
Taylor & Francis Group,
6000 Broken Sound Parkway NW, Suite 300,
Boca Raton, FL 33487-2742

© 2018 by Taylor & Francis Group, LLC

CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-1387-4608-4 (Paperback)

International Standard Book Number-13: 978-1-4987-6211-3 (Hardback)

This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to pub-
lish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the
consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in
this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright
material has not been acknowledged please write and let us know so we may rectify in any future reprint.

Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any
form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming,
and recording, or in any information storage or retrieval system, without written permission from the publishers.

For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.
copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400.
CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been
granted a photocopy license by the CCC, a separate system of payment has been arranged.

Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification
and explanation without intent to infringe.

Visit the Taylor & Francis Web site at

http://www.taylorandfrancis.com

and the CRC Press Web site at

http://www.crcpress.com
To Pradnya for her unending love, patience, and support
and
To my parents, Komal and Satish Kaisare
Contents

Preface, xix
Author, xxiii

Chapter 1   ◾    Introduction 1

1.1 OVERVIEW 1
1.1.1 A General Model 1
1.1.2  A Process Example 2
1.1.3  Analysis of Dynamical Systems 3
1.2  STRUCTURE OF A MATLAB® CODE 3
1.2.1  Writing Our First MATLAB® Script 5
1.2.2 MATLAB Functions
® 7
1.2.3  Using Array Operations in MATLAB 9 ®

1.2.4  Loops and Execution Control 10

1.2.5  Section Recap 11
1.3  APPROXIMATIONS AND ERRORS IN NUMERICAL METHODS 12
1.3.1  Machine Precision 12
1.3.2  Round-Off Error 14
1.3.3  Taylor’s Series and Truncation Error 15
1.3.4  Trade-Off between Truncation and Round-Off Errors 18
1.4  ERROR ANALYSIS 20
1.4.1  Convergence and Stability 20
1.4.2  Global Truncation Error 21
1.5 OUTLOOK 23

vii
viii   ◾    Contents

Section I  Dynamic Simulations and Linear Analysis

Chapter 2   ◾    Linear Algebra 27

2.1 INTRODUCTION 27
2.1.1  Solving a System of Linear Equations 27
2.1.2 Overview 28
2.2  VECTOR SPACES 30
2.2.1  Definition and Properties 30
2.2.2  Span, Linear Independence, and Subspaces 32
2.2.3  Basis and Coordinate Transformation 34
2.2.3.1  Change of Basis 34
2.2.4  Null (Kernel) and Image Spaces of a Matrix 35
2.2.4.1  Matrix as Linear Operator 35
2.2.4.2  Null and Image Spaces in MATLAB® 39
2.3  SINGULAR VALUE DECOMPOSITION 41
2.3.1  Orthonormal Vectors 41
2.3.2  Singular Value Decomposition 42
2.3.3  Condition Number 47
2.3.3.1  Singular Values, Rank, and Condition Number 47
2.3.3.2  Sensitivity of Solutions to Linear Equations 47
2.3.4 Directionality 51
2.4  EIGENVALUES AND EIGENVECTORS 54
2.4.1  Orientation for This Section 54
2.4.2  Brief Recap of Definitions 54
2.4.3  Eigenvalue Decomposition 56
2.4.4 Applications 58
2.4.4.1  Similarity Transform 62
2.4.4.2  Linear Differential Equations 63
2.4.4.3  Linear Difference Equations 64
2.5 EPILOGUE 65
EXERCISES 67

Chapter 3   ◾    Ordinary Differential Equations: Explicit Methods 69

3.1  GENERAL SETUP 69
3.1.1  Some Examples 69
3.1.2  Geometric Interpretation 72
 Contents   ◾    ix

3.1.3  Euler’s Explicit Method 74

3.1.4  Euler’s Implicit Method 76
3.1.5  Stability and Step-Size 78
3.1.5.1  Stability of Euler’s Explicit Method 78
3.1.5.2  Error and Stability of Euler’s Implicit Method 79
3.1.6  Multivariable ODE 80
3.1.6.1  Nonlinear Case 81
3.2  SECOND-ORDER METHODS: A JOURNEY THROUGH THE WOODS 82
3.2.1  Some History 82
3.2.2  Runge-Kutta (RK-2) Methods 83
3.2.2.1  Derivation for RK-2 Methods 83
3.2.2.2  Heun’s Method 84
3.2.2.3  Other RK-2 Methods 86
3.2.3  Step-Size Halving: Error Estimate for RK-2 87
3.2.4  Richardson’s Extrapolation 89
3.2.5  Other Second-Order Methods (*) 91
3.2.5.1  Trapezoidal Rule: An Implicit Second-Order Method 91
3.2.5.2  Second-Order Adams-Bashforth Methods 92
3.2.5.3  Predictor-Corrector Methods 92
3.2.5.4  Backward Differentiation Formulae 93
3.3  HIGHER-ORDER RUNGE-KUTTA METHODS 93
3.3.1  Explicit Runge-Kutta Methods: Generalization 93
3.3.2  Error Estimation and Embedded RK Methods 97
3.3.2.1 MATLAB® Solver ode23 100
3.3.3  The Workhorse: Fourth-Order Runge-Kutta 101
3.3.3.1  Classical RK-4 Method(s) 102
3.3.3.2  Kutta’s 3/8th Rule RK-4 Method 103
3.4 MATLAB® ODE45 SOLVER: OPTIONS AND PARAMETERIZATION 103
3.5  CASE STUDIES AND EXAMPLES 105
3.5.1  An Ideal PFR 106
3.5.1.1  Simulation of PFR as ODE-IVP 106
3.5.1.2  Numerical Integration for PFR Design 108
3.5.1.3  Comparison of ODE-IVP with Integration 110
3.5.2  Multiple Steady States: Nonisothermal CSTR 111
3.5.2.1  Model and Problem Setup 111
x   ◾    Contents

3.5.2.2  Simulation of Transient CSTR 113

3.5.2.3  Step Change in Inlet Temperature 115
3.5.3  Hybrid System: Two-Tank with Heater 116
3.5.4  Chemostat: Preview into “Stiff ” System 120
3.6 EPILOGUE 125
EXERCISES 125

Chapter 4   ◾    Partial Differential Equations in Time 127

4.1  GENERAL SETUP 127
4.1.1  Classification of PDEs 128
4.1.2  Brief History of Second-Order PDEs 128
4.1.3  Classification of Second-Order PDEs and Practical Implications 129
4.1.3.1  Elliptic PDE 129
4.1.3.2  Hyperbolic PDE 130
4.1.3.3  First-Order Hyperbolic PDEs 131
4.1.3.4  Parabolic PDE 132
4.1.4  Initial and Boundary Conditions 132
4.2  A BRIEF OVERVIEW OF NUMERICAL METHODS 133
4.2.1  Finite Difference 133
4.2.2  Method of Lines 134
4.2.3  Finite Volume Methods 134
4.2.4  Finite Element Methods 135
4.3  HYPERBOLIC PDE: CONVECTIVE SYSTEMS 135
4.3.1  Finite Differences in Space and Time 136
4.3.1.1  Upwind Difference in Space 136
4.3.1.2  Forward in Time Central in Space (FTCS) Differencing 138
4.3.1.3  Lax-Friedrichs Scheme 139
4.3.1.4  Higher-Order Methods 139
4.3.2  Crank-Nicolson: Second-Order Implicit Method 140
4.3.2.1  Preview of Numerical Solution 141
4.3.3  Solution Using Method of Lines 141
4.3.3.1  MoL with Central Difference in Space 142
4.3.3.2  MoL with Upwind Difference in Space 145
4.3.4  Numerical Diffusion 149
 Contents   ◾    xi

4.4  PARABOLIC PDE: DIFFUSIVE SYSTEMS 150

4.4.1  Finite Difference in Space and Time 152
4.4.2  Crank-Nicolson Method 153
4.4.3  Method of Lines Using MATLAB ODE Solvers
® 154
4.4.3.1  MoL with Central Difference in Space 154
4.4.4  Methods to Improve Stability 157
4.5  CASE STUDIES AND EXAMPLES 157
4.5.1  Nonisothermal Plug Flow Reactor 157
4.5.2  Packed Bed Reactor with Multiple Reactions 164
4.5.3  Steady Graetz Problem: Parabolic PDE in Two Spatial Dimensions 170
4.5.3.1  Heat Transfer in Fluid Flowing through a Tube 170
4.5.3.2  Effect of Velocity Profile 174
4.5.3.3  Calculation of Nusselt Number 174
4.6 EPILOGUE 176
EXERCISES 177

Chapter 5   ◾    Section Wrap-Up: Simulation and Analysis 179

5.1  BINARY DISTILLATION COLUMN: STAGED ODE MODEL 181
5.1.1  Model Description 181
5.1.2  Model Equations and Simulation 183
5.1.3  Effect of Parameters: Reflux Ratio and Relative Volatility 185
5.2  STABILITY ANALYSIS FOR LINEAR SYSTEMS 186
5.2.1  Motivation: Linear Stability Analysis of a Chemostat 187
5.2.1.1  Phase Portrait at the Steady State 190
5.2.1.2  Trivial Steady State and Analysis 190
5.2.2  Eigenvalues, Stability, and Dynamics 191
5.2.2.1  Dynamics When Eigenvalues Are Real and Distinct 192
5.2.2.2  An Example 197
5.2.2.3 Summary 197
5.2.3  Transient Growth in Stable Linear Systems 198
5.2.3.1  Defining Normal and Nonnormal Matrices 198
5.2.3.2  Analysis of Nonnormal Systems 199
5.3  COMBINED PARABOLIC PDE WITH ODE-IVP: POLYMER CURING 201
xii   ◾    Contents

5.4  TIME-VARYING INLET CONDITIONS AND PROCESS DISTURBANCES 208

5.4.1  Chemostat with Time-Varying Inlet Flowrate 208
5.4.2  Zero-Order Hold Reconstruction in Digital Control 212
5.5  SIMULATING SYSTEM WITH BOUNDARY CONSTRAINTS 215
5.5.1  PFR with Temperature Profile Specified 216
5.6 WRAP-UP 219
EXERCISES 219

Section II  Linear and Nonlinear Equations and Bifurcation

Chapter 6   ◾    Nonlinear Algebraic Equations 225

6.1  GENERAL SETUP 225
6.1.1  A Motivating Example: Equation of State 226
6.2  EQUATIONS IN SINGLE VARIABLE 227
6.2.1  Bisection Method 228
6.2.2  Secant and Related Methods 233
6.2.2.1  Regula-Falsi: Method of False Position 235
6.2.2.2  Brent’s Method 235
6.2.3  Fixed Point Iteration 236
6.2.4  Newton-Raphson in Single Variable 238
6.2.5  Comparison of Numerical Methods 240
6.3  NEWTON-RAPHSON: EXTENSIONS AND MULTIVARIATE 241
6.3.1  Multivariate Newton-Raphson 241
6.3.2  Modified Secant Method 245
6.3.3  Line Search and Other Methods 247
6.4 MATLAB® SOLVERS 249
6.4.1  Single Variable Solver: fzero 249
6.4.2  Multiple Variable Solver: fsolve 250
6.5  CASE STUDIES AND EXAMPLES 253
6.5.1  Recap: Equation of State 253
6.5.2  Two-Phase Vapor-Liquid Equilibrium 253
6.5.2.1  Bubble Temperature Calculation 254
6.5.2.2  Dew Temperature Calculation 254
6.5.2.3  Generating the T–x–y Diagram 255
6.5.3  Steady State Multiplicity in CSTR 257
 Contents   ◾    xiii

6.5.4  Recap: Chemostat 261

6.5.5  Integral Equations: Conversion from a PFR 262
6.5.5.1  First-Order Kinetics 263
6.5.5.2  Complex Kinetics 266
6.6 EPILOGUE 268
EXERCISES 271

Chapter 7   ◾    Special Methods for Linear and Nonlinear Equations 273
7.1  GENERAL SETUP 273
7.1.1  Ordinary Differential Equation–Boundary Value Problems 274
7.1.2  Elliptic PDEs 274
7.1.3  Outlook of This Chapter 275
7.2  TRIDIAGONAL AND BANDED SYSTEMS 275
7.2.1  What Is a Banded System? 275
7.2.1.1  Tridiagonal Matrix 276
7.2.2  Thomas Algorithm a.k.a TDMA 276
7.2.2.1  Heat Conduction Problem 277
7.2.2.2  Thomas Algorithm 281
7.2.3  ODE-BVP with Flux Specified at Boundary 285
7.2.4  Extension to Banded Systems 288
7.2.5  Elliptic PDEs in Two Dimensions 289
7.3  ITERATIVE METHODS 290
7.3.1  Gauss-Siedel Method 291
7.3.2  Iterative Method with Under-Relaxation 295
7.4  NONLINEAR BANDED SYSTEMS 296
7.4.1  Nonlinear ODE-BVP Example 296
7.4.1.1  Heat Conduction with Radiative Heat Loss 297
7.4.2  Modified Successive Linearization–Based Approach 298
7.4.3  Gauss-Siedel with Linearization of Source Term 302
7.4.4 Using fsolve with Sparse Systems 304
7.5 EXAMPLES 304
7.5.1  Heat Conduction with Convective or Radiative Losses 304
7.5.2  Diffusion and Reaction in a Catalyst Pellet 305
xiv   ◾    Contents

7.5.2.1  Linear System and Thiele Modulus 305

7.5.2.2  Langmuir-Hinshelwood Kinetics in a Pellet 308
7.6 EPILOGUE 311
EXERCISES 311

Chapter 8   ◾    Implicit Methods: Differential and Differential Algebraic

Systems 313
8.1  GENERAL SETUP 313
8.1.1  Stiff System of Equation 313
8.1.1.1  Stiff ODE in Single Variable 315
8.1.2  Implicit Methods for Distributed Parameter Systems 316
8.1.3  Differential Algebraic Equations 316
8.2  MULTISTEP METHODS FOR DIFFERENTIAL EQUATIONS 317
8.2.1  Implicit Adams-Moulton Methods 318
8.2.2  Higher-Order Adams-Moulton Method 319
8.2.3  Explicit Adams-Bashforth Method 320
8.2.4  Backward Difference Formula 322
8.2.5  Stability and MATLAB Solvers
® 325
8.2.5.1  Explicit Adams-Bashforth Methods 325
8.2.5.2  Implicit Euler and Trapezoidal Methods 325
8.2.5.3  Implicit Adams-Moulton Methods of Higher Order 325
8.2.5.4  BDF/NDF Methods 325
8.2.5.5 MATLAB® Nonstiff Solvers 326
8.2.5.6 MATLAB® Stiff Solvers 326
8.3  IMPLICIT SOLUTIONS FOR DIFFERENTIAL EQUATIONS 327
8.3.1  Trapezoidal Method for Stiff ODE 327
8.3.1.1  Adaptive Step-Sizing 329
8.3.1.2  Multivariable Example 330
8.3.2  Crank-Nicolson Method for Hyperbolic PDEs 331
8.3.2.1  Exploiting Sparse Structure for Efficient Simulation 337
8.4  DIFFERENTIAL ALGEBRAIC EQUATIONS 337
8.4.1  An Introductory Example 338
8.4.1.1  Direct Substitution 338
8.4.1.2  Formulating and Solving a DAE 339
 Contents   ◾    xv

8.4.2  Index of a DAE and More Examples 340

8.4.2.1  Example 2: Pendulum in Cartesian Coordinate System 341
8.4.2.2  Example 3: Heterogeneous Catalytic Reactor 341
8.4.3  Solution Methodology: Overview 342
8.4.3.1  Solving Algebraic Equation within ODE 343
8.4.3.2  Combined Approach 345
8.4.4  Solving Semiexplicit DAEs Using ode15s in MATLAB® 348
8.5  CASE STUDIES AND EXAMPLES 351
8.5.1  Heterogeneous Catalytic Reactor: Single Complex Reaction 351
8.5.2  Flash Separation/Batch Distillation 353
8.6 EPILOGUE 359
EXERCISES 360

Chapter 9   ◾    Section Wrap-Up: Nonlinear Analysis 363

9.1  NONLINEAR ANALYSIS OF CHEMOSTAT: “TRANSCRITICAL”
BIFURCATION 364
9.1.1  Steady State Multiplicity and Stability 364
9.1.2  Phase-Plane Analysis 365
9.1.3  Bifurcation with Variation in Dilution Rate 366
9.1.4  Transcritical Bifurcation 368
9.2  NONISOTHERMAL CSTR: “TURNING-POINT” BIFURCATION 372
9.2.1  Steady States: Graphical Approach 372
9.2.2  Stability Analysis at Steady States 374
9.2.3  Phase-Plane Analysis 376
9.2.4  Turning-Point Bifurcation 377
9.3  LIMIT CYCLE OSCILLATIONS 379
9.3.1  Oscillations in Linear Systems 379
9.3.2  Limit Cycles: van der Pol Oscillator 381
9.3.2.1  Relaxation vs. Harmonic Oscillations 382
9.3.3  Oscillating Chemical Reactions 383
9.4  SIMULATION OF METHANOL SYNTHESIS IN TUBULAR REACTOR 387
9.4.1  Steady State PFR with Pressure Drop 388
9.4.1.1  Reaction Kinetics 388
9.4.1.2  Input Parameters and Initial Processing 389
9.4.1.3  Steady State PFR Model 391
9.4.2  Transient Model 394
xvi   ◾    Contents

9.5  TRAJECTORY OF A CRICKET BALL 398

9.5.1  Solving the ODE for Trajectory 399
9.5.2  Location Where the Ball Hits the Ground 400
9.5.3 Animation 403
9.6 WRAP-UP 405
EXERCISES 405

Section III  Modeling of Data

Chapter 10   ◾    Regression and Parameter Estimation 409

10.1  GENERAL SETUP 409
10.1.1 Orientation 410
10.1.2  Some Statistics 411
10.1.3  Some Other Considerations in Regression 413
10.2  LINEAR LEAST SQUARES REGRESSION 413
10.2.1  Fitting a Straight Line 413
10.2.2  General Matrix Approach 415
10.2.3  Goodness of Fit 418
10.2.3.1  Maximum Likelihood Solution 418
10.2.3.2  Error and Coefficient of Determination 419
10.3  REGRESSION IN MULTIPLE VARIABLES 423
10.3.1  General Multilinear Regression 423
10.3.2  Polynomial Regression 424
10.3.3  Singularity and SVD 428
10.4  NONLINEAR ESTIMATION 429
10.4.1  Functional Regression by Linearization 429
10.4.2 MATLAB® Solver: Linear Regression 432
10.4.3  Nonlinear Regression Using Optimization Toolbox 434
10.5  CASE STUDIES AND EXAMPLES 437
10.5.1  Specific Heat: Revisited 437
10.5.2  Antoine’s Equation for Vapor Pressure 438
10.5.2.1  Linear Regression for Benzene 439
10.5.2.2  Nonlinear Regression for Ethylbenzene 440
 Contents   ◾    xvii

10.5.3  Complex Langmuir-Hinshelwood Kinetic Model 441

10.5.3.1 Case 1: Experiments Performed at Single
Concentration of B 442
10.5.3.2 Case 2: Experiments Performed at Different Initial
Concentrations of B 444
10.5.4  Reaction Rate: Differential Approach 445
10.6 EPILOGUE 448
10.6.1 Summary 448
10.6.2  Data Tables 449
EXERCISES 450

APPENDIX A: MATLAB® PRIMER, 451

APPENDIX B: NUMERICAL DIFFERENTIATION, 475

APPENDIX C: GAUSS ELIMINATION FOR LINEAR EQUATIONS, 485

APPENDIX D: INTERPOLATION, 499

APPENDIX E: NUMERICAL INTEGRATION, 511

BIBLIOGRAPHY, 527

INDEX, 529
Preface

S tudents today are expected to know one or more of the several computing or simu-
lation tools as part of their curriculum, due to their widespread use in the industry.
MATLAB® has become one of the prominent languages used in research and industry.
MATLAB is a numerical computing environment that is based on a MATLAB scripting
language. MathWorks, the makers of MATLAB, describe it as “the language of technical
computing.” The focus of this book will be to highlight the use of MATLAB in technical
computing or, more specifically, in solving problems in the analysis and simulation of pro-
cesses of interest to engineers.
This is intended to be an intermediate-level book, geared toward postgraduate students,
practicing engineers, and researchers who use MATLAB. It provides advanced treatment
of topics relevant to modeling, simulation, and analysis of dynamical systems. Although
this is not an introductory MATLAB or numerical techniques textbook, it may however
be used as a companion book for introductory courses. For the sake of completeness, a
primer on MATLAB as well as introduction to some numerical techniques is provided in
the Appendices. Since mid-2000s,we have always used MATLAB in electives in IIT Madras.
The popularity of MATLAB among students led us to start a core undergraduate (sopho-
more) and a postgraduate (first-year masters) laboratory. Since 2016, I have started teach-
ing a massive open online course (MOOC) on MATLAB programming on the NPTEL
platform.* The first two years of this course had over 10,000 enrolled students. Needless to
say, MATLAB has become an important tool in teaching and research. The focus of all the
above courses is to introduce students to MATLAB as a numerical methods tool. Some of
the students who complete these courses inquire about the next-level courses that would
help them apply MATLAB skills to solve engineering problems. This book may also be used
for this purpose. In introductory courses, a significant amount of time is spent in develop-
ing the background for numerical methods itself. In our effort to make the treatment gen-
eral and at a beginner’s level, we eschew real-world examples in favor of abstracted ones.
For example, we would often introduce a second-order ODE using a generic formulation,
such as y″ + ay′ + b(y − c) = 0. A sophomore who hasn’t taken a heat transfer course may
not yet appreciate a “heating in a rod” problem. An intermediate-level text means that it
is more valuable to use a real example, such as T″ + r−1T′ + β(T − Ta) = 0. The utility of such

*  NPTEL stands for National Programme for Technology Enhanced Learning and is a Government of India−funded initiative
to bring high-quality engineering and science courses on an online (MOOC) platform to enhance students’ learning.

xix
xx   ◾    Preface

an approach cannot be understated, since it allows the freedom to introduce some of the
complexity that engineers, scientists, and researchers face in their work.
The value of using real-world examples was highlighted during my experience in indus-
trial R&D, where we used MATLAB extensively. We needed to interface with cross-func-
tional teams: engineering, implementation, and software development teams. Individuals
came from a wide range of backgrounds. These interactions exposed me to a new experi-
ence: Your work must be understood by people with very different backgrounds, who may
not speak the same technical language. The codes had to bridge the “language barrier”
spoken in different teams, and the codes were to be combined with a reasonably intuitive
interface. I have tried to adopt some of these principles in this book, without moving too far
from the more common pedagogy in creating such a book.
Thus, a practically oriented text that caters to an intermediate-level audience is my objec-
tive in writing this book.

ORIGIN OF THIS BOOK

There are several excellent books on numerical techniques for engineers. Laurene
Forsell’s book, Numerical Methods Using MATLAB, provides a MATLAB-based
approach to learning numerical techniques. The books on numerical techniques by
Chapra and Canale and by S.K. Gupta are excellent undergraduate textbooks, which
introduce undergraduates to this subject for the first time. Thus, their focus is concep-
tual understanding of numerical techniques themselves. While undergraduate teaching
is in good stead, a textbook that covers core requirements for a balanced postgraduate
curriculum is missing. Such a book will also be useful to practicing engineers, scien-
tists, and researchers who use MATLAB.
This book is borne out of my experience in teaching a postgraduate course called
Process Analysis and Simulation, postgraduate lab in Process Simulation, and theory of
computational techniques. They provide the first-year postgraduates the basis to tackle
research problems in their theses. The former course takes a balanced focus on model-
ing, simulation, and analysis of chemical process systems, while the process simulation
lab gives them a numerical methods perspective. Postgraduate-level books, such as the
evergreen Numerical Recipes by Press et al., are rather advanced and focused on numeri-
cal methods. On the other hand, the book by Strogatz on nonlinear dynamics or other
similar books are not general enough for the needs of an audience interested in simula-
tions. A “bridge” book, which assumes some familiarity with undergraduate material, but
still covers the basics, is missing.
Having said this, I do not intend this to be a postgraduate numerical methods text. This
book aims to introduce students and practitioners to simulation and analysis of process
systems in MATLAB. We often find it difficult to connect the numerical tool to the physical
analysis of a system. This book intends to bring in a strong process simulation treatment to
linear stability and nonlinear analysis.
Thus, this book intends to bring a practical approach to expounding theories: both
numerical aspects of stability and convergence, as well as linear and nonlinear analysis of
 Preface   ◾    xxi

systems. The “process” is the focus. Numerical methods are introduced insofar as is essen-
tial to make a judicious choice of algorithms for simulation and analysis.

PREREQUISITES
Since this is a postgraduate-level text, some familiarity with an undergraduate-level
numerical techniques or an equivalent course is assumed, though we will review all the
relevant concepts at the appropriate stage. So, the students are not expected to remem-
ber the details or nuances of “Newton-Raphson” or “Runge-Kutta” methods, but this
book is not the first time they hear these terms.
Some familiarity with coding (MATLAB, Fortran, C++, Python, or any language)
will be useful, but not a prerequisite. MATLAB primer is provided in the Appendix for
first-time users of MATLAB. Finally, with respect to writing MATLAB code, I focus on
“doing it right the first time” approach—by bringing in good programming practices
that I have learnt over the years. Things like commenting and structuring your code,
scoping of variables, etc., are also covered, not as an afterthought but as an integral part
of the discussion. However, these are dealt with more informally than a “programming
language” course.

HOW THIS BOOK IS LAID OUT

This book derives examples from three different courses I have taught: (i) Numerical
Methods, (ii) Process Analysis and Simulation, and (iii) Computational Programming
Lab. It is structured so that it may be used for any of the three courses. Each chapter
deals with one approach to solving computational problems (e.g., ODEs, PDEs, nonlin-
ear equations, etc.), culminating in case studies that utilize the concepts discussed in the
chapter.
I have split the book into three sections, which are laid out with a “Process Analysis”
viewpoint: Section I covers system dynamics and linear system analysis; Section II covers
solving nonlinear equations, including differential algebraic equations (DAEs); and Section
III covers function approximation and optimization for modeling of data. The following
table summarizes the various chapters in the book:

Basics Chapter 1 Appendix A

Introduction MATLAB® Primer
Appendices Appendix B Appendix C Appendix E
Differentiation Linear Equations Integration
Section I. Chapter 2 Chapter 3 Chapter 4 Chapter 5
Dynamics Linear Algebra ODE-IVP Transient PDEs Simulation
Section II. Chapter 6 Chapter 7 Chapter 8 Chapter 9
Equations Nonlinear Equations Special Methods Implicit Methods Nonlinear Analysis
(ODE-BVP/PDE) (DAEs)
Section III. Appendix D Chapter 10
Data Fitting Interpolation Regression
xxii   ◾    Preface

LAYOUT FOR PROCESS ANALYSIS

The layout of this book is largely based on the postgraduate-level process simulation and
analysis course. The material I cover in this course is chronologically as laid out in the book.
The course starts with an introduction to the role of simulation and analysis in engineering,
and a primer on MATLAB. Thereafter, I introduce concepts in linear algebra (Chapter 2),
ODEs (Chapter 3), and solving hyperbolic and parabolic PDEs (Chapter 4). Problems in
either linear analysis or dynamical simulations (Chapter 5) typically form mid-term proj-
ects for students. The second part of the course also follows a similar structure, with nonlin-
ear equations (Chapter 6), ODE-BVPs and elliptic PDEs (Chapter 7), and DAEs (Chapter 8)
providing the adequate background for end-semester projects involving nonlinear analysis
and bifurcation (Chapter 9). I have added Chapter 10 (Parameter Estimation) for the sake
of completion.

LAYOUT FOR NUMERICAL METHODS

This book may also be used for an advanced numerical methods course. In such a case,
I suggest treating the material column-wise. This course may start with the first row to
cover the basics (Introduction, MATLAB Primer, Differentiation, Integration, and Linear
Equations). Thereafter, Chapter 2 and Chapter 6 may be covered, to equip students to solve
linear and nonlinear equations. Chapters 3 and 7 cover ODE-IVP and ODE-BVP, respec-
tively, followed by Parameter Estimation (Chapter 10). A four-credit course may also cover
PDEs (Chapter 4). Typically, Chapters 5 and 9 will be beyond the scope of such a course.

LAYOUT FOR NUMERICAL DIFFERENTIAL EQUATIONS

The shaded chapters (Chapters 3, 4, 5, 7, 8, and 9), along with appendices on numerical
differentiation and integration, can form a numerical differential equations course.

FOR PRACTICING ENGINEER OR NEW RESEARCHER

A practicing engineer or researcher can embark on a self-guided journey through case
studies and examples covered in this book. This includes not only the case studies analyzed
in Chapters 5 and 9 but also the ones discussed in other chapters (penultimate section in
the other chapters).

MATLAB® is a registered trademark of The MathWorks, Inc. For product information,

please contact:

The MathWorks, Inc.

3 Apple Hill Drive
Natick, MA 01760-2098 USA
Tel: 508-647-7000
Fax: 508-647-7001
E-mail: [email protected]
Web: www.mathworks.com
Author

Dr. Niket S. Kaisare is currently an associate professor in the Department of Chemical

Engineering at IIT Madras. He received his PhD in chemical engineering from Georgia
Institute of Technology, working in the area of model-based advanced process control.
He  then joined the Department of Chemical Engineering at the University of Delaware,
where he worked on multiscale modeling of reacting flows in microreactors, as a postdoc-
toral researcher. After this, he joined IIT Madras as assistant professor in 2007. While in IIT
Madras, he taught several courses in process analysis and simulation, computational tech-
niques, process simulation laboratory, and advanced control theory. MATLAB was used
extensively in most of these courses. He has also taught an online course called “MATLAB
Programming for Numerical Computations” as a part of NPTEL (National Programme for
Technology Enhanced Learning). This course was popular, with more than ten thousand
students enrolling in it.
He spent three years, from mid-2011 to 2014, in industrial R&D. During this stint, he
worked on numerous simulation problems related to modeling of vehicle catalytic conver-
tors, cryogenic hydrogen storage, monitoring and control of oil and gas wells, and auto-
mation engineering. As a part of the R&D team, he used MATLAB extensively and spent
a significant part of his time interfacing with engineering and development teams.
He has extensive experience working in MATLAB and FORTRAN as well as simulation
softwares Fluent and Comsol. He also has good working experience with various other
simulation tools, such as Aspen-Plus/Unisim, Gaussian, and Abacus. His current research
program is focused on “multiscale modeling, analysis, and control of catalytic microreac-
tors for energy- and fuel-processing applications.”

xxiii
 CHAPTER 1

Introduction

1.1 OVERVIEW
1.1.1 A General Model
This book is targeted toward postgraduate students, senior undergraduates, researchers, and
practicing engineers to provide them with a practical guide for using MATLAB® for process
simulation and numerical analysis. MATLAB was listed among the top ten programming
languages by the IEEE Spectrum magazine in 2015 (a list that was topped by Java, followed by
C and C++). While the basics of MATLAB can be learnt through various sources, the focus
of this book is on the analysis and simulation of processes of interest to engineers.
The terms “analysis” and “simulation” are generic terms that define a rather broad spectrum
of problems and solution techniques. Engineering is a discipline that deals with the transfor-
mation of raw material, momentum, or energy. Thus, this book will focus on those process
examples where the variables of interest vary with time and/or space, including the relationship
of these state variables with their properties. I will use an example of a reactor-separator process
in Section 1.1.2 to illustrate this. While this is a chemical engineering example, the treatment in
this book is general enough for other engineering and science disciplines to also find it useful.
The problems mentioned above that are considered in this book include ordinary and
partial differential equations (ODEs and PDEs), algebraic equations (either linear or non-
linear), or combinations thereof. The three sections of this book are organized based on the
computational methodology and analysis tools that will be used for the respective problems.
Section I of this book includes Chapters 2 through 5 and deals with ODE-IVPs (initial
value problems) as well as the problems that can be converted into a standard form that can
be solved with ODE-IVP tools. A generic ODE-IVP is of the type
dy
= f ( t ,y ;f
f) (1.1)
dt
where
t is an independent variable
y ∈ R n is a vector of dependent variables
ϕ represents parameters
1
2   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Examples include simulations of level and temperature in a stirred tank, simulations of a

reactor, mass-spring-damper, pendulum (in cylindrical coordinates), and others.
Section II of this book includes Chapters 6 through 9 and deals with the problems of
the type

0 = g ( x;f
f) (1.2)

where
x ∈ R m is a vector of dependent variables
ϕ represents parameters

Nonlinear algebraic equations, such as Equation 1.2, fall under this category. Moreover,
ODE-BVPs (boundary value problems) and several PDEs are also converted into the form
of Equation 1.2. Section II will not only cover techniques to solve algebraic equations but
also expound methods to convert ODEs/PDEs to this form. A combination of Equations 1.1
and 1.2, called differential algebraic equations (DAEs), is covered in Chapter 8. Chapters 5
and 9 are the concluding chapters of the first two sections. They build on the concepts from
the preceding chapters in the respective sections for the analysis of dynamical systems and
provide an introduction to advanced topics in simulations.
Finally, Chapter 10, included in Section III, deals with the parameter estimation prob-
lem, that is, to compute the parameter vector, ϕ, that best fits the experimental data.

1.1.2 A Process Example

I will use an example from a typical chemical process to motivate the discussion. Figure 1.1
shows a flow sheet of a typical process with a recycle. A reaction of the type A → B takes
place in the plug flow reactor (PFR); the two species are separated in the distillation column;
product B is obtained as the bottoms product, whereas the lighter species A is recycled back.
The PFR is modeled using the following ODE:

dx A
F = -r ( x A ) , x A V =0 = xin (1.3)
dV

Ffeed Fr, xr P, xp

D, xD Purge
Fin, xin

F, xf

F, xf

B, xB

FIGURE 1.1  A typical process consisting of a reactor and a separator, with a recycle.
 Introduction   ◾    3

The reactor outlet conditions are obtained by solving the ODE-IVP above. ODE-IVP prob-
lems are covered in Chapter 3 of this book. If a dynamic response of the PFR is required,
the resulting model is a PDE, where the state variable of interest varies in both space and
time. Solutions to transient PDEs are covered in Chapter 4. Advanced topics in simulation
are presented in Chapter 5, for example, when the inlet conditions or model parameters
vary with time and/or space.
The distillation column consists of N nonlinear algebraic equations in N unknowns (mole
fractions on each tray). For example, one of the model equations for the kth tray is given by

ax i
0 = ( Li -1 xi -1 - Li xi ) + (Vi +1 yi +1 - Vi yi ) where yi = (1.4)
1 + ( a - 1) xi

Such balance equations are written for each ideal stage of the distillation column, resulting
in N nonlinear algebraic equations that need to be solved simultaneously to obtain N vari-
ables. These are further discussed in Chapter 6.
Axial dispersion is neglected while deriving the model (Equation 1.3). Inclusion of the
axial dispersion term converts this IVP to a BVP, which is covered in Chapter 7. Discretizing
the ODE-BVP results in a set of equations with a special matrix structure. Mass transfer
limitations result in DAEs, which are covered in Chapter 8.

1.1.3 Analysis of Dynamical Systems

There is an equal amount of focus on the analysis of dynamical systems. To this end,
Chapter 2 revisits concepts in linear algebra. I present a more contemporary treatment of
linear algebra. Chapter 5 presents transient analysis of dynamical systems and their linear
stability behavior. In addition to stability and dynamics based on eigenvalues of the linear
dynamical system, the topic of transient growth in nonnormal systems is discussed. Related
concepts of directionality and analysis using eigenvalue and singular value decompositions
are discussed.
Chapter 9, which wraps up Section II of this book, is dedicated to nonlinear analysis
and bifurcation. Well-known examples of stirred reactor, chemostat, mass-spring-damper
system, and van der Pol oscillator will be used in this chapter. Chapter 10 is devoted to an
important topic of parameter estimation.
Furthermore, advanced topics in efficient simulation and analysis are also presented.
These include handling time-varying inputs and boundary constraints (Chapter 3), com-
bination of ODE and PDE (Chapter 5), and a fun example of tracking the trajectory of a
cricket ball (or baseball) with simulation and animation.
Before we get to these examples, I will review good practices and structuring of MATLAB
codes as well as errors in numerical approaches.

1.2 STRUCTURE OF A MATLAB® CODE

A brief introduction to some programming practices specific to MATLAB is covered in
this section. The intention of this section is to introduce the reader to good MATLAB
programming practices, rather than “Introduction to MATLAB.” A basic primer on using
4   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

MATLAB is instead provided in Appendix A. This book follows the principle of “learn it
right the first time.” Good programming hygiene, in writing MATLAB codes, is evange-
lized and implemented right from the first example. The book follows another principle
that the best way to learn programming is through extensive practice. MathWorks, the
parent company that develops MATLAB, has good introductory video tutorials, available
at: http://in.mathworks.com/products/matlab/videos.html.* A beginner may want to start
with their “Getting Started” videos.† I also have an introductory MOOC course on using
MATLAB for numerical computations on National Programme for Technology Enhanced
Learning.‡
Figure 1.2 shows a screenshot of MATLAB window. The main section contains two
­windows: MATLAB editor at the top and MATLAB command window at the bottom. The
MATLAB editor currently shows the MATLAB file firstFlowSheet.m, which is a
“driver script” to simulate the reactor-separator flow sheet described above. Line number
13 shows the following statement:

[F,x,err] = solveFlowSheet(Ffeed,Vpfr,purge,initVal);

FIGURE 1.2  Screenshot of MATLAB® window.

*  Last accessed on October 13, 2015.

†  http://in.mathworks.com/videos/getting-started-with-matlab-68985.html.

‡  http://nptel.ac.in/courses/103106118/ (Last accessed on June 16, 2017).

 Introduction   ◾    5

A careful look at the directory listing (left-top window) shows a file solveFlowSheet.m.
This is a MATLAB function file. A brief description of MATLAB script and function files
is presented in Appendix A (Section A.6). In this example, this function takes in the input
and initial conditions for the flow sheet and computes all the flowrates and mole fractions.
These are returned to the calling program and are captured in variables F and x (which are
standard notations for flowrate and mole fraction, respectively). Some of the basic principles
of programming in MATLAB, illustrated in Figure 1.2, include the following:

• Codes are sectioned using this new feature* in MATLAB editor. Each program has
input, executing, and output blocks. Sanctity of these blocks is maintained, as far as
possible.
• Codes are well-commented.
• Codes are modular, where each MATLAB function is intended to perform a
specific task.
• Appropriate use of MATLAB functions and scripts.
• Using standard or descriptive names for variables.
• Careful attention to variable definitions and scoping.

These aspects of MATLAB coding are described in this section. Another aspect discussed
presently is to use the powerful matrix and linear algebra capabilities to write efficient
and highly readable codes. Some of these features will be described using factorial and
Maclaurin series expansion of exponent:

x2 xn
ex = 1+ x + + + (1.5)
2! n!

1.2.1 Writing Our First MATLAB® Script

The first MATLAB script we will write is to compute a factorial. The script is also written to
interact with the user for input/output. The reader is encouraged to view the corresponding
tutorial video at http://in.mathworks.com/videos/writing-a-matlab-program-69023.html.

Example 1.1  Computing a Factorial

Problem: Write a MATLAB script to compute a factorial of a number input by the user.
Solution: The script file for computing factorial is given below:

%% User Inputs
n = input('Please enter a number: ');

*  Since MATLAB 2009. So, this feature is not really new!

6   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

% Checking for non-negative number input by user

if (n<0)
error('Negative numbers are not allowed');
end

%% Computing factorial
fact = 1;
for i = 1:n
fact = fact*i;
end

%% Display Results
disp([num2str(n), '! is ', num2str(fact)]);

The code consists of three sections: (i) user input section, where the input parameters for
the code are specified; (ii) computing section, which forms the main core of the code; and
(iii) results/output section, that is, the last line where the result is displayed. The lines start-
ing with “%%” (two percentage signs) as the first two characters in a line indicate the start
of a new section. Sectioning helps keep the code clean and easy to understand. Additionally,
comments are provided in the code to help readability.

PERSONAL EXPERIENCE
While this may seem unnecessary for short codes, good coding habits need to be devel-
oped right from the start. It is generally accepted that commenting makes codes readable
and shareable with others. However, advantages of structuring and commenting your code
go beyond that. Comments help us understand our own codes better and faster. It helps in
coding by making one think about the skeletal structure of the code before they start writing
the code, thus reducing the number of errors. It also reduces the time taken for debugging
a code.

The above code is how most students write their first code in MATLAB. However, this
does not take advantage of the powerful array operations provided by MATLAB. For
example, the command prod(1:n) will calculate the product of vector [1:n], which
is nothing but the factorial itself. Indeed, the entire computing section can be replaced
by a single line:

fact = prod(1:n);

If factorials for all integers from 1 through n are desired, then it is more efficient to use
cumprod(1:n). This will return a 1 × n vector, whose ith element is i!. At the command
prompt, type ‘help cumprod’ to understand its use.
 Introduction   ◾    7

1.2.2 MATLAB® Functions
A MATLAB script, shown in Example 1.1, is a MATLAB file that contains statements that
are executed sequentially by MATLAB (as if they were typed on the command prompt).
The script is executed by calling it using the file name. The script shares workspace with
the entity that calls it; in most cases, that is the command window workspace. MATLAB
functions, on the other hand, are intended to execute commands (which may call other
functions or subfunctions) for a specific purpose, with a set of input and output parameters.
The variables defined in a function have a local scope. In other words, these variables are
not available in the MATLAB workspace. The variables defined in the script, on the other
hand, are available in the main MATLAB workspace.
The first line in a MATLAB function is the function definition:
function [out1, out2, ...] = funName(in1, in2, ...)

Here, function is a keyword that defines function and funName is the name of the
function. The function command also defines a comma-separated list of input and output
variables. The name of the m-file containing the function should be the same as the func-
tion name.* If the file name is different than the function name, the function is known to
MATLAB through its file name. It is a good programming practice to use the same name
for the function and the m-file.
Let us redo the factorial problem of Example 1.1 using the function.

Example 1.2  Example 1.1 Revisited

Problem: Write a MATLAB function to compute the factorial of n.
Solution: The MATLAB function is given below. It may be compared with the script
file from Example 1.1.
function factVal = myFact(n)
% Function to calculate factorial of n
% Function usage:
% factVal = myFact(n)
if (n<0)
error('Negative numbers are not allowed');
else
factVal = prod(1:n);
end

The above function is saved in a file, myFact.m, which has the same name (without the
extension “.m”) as the function name. myFact calculates the factorial of n when invoked
at command prompt:
>> fact = myFact(5)
fact =
120

*  Exception is a nested or daughter function, which will not be considered in this book.
8   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

When the first example is executed, the commands in the script file are executed in the same
workspace as the MATLAB command workspace. Thus, all the variables, n, fact, and i,
are available in the command workspace. If, on the other hand, function myFact is used,
only the variable fact appears on the MATLAB workspace. If user interaction is required
similar to that in Example 1.1, a separate MATLAB script may be written as

% File: factDriver.m
% User Input
n = input('Please enter a number: ');
% Calculate factorial and display
disp([num2str(n), '! is ', num2str(myFact(n))]);

Following are a few tips regarding functions and scripts. Let us take an analogy with C++.
When it comes to large projects, I treat a “driver” script similar to the void main{...}
of C++. While this distinction is actually incorrect, it is a good programming practice in
MATLAB to have a single driver script, whereas all other tasks are executed in individual
functions.
Alternatively, the way to think about scripts vs. functions (usually for stand-alone prob-
lems) is to look at the purpose of the file. If the file executes a sequence of commands toward
a particular end, a script is perhaps more suitable, for example, the computation of factorial
when the purpose is to compute the factorial. Function, on the other hand, may be used

• To define a function f(x, y, …) of one or more variables

• To calculate output variable(s) or properties as a function of input conditions, such as
reaction rate r(T, Ci) and specific heat cp(T)
• To define a function f(x, y, …) to be passed as an argument to a MATLAB solver
• To perform computations for individual task, unit operation, equipment, or system
(such as the PFR or distillation column in the flow sheet Figure 1.1)

The above are good practices and not really a syntactic requirement from MATLAB. Thus, if
one’s purpose is to compute a factorial, Example 1.1 should be used; instead, if the purpose
is to use the factorial in Maclaurin series expansion, Example 1.2 is the chosen alternative.
With this background, the following example will show the computation of Maclaurin
series expansion of ex as per Equation 1.5.

Example 1.3  Maclaurin Expansion of Exponent

Problem/Solution: The following code computes e2 using Maclaurin series up to x10
terms:

%% Input values
x = 2;
n = 10;
 Introduction   ◾    9

%% Calculation of e^x
expVal = 1.0;
for i = 1:n
currTerm = x^i/myFact(i); % Calculate i-th term
expVal = expVal + currTerm;
end

%% Displaying results
disp(['exp(2) = ', num2str(expVal)]);

The result of executing of the above script is:

exp(2) = 7.3889

The above example is shown for pedagogical purposes. This is a very inefficient way of
coding; the example is primarily used to introduce the reader to the difference between
functions and scripts and to show how to use functions (myFact.m in this example) in
MATLAB. The inefficiency of the code is that a large number of computations were unnec-
essarily used in calculating the value of currTerm in each for loop iteration. A better way
to do this is a recursive computation:

currTerm = currTerm*(x/i);

An astute reader will also recognize the use of brackets here, to reduce the chance of round-
off error.

1.2.3 Using Array Operations in MATLAB®

If a user has experience with coding in C++, Java, or FORTRAN, this is the method
employed to compute the functions using Maclaurin series. However, the most intermedi-
ate and advanced users of MATLAB will exploit highly powerful matrix operations that
MATLAB natively provides. Consider the vector:

éx x x xù
v=ê  ú
ë1 2 3 n û

MATLAB function cumprod (see Appendix A for a MATLAB Primer) computes cumula-
tive product. Thus, first element is itself, second is a product of the first two elements, third
is a product of first three elements, and so on:

éx x2 x3 xn ù
cumprod ( v ) = ê  ú
ë1 1× 2 1× 2 × 3 n! û
10   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 1.3  (Continued)

The entire code for computing the Maclaurin series of ex can be written as

expVal = 1.0 + sum(cumprod(x./[1:n]));

The term in the inner brackets, x./[1:n], generates the vector v. Note the use of
element-wise division operator “./”—a unique feature of MATLAB’s matrix capabili-
ties. The result of cumprod is all terms in the series expansion but leading 1.
As an exercise, compute the Maclaurin series expansions of

x3 x5
sin ( x ) = x - + +
3! 5!

x2 x 4
cos ( x ) = 1 - + -
2! 4!

using array operations, without using loops. Hint:

é -x ( -1)xn ù
n
x2 -x 3
cumprod ( -v ) = ê  ú
ê 1 1× 2 1× 2 × 3 n! ú
ë û

1.2.4 Loops and Execution Control

An introduction to for/while loops and if-then-else conditions is provided in
Appendix A (Section A.6). In this section, we will use these statements to write our first
code for an iterative numerical technique, which is one of the most important classes of
numerical techniques. Héron’s method, described in the first century AD, is arguably one of
the oldest iterative numerical techniques. It is used for computing the square root of 2 (or
any number n). The working principle of the method is that for any positive real number, x,
the solution 2 always lies between x and 2/x. Starting with an arbitrary guess, x(i), the next
guess is taken as arithmetic mean of x(i) and 2/x(i).

Example 1.4  Héron’s Method

Problem/Solution: Starting with an initial guess of x(0) = 2, use 10 iterations of Héron’s
method:

1æ i 2 ö
x ( ) = ç x ( ) + (i )
i +1

2è ÷
x ø

% Square root of 2 using Heron's algorithm

x = 2; % Initial guess
 Introduction   ◾    11

%% Iterations
for i = 1:10
x(i+1) = (x(i)+2/x(i))/2;
end
%% Display results
disp(['Herons Square Root: ', num2str(x(end))]);

All the intermediate values x(i) can be displayed as below:

>> disp(x)
2.0000 1.5000 1.4167 1.4142 1.4142 1.4142

Starting with an initial guess of 2.0, the value of x rapidly converges to 1.4142 in the
fifth iteration. Taking the difference of the consecutive terms of x gives us

>> disp(diff(x));
-0.50 -0.0833 -0.0025 -2.124e-6 -1.595e-12 0

The fourth iteration result of 1.4142 differs from the previous by 2.124 × 10−6. Often,
this is considered as sufficiently accurate for a numerical technique.

1.2.5 Section Recap
We started this section with a quick view of the structure of a typical MATLAB code in
Figure 1.2. The importance of creating a good skeletal structure for MATLAB codes was
discussed. Sectioning and comments are very useful in this aspect to keep the code clean,
readable, and easy to debug. The importance of having clear demarcation between (1)
input/parameter definition, (2) computation, and (3) output/wrap-up sections in a code
cannot be emphasized enough. It is far too common to see programmers define their model
parameters at multiple points in a code. This was emphasized by using input-computation-
output sectioning in smallest of projects (see Example 1.1 or Example 1.3). Example 1.2 was
used to highlight the use of a function. Unlike a project driver script file, a function gets its
inputs as input arguments, and returns output arguments. Thus, most functions primarily
have a computation section.
The choice of variable names used is also important. When the context was clear,
variable names x or i were used. However, it is best to have more descriptive names,
such as currTerm to represent “current term” and expVal to represent “value of
exponential.” Also note capitalization of the first letter of an English word in the vari-
able name to improve readability. A variable currTerm is more easily readable than
currterm.
Finally, as users will see later in this book, the use of global for sharing variables
between functions or workspaces is avoided. We pay attention to variable scoping and treat
workspaces as sacrosanct.
12   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

1.3 APPROXIMATIONS AND ERRORS IN NUMERICAL METHODS

We have considered two examples of numerical methods in the previous section: ex from
truncated infinite series and calculation of x = 2 using an iterative algorithm. The true
value of e2 = 7.3890561. The value computed using the truncated Maclaurin series was 7.3889.
The  difference between the two values is the error in numerical computation using the
numerical approximation. Before proceeding further, we will now formally define error.

DEFINITION: ERRORS
The true value of a variable x is represented as x∗ while the current approximation as x(i).
The absolute (true) error is defined as

E = x* - x ( i )

and the relative (true) error is defined as

E =
( x* -x( ) )
i

x*

Typically, the true solution is not known a priori. Hence, the following two definitions
of approximation errors are defined. Herein, the error is defined based on the difference
between subsequent approximations of the solution. Thus

x ( i +1) - x ( i )
e = x ( i +1) - x ( i ) and e =
x(i )

EXAMPLE
With these definitions, the absolute error in the calculation of e2 using Maclaurin series
through x10 terms is

E = 6.139 ´ 10-5

Consider the fourth iteration value in Héron’s algorithm of 1.4142 (x(5) in Example 1.4,
since x(1) is the initial guess). The true and approximation errors are

E ( 4) = 2 - x ( 4) = 1.595 ´ 10-12 and e( 4) = x ( 4) - x ( 3) = 2.124 ´ 10-6

The error occurs due to two reasons: (1) truncation of the infinite series to finite number of
terms and (2) finite precision representation leading to rounding off.

1.3.1 Machine Precision
A computer is a finite precision machine. While integers are exactly represented in a com-
puter representation, real number representation is inexact. Real numbers are represented
using a finite number of bits (or binary digits) in floating-point representation in a computer.
 Introduction   ◾    13

Consider two real numbers r1 , r2 ∈ R; there are infinite number of real numbers between r1
and r2. However, in computer representation of real numbers, there are only a finite num-
ber of real numbers between r1 and r2. To understand this concept better, let us consider an
example of decimal floating-point representation of real numbers. Consider that our “mind-
computer” represents a positive real number using six digits: five decimal digits and a single
signed decimal exponent. The five decimal digits form mantissa m, whereas the sixth digit
is the signed exponent. The floating-point representation of this number may be written as

e -5
0  ´ 10
.xxxxx
 
m

The mantissa lies between 1 and 1/base (base=10 in decimal system), that is, m ∈ [0, 1).
The digit in the exponent, e, also takes the value between 0–9; thus with a bias of –5 shown
above, the exponent takes values from 10−5 − 104. The number 314.27 is represented as

0.31427 ´ 108 -5

The next number that can be represented in this system is therefore

0.31428 ´ 108 -5

The decimal computer cannot represent any other number between the two numbers, 314.27
and 314.28. With the five-digit mantissa, the number 314.2712 cannot be distinguished from
314.27. Thus, the last two digits get chopped off as a consequence of finite precision represen-
tation of a number. In summary, the floating-point representation is of the form

m ´ be - F (1.6)

where
m is the mantissa, with 1/b ≤ m < 1
e is the exponent
b is the base (2 in binary; 10 in decimal)
F is the exponent bias (fixed for a computer)

Thus, real number representation in a computer has a “least count.” This least count, when
normalized, depends on the mantissa and is known as machine precision.

DEFINITION: MACHINE PRECISION

Machine precision ϵ is defined as the maximum relative error in the floating-point repre-
sentation of real numbers. In practice, it is the smallest positive real number such that the
number (1 + ϵ) can be distinguished from 1.
14   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

MATLAB uses double precision numbers with a word length of 64 bits: 1 sign bit, 52 man-
tissa bits, and 11 exponent bits. The machine precision in MATLAB is obtained using the
keyword eps. It is typically 2−52. Consider the following statements typed on the command
prompt:

>> x = 1+2^-52;
>> disp(x-1.0)
2.2204e-16
>> x = 1+2^-53;
>> disp(x-1.0)
0

The second result is a consequence of the “least count” in MATLAB. Example 1.5 below
contains a code to recursively compute machine precision in MATLAB. Starting with an
initial value of ϵ = 1, the following procedure is adopted. The value of ϵ is halved; (1 + ϵ) is
computed and compared with 1. If the two cannot be distinguished, the value of ϵ has fallen
below the machine precision; else, the above procedure is repeated until 1 and (1 + ϵ) are
undistinguishable.

Example 1.5  MATLAB® Code to Compute Machine Precision

% Code for finding machine precision
epsilon = 1.0;
iFlag = true;
while(iFlag)
epsilon = epsilon/2.0;
testNum = 1+epsilon;
if (testNum-1.0 == 0)
iFlag = false;
end
end
disp(['Machine Precision = ', num2str(epsilon*2)]);

1.3.2 Round-Off Error
The finite precision of a computer leads to round-off errors, errors that result due to inexact
representation of real numbers in a computer. Note that a computer chops off the addi-
tional digits (thus, 314.2712 and 314.2772 are both represented as 314.27). Continuing
with the example of six-digit decimal floating-point representation, the following example
highlights the origins of round-off errors. The values of x satisfying quadratic equation
x2 − bx + c = 0 are

b ± b2 - 4c
x=
2
 Introduction   ◾    15

Example 1.6  Quadratic Equations

Problem: Solve the quadratic equation x2 − 97x + 1 = 0 using floating-point representa-
tion. The true solutions of the equation are 96.98968 and 0.01031037.
Solution: Consider the term p = b2 - 4c :

( 0.97e2 ) - ( 0.4e1) =
2
p= 0.94090e 4 - 0.00040e 4

The digits of the mantissa are moved during subtraction so that the two numbers have
the same exponent. If one of the numbers is much smaller than the other, precision is lost.
In this example, p = 0.94050e 4 = 0.96979e2.
The value of p is obtained accurately for five significant digits. The two solutions
therefore are

ìï 0.96989 ´ 102
x = 0.5 ( 0.97000e2 ± 0.96979e2 ) = í -1
ïî0.10500 ´ 10

Note the second solution, true value is 0.01031 and computed value is 0.01050. This
is due to the fact that the values of b and p are fairly close to each other; thus chop-
ping off the trailing digits in p before subtraction results in a rather large round-off
error.
An alternative formula for the second solution is

2c
x=
b + b 2 - 4c

x = 0.20000e1 ¸ ( 0.97000e2 + 0.96979e2 ) = 0.10310 ´10-1

Thus, avoiding subtraction between two close numbers results in better error behavior.

The above example demonstrates how the machine precision gives rise to round-off
errors. The computer-stored value x is related to the true value x as

x = x (1 + emach )

As we shall see in Section 1.3.4, subtraction of two very close numbers results in errors in
numerical differentiation. Before that, we will introduce the other type of error, truncation error.

1.3.3 Taylor’s Series and Truncation Error

Consider Taylor’s series expansion:
h2 hn éënùû
f ( a + h ) = f ( a ) + hf ¢ ( a ) + f ¢¢ ( a ) +  + f ( a ) + En (1.7)
2! n!
16   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Taylor’s series expansion is used, either directly or indirectly, for the derivation of a large
number of numerical algorithms described in this text. Finite number of terms in Taylor’s
series are retained (e.g., 10 terms were used in computing e2). The error resulting from
truncating an infinite series in deriving a numerical approximation is known as truncation
error. The nth order error term is

hn+1
f éë ùû ( x ) , where x Î éëa, ( a + h ) ùû
n +1
En =
( )
n + 1 !

This is often represented as

( )
O hn+1

and the error is said to be of the order of hn + 1.

The greater the number of terms retained in Taylor’s series, the smaller is the error; the
smaller the value of h chosen, the smaller is the error. Recall that the error in computing e2
using series expansion until the 10th term was E = 6.139 × 10−5.
We demonstrate the concept of order of accuracy and error using the example of numer-
ical integration. Classical Newton-Cotes integration formulae (see Appendix E for more
information on numerical integration), namely, the trapezoidal rule and Simpson’s 1/3rd
rule, will be used to demonstrate this. An integral can be approximated using these rules as
b
h
Trapezoidal rule: h = ( b - a )
ò f ( x ) dx = 2 éë f a ( )
+ fb ùû + O h3 (1.8)
a
b

Simpson’s 1/3rd rule: h = ( b - a ) / 2

ò f ( x ) dx =
h ( )
éë f a + 4 f a +h + fb ùû + O h
5
(1.9)
3
a

The last term in both the equations indicate how the truncation errors in using the above
formula depend on the step-size, h. Consider the numerical example below that illustrates
truncation error and order of accuracy.

Example 1.7  Truncation Error in Numerical Integration

Problem: Use the trapezoidal and Simpson’s 1/3rd rules to compute (for different
­values of h):
h
1

ò
0
1 + x2
dx

The true solution is tan−1(h). The aim is to compute errors in numerical integration.
 Introduction   ◾    17

Solution: The code for calculating the numerical integral is given below. The inte-
gral is computed for four different values of step-size h. Although the first instinct is
to use a for loop to loop over different values of h, we will exploit the powerful array
operations in MATLAB to write an efficient code:

% Integral using Newton-Cotes (single application)

h = [1, 0.1, 0.01, 0.001]; % Various step sizes
f1 = 1; % f(a) = f(0)

%% Trapezoidal Rule
trueInt = atan(h); % True values of integral
f2 = 1./(1+h.^2); % f(a+h)
trapInt = h/2.*(f1+f2);
trapErr = abs(trueInt-trapInt);

%% Simpson's 1/3rd Rule

trueInt = atan(2*h); % True value of integral
f3 = 1./(1+(2*h).^2); % f(a+2h)
simpInt = h/3.*(f1+4*f2+f3);
simpErr = abs(trueInt-simpInt);

%% Plotting results
loglog(h,trapErr,'-b', h,simpErr,'--r');
xlabel('step size, h'); ylabel('error');

The atan function used in line 5 returns a vector of the same size as vector h, wherein
each element is tan−1(⋅) of the corresponding element of h. The next line contains
computation of f(a + h) = f(h) for all values of h. Notice the use of element wise division
(./) and power (.^) operators.
Figure 1.3 shows log-log plot of error in the numerical computation of integral
vs. step-size h. Both of these are approximately straight lines. The error is lower
with Simpson’s 1/3rd rule and falls faster with step-size compared to the trapezoi-
dal rule. The step-size falls by three orders of magnitude. Corresponding error
using the trapezoidal rule falls by nine orders of magnitude (from ~10−1 to ~10−10).
Similarly, error in Simpson’s 1/3rd rule falls by 15 orders of magnitude (from ~10−1
to ~10−16).

Alternatively, one can plot log ( E ) vs. log ( h ) on a linear plot. The straight line for the
trapezoidal rule has a slope of approximately 3, whereas that for Simpson’s 1/3rd rule is 5.
()
In other words, log(etrap) ~ 3 log(h) = log(h3) and log ( esimp ) ~ 5 log h = log æç h ö÷. Note that
5

è ø
this corresponds to the order of the error term in Equations 1.6 and 1.7.
18   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

100

10–5

Error
10–10

10–15

10–20
10–2 100
Step-size, h

FIGURE 1.3  Truncation error vs. step-size for single application of the trapezoidal (solid) and
Simpson’s 1/3rd rules (dashed).

1.3.4 Trade-Off between Truncation and Round-Off Errors

Consider the example of a numerical approximation of a derivative, given by

f ( xi + h ) - f ( xi )
f ¢( x ) = + O (h ) (1.10)
xi h

f ( xi + h ) - f ( xi - h )

f ¢( x )
xi
=
2h
( )
+ O h2 (1.11)

Equation 1.10 is known as forward difference approximation, whereas Equation 1.11 is the
central difference. Refer to Appendix B for more details on numerical derivatives.

Example 1.8  Numerical Derivatives and Truncation Error

Problem: Find the numerical derivative of f(x) = tan−1(x) at x = 1 using forward and
( )
-1
central difference formulae for different values of h. True solution is f ¢ ( x ) = 1 + x 2 .
Solution: This problem will be solved in two parts. First, numerical derivatives
will be obtained for h = 0.01 and h = 0.0001 using both the methods. Using forward
difference

f ¢ ( x ) » 0.497508 and f ¢ ( x ) » 0.499975

e0.01 = 2.492 ´ 10-3 and e0.0001 = 2.4999 ´ 10-5

Thus, decreasing the step-size h by two orders of magnitude resulted in a reduction in

the error by two orders of magnitude. That is because the error is proportional to h1.
Consider the results for central difference:

e0.01 = 8.333 ´ 10-6 and e0.0001 = 8.332 ´ 10-10

 Introduction   ◾    19

10–3

Forward diff

10–6

Error
10–9

Central diff
10–12
10–10 10–8 10–6 10–4 10–2
Step-size, h

FIGURE 1.4  Effect of step-size on error in computing numerical derivative using forward and cen-
tral difference formulae.

Not only is the error in the central difference formula lower than forward differ-
ence but reducing the step-size by two orders of magnitude improves the error by
four orders of magnitude: a consequence of error being proportional to h2 for central
differences.
Figure 1.4 shows the error vs. step-size plot (on a log-log scale) using forward and
central difference formulae to compute the numerical derivative of tan−1(x). The fol-
lowing code was used for this purpose:

% Numerical derivatives with forward/central differences

x = 1;
trueVal = 1/(1+x^2);

%% Forward difference
hFwd = 10.^[-9:-3];
df_fwd = (atan(x+hFwd)-atan(x)) ./ (hFwd);
errFwd = abs(df_fwd-trueVal);

%% Central difference
hCtr = 10.^[-7:-2];
df_ctr = (atan(x+hCtr)-atan(x-hCtr)) ./ (2*hCtr);
errCtr = abs(df_ctr-trueVal);

%% Plotting
loglog(hFwd,errFwd,'-b',hCtr,errCtr,'--r');

The above example highlights the trade-off between truncation and round-off errors.
The  truncation error decreases as step-size is reduced, whereas the round-off error
increases at very low step-sizes. Thus, there is an optimal step-size at which the net
20   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

error is minimum. In case of numerical differentiation, the optimal choice of step-size

for forward and central difference formulae is

fwd
hopt = e1mach
/2 fwd
and hopt = e1mach
/3
(1.12)

where εmach is the machine precision. Therefore, the optimal values of step-sizes for forward
and central difference formulae are ~10−8 and ~10−5, respectively. When the step-size is
greater than these respective values, slopes of eh vs . h curves are 1 and 2, respectively, for the
( )
two formulae. Note that this slope corresponds to the order of accuracy, O h1 and O h2 , ( )
respectively.

1.4 ERROR ANALYSIS
A basic understanding of some key numerical issues is important to make an appropriate
choice of numerical method used to solve process simulation problems. Some of these con-
cepts are introduced presently. Numerical methods broadly work in three ways. First is the
direct way of computation, such as approximation of e2 from truncated Taylor’s series or
numerical derivatives shown above. Second is an iterative way, such as the Héron’s method
in computing 2. Third is step-wise recursive method, such as multiple applications of
Newton-Cotes integration formulae (see Appendix E for details). Solutions of differential
equations (see Chapter 3, for example), optimization, etc., also fall under this category.
Error analysis introduced in this section is applicable to iterative and recursive methods.
A general introduction to some key concepts will be presented. As defined before, x(i) is the
current numerical solution, and x  ∗ is the true solution. We can write x(i) = x  ∗ + E(i), where E(i)
is the error. As we have seen in the examples before, the numerical solution changes with
the step-size and/or number of recursions. The next value x(i + 1) is computed as some func-
tion of x(i):

i +1
( )
i
(
x( ) = f x( ) = f x* + E( )
i
)
Thus, it is possible to write

i +1
(
E( ) = F E( ) ; x* , x( )
i i
)
indicating that the error depends on the previous error (as also on the true solution and
numerical solution). Issues regarding behavior of the numerical solution x(i) and error E(i)
are discussed.

1.4.1 Convergence and Stability

Convergence and stability are properties of interest to iterative and recursive methods.
A numerical method is said to be convergent if the numerical errors E(i) go to zero as i
increases. In other words, as the number of iterations increase or step-size decreases, the
 Introduction   ◾    21

solution x(i) approaches the true solution x ∗. Stability is a related property. The error E(i) is
a result of incorrect initial conditions and round-off errors. A method is said to be stable if
the effect of these errors do not grow with the application of the numerical method. In other
words, E(i) should decrease (or at least not increase in unbounded manner) as i increases.
An important consideration in choosing a numerical method is its convergence behav-
ior. All the examples considered so far were stable and convergent. The next consideration
is “how fast does the numerical method converge.” The order of convergence of an iterative
numerical method is said to be n if

n
E( ) = k éE( ) ù
i +1 i

ë û

Consider the errors in Example 1.4. Subsequent iterations of Héron’s algorithm result in the
following errors:

{
e ( ) = 5 ´ 10-1
i
8.33 ´ 10-2 2.5 ´ 10-3 2.12 ´ 10-6 1.6 ´ 10-12 0}
It can be inferred that the algorithm has a quadratic order of convergence, that is, n = 2.
Besides, the constant κ is also important. For example, when n = 1 (linearly convergent
method), the numerical method is convergent if |κ| < 1.
The terms stability and convergence have different meanings. Stability refers to whether
or not errors grow with iterations or recursions, whereas convergence means whether the
numerical solution reaches the true solution.

1.4.2 Global Truncation Error

Let us revisit the numerical integration to motivate this section. The accuracy of numerical
integration can be increased by dividing the region into multiple intervals and using mul-
tiple applications of the trapezoidal and Simpson’s 1/3rd rules, which is given by
b
h

ò
Trapezoidal rule : f ( x ) dx =
a
2ë
é f1 + 2 f 2 + 2 f 3 +  + 2 fn + fn+1 ùû

(1.13)

b
h

ò
Simpson’s 1 / 3rd rule : f ( x ) dx =
a
3ë
é f1 + 4 f 2 + 2 f 3 + 4 f 4 +  + 4 fn + fn+1 ùû

(1.14)

In the above, h = (b − a)/n. We choose n as an even number. While number of intervals is n,

there are (n + 1) nodes, with f1 = f(a) , fi + 1 = f(a + ih) and fn + 1 = f(b).
Let us take the last example as a segue into using numerical solutions for the design,
simulation, and analysis of process systems. The design equation of a PFR is given by

a
F dX

V = 0m
kC0 ò r ( X )
0
(1.15)
22   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

where X is the conversion, F0 is the inlet flowrate and the reaction rate is given by kC0mr ( X ) .
The design problem is to find the volume V of the PFR for the desired conversion, a.

Example 1.9  Newton-Cotes Formulae for Design of a PFR

Problem: Use multiple applications of the trapezoidal and Simpson’s 1/3rd rules to com-
pute the volume of PFR required for 80% conversion, when Equation 1.15 simplifies to

0. 8
dX

V = 0. 5
ò (1 - X )
0
1.25

Solution: The true solution is given by Vtrue = 2[(1 − a)−0.25 − 1] = 0.9907 m3.

The following code is written to calculate the volume using n intervals:

% Newton Cotes for PFR Design

b = 0.8; % Conversion
trueVal = 2 * ((1-b)^-0.25 - 1); % PFR volume
N = [8, 32, 128, 512, 800]; % # of intervals

%% Solving design equation

for i = 1:length(N)
n = N(i); h = b/n;
x = [0:h:b];
fx = 0.5 ./ (1-x).^1.25;
% Trapezoidal Rule
V_trap(i) = h/2*(fx(1)+fx(n+1)) + h*sum(fx(2:n));
% Simpson's 1/3 Rule
V_simp(i) = h/3*(fx(1)+fx(n+1)) + ...
h/3*4*sum(fx(2:2:n)) + h/3*2*sum(fx(3:2:n));
end

%% Display results
trapErr = abs(trueVal-V_trap);
simpErr = abs(trueVal-V_simp);
loglog(b./N,[trapErr;simpErr]);

Figure 1.5 shows the effect of step-size on error for the two methods. The step-size h is
decreased by two orders of magnitude. The error using trapezoidal rule reduces from
10−2 to 10−6, that is, by four orders of magnitude, whereas the error using Simpson’s
rule decreases by eight orders of magnitude.
The PFR volumes obtained using the two numerical methods are

V_trap = 1.0091 0.9919 0.9908 0.9907 0.9907

V_simp = 0.9922 0.9907 0.9907 0.9907 0.9907
 Introduction   ◾    23

10–1

10–3

10–5

Error
10–7

10–9

10–11
10–3 10–2 10–1
Step-size, h

FIGURE 1.5  Error analysis for the trapezoidal and Simpson’s 1/3rd rules.

Example 1.9 shows the application of the numerical integration technique to solve a PFR
design problem. The solution obtained is accurate even with a reasonably small number
of intervals used. The main intention of this example was, however, to demonstrate error
analysis for the integration formulae. According to Equation 1.8, the truncation errors in
( )
the trapezoidal rule are O h3 . However, Figure 1.5 shows that the error vs. step-size curve
has a slope of 2. This is because the global truncation error incurred in multiple applications
of the trapezoidal rule is of the order h2.
Equations 1.8 and 1.9 showed the local truncation error, error resulting from a single
application of the numerical technique. When multiple applications of the numerical tech-
nique are used, we encounter the local error, as well as an error resulting from the accumu-
lation of errors until the current point. The net effect of this is to typically reduce the order
of accuracy of the numerical technique. In case of the two Newton-Cotes formulae, global
truncation errors are given by

( ) ( )
µ h2 f ¢¢ ( x ) , Esimp µ h 4 f ¢¢¢¢ ( x )
gte gte
Etrap

1.5 OUTLOOK
Example 1.9 was our first glimpse into Process Simulation using MATLAB, where we
used numerical integration to compute the volume of the PFR. Section 1.4.2 started with
a discussion on an integration problem (Equations 1.13 and 1.14), followed by a practical
example (design of PFR), and ending with Example 1.9 showing the solution and results in
MATLAB. We will follow a similar structure in most of the chapters: First, the numerical
techniques of importance will be discussed, followed by a concise description of the prob-
lem to be simulated or analyzed, and ending with the application of those techniques to
solve the problem.
The chapters are organized based on the approach to solving the problem. In this context,
the treatment in this book differs from introductory textbooks. For example, Chapter  3
24   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

covers ODE-IVPs of nonstiff systems. On the other hand, ODE-BVPs are covered in
Chapter 7 along with elliptic PDEs since they both involve systems that are diffusive in one
or more dimensions, respectively. Solutions of stiff ODEs and DAEs, which require a simi-
lar set of tools for simulation and analysis, are covered in Chapter 8. Numerical techniques
that are more generic in nature, such as numerical differentiation, integration, and solving
linear equations, are covered in the Appendices.
 I
Dynamic Simulations and Linear Analysis

25
 CHAPTER 2

Linear Algebra

2.1 INTRODUCTION
Linear algebra is typically introduced in an introductory engineering mathematics course
in the context of solving a set of n linear equations in n unknowns. Consider the following
example:

x + 2y = 1
(2.1)
x-y =4

The above set of linear equations is written in the standard form as

é1 2 ù é x ù é1 ù
ê úê ú = ê ú (2.2)
ë1 -1û ë y û ë 4 û
 

A x b

The geometric interpretation that is commonly discussed in introductory courses is that the
solution (3, − 1) is the point of intersection of the two lines. This is a useful way of introduc-
ing the problem of solving linear equations. However, as explained by Strang in his Linear
Algebra text, a more powerful and versatile visualization is through vector spaces.
Before moving to introduce vectors and vector spaces, I will very briefly review some
results in the solution of a system of linear equations.

2.1.1 Solving a System of Linear Equations

Let us extend Equations 2.1 and 2.2 to a system of equations with n unknowns. A general
linear equation in n unknowns is written as

ai1 x1 + ai 2 x2 +  + ain xn = bi (2.3)

27
28   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

We will define the solution vector

é x1 ù
ê ú
x2
x=ê ú (2.4)
êú
ê ú
êë xn úû

and the linear equation (2.3) may then be written as

éëai1 ai 2  ain ùû x = bi (2.5)

There may be n such equations in n unknowns. All such equations are then written together
and converted into the following standard form:

é a11 a12  a1n ù é x1 ù é b1 ù

ê úê ú ê ú
êa21 a22  a2n ú ê x2 ú êb2 ú
= (2.6)
ê     úê  ú ê  ú
ê úê ú ê ú
êëan1 an2  ann úû 
ê xn ú êbn ú
  ë û ëû
A x b

Here, the boldface small letters are used to represent vectors. Vectors can be both row and
column vectors. However, for consistency of notation, we will write vectors as n × 1 column
vectors (unless specified otherwise). The vectors x and b in the above equation are com-
posed of n elements. Each element, represented as nonbold characters with a subscript, is a
real scalar. We will define vectors and vector spaces in the next section.
The view in Equation 2.5 is a row-wise view of linear equations. The necessary and
sufficient condition for the set of linear equations (2.6) to have a unique solution is that
determinant of A should be nonzero. An equivalent statement is that a unique solution to
Equation 2.6 exists if and only if rank(A) = n. If this condition is met, inverse of A exists and
the solution is given by

x = A -1 b (2.7)

Numerical methods to solve linear equations are not discussed in this chapter. Instead, the
Gauss Elimination and LU decomposition methods are provided in Appendix C for ready
reference. Relevant MATLAB® commands are summarized in Section 2.5 at the end of this
chapter.

2.1.2 Overview
While solving linear equations is one application, in general linear algebra finds wide-
spread use in engineering (as also in science, economics, and other fields). Theories are
often well developed for linear systems, and detailed analysis can provide insights into sys-
tem behavior. It is common to linearize a nonlinear system using Taylor’s series expansion;
 Linear Algebra   ◾    29

the properties of the linearized system give a good qualitative picture of the behavior of the
original nonlinear system. For example, insights into stability, controllability, and dynam-
ics can be obtained by linear system analysis. Nonlinear equations and optimization prob-
lems may be solved by successively linearizing the system. Linear algebra is also useful for
parameter estimation using least squares approach.
The discussion in this chapter will be cast in one of the following three ways. All these are
equivalent but are typically seen in different types of problems. First, the problem is cast in
terms of m linear correlations between n elements of a vector:

é a11 a12  a1n ù é b1 ù

ê ú é x1 ù ê ú
ê a21 a22  a2n ú ê ú ê b2 ú
x2
ê     úê ú = ê  ú (2.8)
ê úê  ú ê ú
ê     úê ú ê  ú
êam1 am2  amn ú  êë xn úû ê ú
ëû x bm û
ë
A b

When m = n, this is same as Equation 2.6 encountered in solving linear equations. In least
squares parameter estimation problems, the number of rows is greater, that is, m > n. In
either cases, one intends to solve the problem to obtain x given the right-hand side vector b.
The second case is where a linear correlation exists between an input vector, x, and an out-
put vector, y. Such a linear mapping is mathematically represented as matrix multiplication:

é b1 ù é a11 a12  a1n ù

ê ú ê ú é x1 ù
b
ê ú ê
2 a21 a22  a2 n ú ê x2 ú
ê  ú=ê     úê ú (2.9)
ê ú ê úê  ú

ê ú ê     ú êx ú
êbm ú êam1 am2  amn ú  êë n úû
ëû  ë û x
y A

The structure of matrix multiplication, Ax, is the same in both Equations 2.8 and 2.9.
However, in this problem, we are interested in analyzing (and perhaps predicting) how the
output responds to changes in the input vector x.
The third case is seen as solving a linear system of differential or difference equations:

é b1 ù é a11 a12  a1n ù é x1 ù

ê ú ê úê ú
d êb2 ú êa21 a22  a2n ú ê x2 ú
(2.10)
=
dt ê  ú ê     úê  ú
ê ú ê úê ú
bn úû êëan1 an2  ann úû êë xn úû
êë
 
y A y

Unlike the second case, here the n-dimensional y-space maps onto itself.
30   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The three problems are somewhat equivalent numerically and require a similar reper-
toire of tools for analysis. However, I will bring out different practical significance for the
three problems so that these tools may be interpreted in relation to engineering problems
of interest.
We need to take a column-wise view of the linear equations (2.8), (2.9), or (2.10). This
calls for definition of vector spaces, which will be covered in Section 2.2. Solution of lin-
ear equations will be interpreted in that context. Thereafter, Sections 2.3 and 2.4 introduce
singular value and eigenvalue decompositions. We will thus build some background in this
chapter, which would be then used in some of the subsequent discussions in this book.
In summary, linear algebra is a versatile and practically relevant field. It is therefore apt
to start this book with a brief discussion on linear algebra. My treatment in this chapter is
inspired heavily by the online course and textbook by Prof. Gilbert Strang.

2.2 VECTOR SPACES
2.2.1 Definition and Properties
Let us first define a vector. A vector may be defined as an ordered list of scalars. A vector
x ∈ R n is a column vector with n elements (real numbers). Geometrically, the vector x ∈ R n
is a point in n-dimensional Euclidean space.
We visualize a vector in the form of a line starting from the origin toward this point in
space, which we often associate with a certain magnitude and direction. The term “magni-
tude” may be generalized in the form of vector norm: Norm is a positive scalar that is indica-
tive of the size of the vector. For example, the two-norm of a vector is what we associate as
the Euclidean distance:

x 2 = x12 + x22 +  + xn2 (2.11)

A vector space consists of a set of vectors, along with rules of addition, and scalar
multiplication:

é x1 + y1 ù é cx1 ù
ê ú ê ú
x2 + y2 ú cx2
x+y =ê , cx = ê ú
ê  ú ê  ú
ê ú ê ú
êë xn + yn ûú êëcxn ûú

Based on the above definition of vector space, several rules apply since a vector space is a
linear space. These rules are well known to the reader as commutative and associative laws
for addition

x + y = y + x, ( x + y ) + z = x + ( y + z ) (2.12)

and laws for scalar multiplication

c ( x + y ) = cx + cy , ( c1 + c2 ) x = c1x + c2 x (2.13)
 Linear Algebra   ◾    31

and that there exists a unique zero vector in the vector space, such that

x + 0 = x , x + ( - x ) = 0 (2.14)

With these definitions of vectors and vector spaces in place, let us revisit Equation 2.2. An
alternative interpretation uses the concept of vector spaces just defined:

v 1 x + v 2 y = b (2.15)

é1ù é2ù
where v 1 = ê ú and v 2 = ê ú are the column vectors that constitute matrix A. In other
  ë1û ë -1û
words, vi is the ith column of the matrix. Thus, the aim of solving linear equations can now
be expressed as finding the values of “coefficients” x and y such that the vector b on the
right-hand side is a linear combination of the vectors v1 and v2. As shown in Figure 2.1a, this
is like “completing a parallelogram” that we studied in high school.
Consider, instead, if the second equation changed so that the two linear equations are

x + 2 y = 1

2x + 4 y = 4

then the system of equations does not have a solution. The two column vectors in this
case are

é1 ù é2 ù
w 1 = ê ú and w 2 = ê ú
ë2 û ë 4 û

These two vectors lie on the same line from the origin. In fact, w2 = 2w1. As shown in
Figure 2.1b, since the vector b does not lie along the same line, there is no solution. If instead,
the second equation was changed so that

x + 2 y = 1

2 x + 4 y = 2

2
2 2

2
1 1
(a) (b) (c)

FIGURE 2.1  Demonstration of case with (a) unique solution, (b) no solution, and (c) infinite solu-
tions. The two thick lines represent the two column vectors of matrix A and the symbol represents
the right-hand side vector, b or d.
32   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

there will be infinitely many solutions. This is because for this case, the three vectors

é1 ù é2 ù é1 ù
w1 = ê ú , w 2 = ê ú , d = ê ú
ë2 û ë4û ë2 û

lie along the same line from the origin. This is shown in Figure 2.1c. It is easy to see that two
solutions are (1, 0) and (0, 0.5). Likewise, infinitely many solutions for the two equations
can be obtained.
As will be discussed presently, the three geometric views in Figure 2.1 are generalizable
and powerful ways to introduce key linear algebra concepts. The utility of linear equation
solving in this chapter was limited to introducing geometrically the concept of vector spaces.
I will not discuss linear equation solving further, but use this visualization to understand
some key concepts.

2.2.2 Span, Linear Independence, and Subspaces

The left-hand side of Equation 2.15 represents a linear combination of two vectors, v1 and
v2. The first definition is that of span. Span of vectors is defined as a vector space formed by
all linear combinations of those vectors. Thus, span{v1} is a line and span{v1, v2} is a plane.
As seen in Figure 2.1a, vectors v1 and v2 span the entire R 2 space.
Generalizing this definition, let x1, x2,  …  ∈ R n be vectors in n-dimensional space. Then

span {x 1 ,¼, x k } = c1 x 1 + c2 x 2 +  + ck x k (2.16)

where ci ∈ ℛ are real-valued scalars.

This brings us to the concept of linear independence. A set of vectors is said to be linearly
independent if no vector in that set can be expressed as a linear combination of the remain-
ing vectors. Mathematically, x1, x2,  …  ∈ R n are linearly independent if

c1 x 1 + c2 x 2 +  + ck x k = 0 implies ci = 0"i (2.17)

In other words, a set of vectors is linearly dependent if one (or more) of the vectors can be
represented as a linear combination of the remaining vectors. Thus, the original vectors

é1ù é2ù
v 1 = ê ú and v 2 = ê ú
ë1û ë -1û

from Figure 2.1a are linearly independent because neither of them can be expressed as a
linear combination of the other. Considering Equation 2.17, the only way they can sum to
0 is if both c1 and c2 are zero. On the other hand, the vectors

é1 ù é2 ù
w 1 = ê ú and w 2 = ê ú
ë2 û ë 4 û

from Figure 2.1b are linearly dependent.

 Linear Algebra   ◾    33

Now we are equipped to understand span a bit better. In the second example,
span{w1, w2} is a line, whereas span{v1, v2} is the entire 2D space. The difference between
Figure 2.1b and c is that the vector b cannot be expressed as a linear combination of
w1 and w2, but there exists at least one set of scalars (in fact, there are infinitely many such
scalars) such that

d = c1 w 1 + c2 w 2

Another way of stating this is that vector d lies in the span{w1, w2}, that is

d Î span {w 1 ,w 2 }

which is said to be a subspace of the R 2 space. A subspace is not merely a subset of a vector
space; it is also a vector space itself. Thus, a line that does not pass through the origin is not
a subspace. This is because it violates the rules in (2.14)* since the zero vector, 0, does not
lie on this line.
Although the discussion above used two vectors in R 2 space, the same arguments are
applicable to higher dimensional vector spaces as well. For example, vectors

é1ù é2ù
ê ú ê ú
1 -1
v 1 = ê ú and v 2 = ê ú
ê1ú ê0ú
ê ú ê ú
êë1ûú êë 1 úû

are two linearly independent vectors in R 4 space, whereas span{v1, v2} will be a 2D subspace
of R 4 space.
Consider another case where

é1 ù é2ù é0 ù
v1 = ê ú , v 2 = ê ú , v 3 = ê ú
ë2 û ë -1û ë1 û

We had seen earlier that vectors v1 and v2 span the entire R 2 space. Hence, v3 can be
expressed as a linear combination of v1 and v2 (one can verify that v3 = 0.4v1 − 0.2v2). Thus,
span{v1, v2, v3} is still the 2D R 2 space.
Finally, I end this subsection with the definition of dimension:
Dimension of a subspace is defined as the number of linearly independent vectors that
span the subspace.

*  It violates some other rules also, but it is obvious that (2.6) is violated since 0 is not on the line.
34   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

2.2.3 Basis and Coordinate Transformation

Let v1, v2,  … , vk ∈ R n be k vectors in an n-dimensional space. Based on the above discus-
sions, it would be clear that if k > n, then the vectors are linearly dependent. At most,
n ­vectors in R n space can be linearly independent.
If vectors v1, v2,  … , vn ∈ R n are linearly independent, then span{v1, v2,  …, vn} is the R n
space itself. Thus, any vector x ∈ R n can be represented uniquely as a linear combination:

x = a1 v 1 + a2 v 2 +  + an v n (2.18)

The proof for this statement is left as an exercise. Therefore, the vectors {v1, v2,  …, vn}
together can form the basis of R n. The matrix formulation

é a1 ù
ê ú
a2
x = éë v 1 v2  v n ùû ê ú (2.19)
ê ú
ê ú
êëan úû

is equivalent to Equation 2.18. This works exactly in the same manner in which Equation 2.15
was obtained from Equation 2.1. The proof for the above is also left as an exercise.
Basis vectors are therefore a set of linearly independent vectors that span the vector space.
The set of coordinate vectors

é1 ù é0 ù é0 ù
ê ú ê ú ê ú
0 1 
e1 = ê ú , e 2 = ê ú ,  , en = ê ú (2.20)
ê ú ê ú ê0 ú
ê ú ê ú ê ú
êë0 úû êë0 úû êë1 úû

is called natural basis.

2.2.3.1 Change of Basis
Let vector x ∈ R n be represented as

é x1 ù
ê ú
x2
x=ê ú
êú
ê ú
êë xn úû

in the natural basis. Let us say we want to change the basis to the vectors {v1, v2,  …, vn}. This
is possible, since these are linearly independent vectors that span the R n space. The vector x
 Linear Algebra   ◾    35

is represented by Equation 2.19. Since the vector in the natural basis and {v1, v2,  …, vn} basis
is the same point, the following equality holds:

é x1 ù é a1 ù
ê ú ê ú
x2 a2
éëe1 e2  en ùû ê ú = éë v 1 v 2  v n ùû ê ú (2.21)
ê  ú  ê  ú
ê ú T ê ú
êë xn úû êëan ûú

The first matrix on the left-hand side is the identity matrix. Thus, coordinate transformation
to the new basis is given by

é a1 ù é x1 ù
ê ú ê ú
ê a2 ú = T -1 ê x2 ú (2.22)
ê ú êú
ê ú ê ú
êëan ûú êë xn úû

where the coordinate transformation matrix T is an n × n matrix whose n columns are the
n basis vectors. Change of basis is an important operation that we will use in the analysis
of linear systems and stiff ordinary differential equations (ODEs) (in Chapters 5 and 8,
respectively).

2.2.4 Null (Kernel) and Image Spaces of a Matrix

2.2.4.1 Matrix as Linear Operator
The discussion so far focused on vectors and vector spaces. Let us now turn to looking
at the matrix A. Let x ÎX be n-dimensional input vector and y Î Y be an m-dimensional
output vector. In general, a model that correlates the inputs and outputs (at steady state) is
given by

y = f ( x ) (2.23)

The above is a nonlinear mapping between the inputs and outputs of the system. A linear
mapping between the inputs and outputs will be given by*

y = Ax (2.24)

*  The mapping, y = Ax + b is known as affine mapping, and not a linear mapping. If y1 = Ax1 + b and y2 = Ax2 + b, then
A ( c1x1 + c2 x 2 ) + b ¹ c1y 1 + c2 y 2

Although affine functions are not linear, it is easy to convert them to linear:
- b2 = A ( x + b1 )
y

  
y x

where b = Ab1 + b2.

36   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

This brings us to an important result. Let X be an n-dimensional vector space and Y be an

m-dimensional vector space. A linear operation between X to Y can be represented as a
matrix multiplication, as shown in Equation 2.24.
The blending operation example is provided in the box below to show an example of
linear operator and its matrix representation.

Example 2.1  Blending Operation Example

Blending is an important operation in refineries. Raw materials from various sources
differ in their quality. They are blended together, along with a makeup stream, in order
to meet both quantity and product specification requirements. Let us consider a sim-
plified case where two streams are being mixed with a third makeup stream, and the
final requirement from the blending operation is to obtain the output stream at a
certain production rate (say, F kg/minute) with a specific amount of the primary com-
ponent (given by mass fraction ω in the outlet stream). At steady state, the overall
mass balance

F = F1 + F2 + F3 (2.25)

and balance on the primary component

F w = F1w1 + F2 w2 + F3 w3 (2.26)

give a mathematical model for the operation.

The input vector

é F1 ù
ê ú
x = ê F2 ú
ê F3 ú
ë û

consists of the three mass flowrates. If the desired output is in terms of total mass flow
and composition of the primary component, the output vector consists of

éF ù
y = ê ú
ë wû

The first model equation (2.25) is linear, whereas Equation 2.26 is nonlinear:

1
w=
F
( F1w1 + F2 w2 + F3w3 )

Thus, the mapping between x and y is nonlinear.

 Linear Algebra   ◾    37

It is possible, however, to define the output vector as total mass flow and mass flow of
the primary component Fprim at the outlet. Thus

é F ù
y=ê ú
ë Fprim û

and the linear operator that models the steady state blending operation is

é1 1 1ù
y=ê úx (2.27)
ëw1 w2 w3 û

C

The matrix C is a linear mapping between the three inlet flowrates and the net produc-
tion rates from the blending system. It is represented as

C : X ® Y

where X and Y are 3D and 2D spaces, respectively.

Although I have stated this before, it bears repeating. The linear equation, Ax = b, was intro-
duced to motivate the concept of vectors and vector spaces. Thereafter, Section 2.2.2 intro-
duced the concept of span and linear independence; Section 2.2.3 introduced the concept
of basis; and this subsection introduced the concept of matrix as a linear operator. It would
help to “upgrade our thinking” in terms of input vector x, output vector y, and linear trans-
formation represented by the matrix A.
Null space or Kernel of a matrix is defined as the complete set of vectors x ÎX such that
their linear transformation under matrix A maps to the zero vector. Mathematically

ker ( A ) = {x : Ax = 0} (2.28)

In previous subsections, we have defined the column vectors of the matrix as the m vectors
that form individual columns of the matrix. Consider the case when the two column vec-
tors, v1 and v2, were linearly independent. In such a case

é1 2ù
ê úx =0
1 -1û
ë

A

has a unique solution, x = 0. Thus, when the column vectors of A are linearly independent,
the null space of the matrix is a single point, the origin.
38   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The second case is when the two column vectors, w1 and w2, are linearly dependent.
The set of x that satisfies the equation

é1 2 ù
ê úx =0
ë2 4û

A

includes all the vectors

é -2a ù
ê ú
ë a û

The physical consequence (or interpretation) of null space is as follows: Any input set in the
null space will lose its information when acted upon by the linear transformation A.
Note that the null space or kernel is a subspace of the input space.
Image space of a matrix is the set of output vectors y Î Y that are obtained by the trans-
formation of all x ÎX through the matrix A. Stated in a different way, the image space of
matrix A is all y that satisfy

im {A} = {y | y = Ax : x Î X } (2.29)

The image space for

é1 2ù
y=ê úx
1 -1û
ë

A

is the entire 2D space. Consider the other system

é1 2 ù
y=ê úx
ë2 4û

A

which can then be written as

é1 ù é2 ù
y = x1 ê ú + x2 ê ú
ë2 û ë4û

Thus, the image space of this matrix is the 1D subspace along the vector w1 = [1  2]T.
 Linear Algebra   ◾    39

IMAGE SPACE AND COLUMN SPACE

In Section 2.2.1, we introduced v1 and v2, and w1 and w2 as the column vectors of matrix A,
and defined span of vectors in Section 2.2.2. I have deferred defining the column space of
a matrix until this point.
Column space of a matrix is defined as the span of its column vectors. Thus, column
space for the two examples from Section 2.2.1 are

c1v1 + c2v 2 or c1w1 + c2w 2

respectively. Thus, the condition that the equation Ax = b has a solution is as follows: The vec-
tor b is in the column space of A.
Now, look at the definition of image space: It is the set of all output vectors y such that

y = x1v1 + x2v 2 ( for the first example )

y = x1w1 + x2w 2 ( for the second example )

Notice that the two definitions are similar since (x1, x2) or (c1, c2) are real numbers. So, what
is the difference between image space and column space?
One way to look at them is to realize that image and column space are numerically the
same: They are both the linear combinations of the column vectors of a matrix.
Another way to look at this is the physical interpretation. The term “column space” was
invoked when we discussed solving a linear equation: One or more solutions exist when
the vector on the right-hand side of Equation 2.2 lies in the column space of A. Figure 2.1
illustrates the statement “the equation Ax = b has solution(s) if the vector b lies in the column
space of matrix A.”
On the other hand, “image space” does not talk about solving linear equations; instead it
is introduced in the context of linear transformation. When the input vector x is acted upon
by a linear operation, the corresponding output vector lies in the image space. In the top
panels of Figure 2.2, the image of any arbitrary vector in X may lie anywhere on the 2D
2
space. So, the image space is the entire R space.
In the bottom panels, the image space of the matrix A was im(A) = [1  2]T. Note that all
the dots lie on this line. Furthermore, ker(A) = [−2  1]T, implying all the open circles on the
left-bottom panel map to the origin in the Y -space on the right-bottom panel. The example
also illustrates the fact that the image space is a subspace of the output space, Y , whereas
the null space is a subspace of the input space, X .

2.2.4.2 Null and Image Spaces in MATLAB®

With the matrix A defined as above, the null space of a matrix can be obtained in MATLAB as

>> disp(null(A))
-0.8944
0.4472
40   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

(a)

(b)

FIGURE 2.2  Linear transformation from X ® Y for the two different A matrices. (a) The column
vectors of A matrix are linearly independent; (b) the column vectors are linearly dependent. Dots/
circles on the X -space on the left map to dots/circles on the Y-space on the right.

Note that the above is same as the vector

é -2a ù
ê ú
ë a û

(where a = 1/ 5 ). The image space can be obtained using the command orth. The image
space is also called range of the matrix.
>> disp(orth(A))
-0.4472
-0.8944

Example 2.1 Revisited:  Blending Operation Example

Consider the example of blending operations. First point to note is that if we imple-
ment the constraint that the flowrates must be positive, the sets X and Y are no longer
vector spaces (because, for example, - x Ï X and - y Ï Y ).
Case 1: For this exercise, let us abandon the requirement that Fi ≥ 0. To still give it a
“physical meaning,” let us undertake a pedagogical exercise that if any of the flowrates,
Fi, are negative, it implies that the flow is taken out from the blender. Consider the case
where the first stream does not contain any primary component, the second stream has
ω2 = 0.5, and the third stream is the pure primary component. Thus, in Equation 2.27

é1 1 1ù
C=ê ú
ë0 0. 5 1û
 Linear Algebra   ◾    41

The image space, im(C), is the entire R 2 space, since it is possible to get any net and
primary component flowrates through linear combinations of F1, F2, and F3. What is
the null space, ker(C)? It is the combination of the three flowrates such that both the
net flowrate, F, and primary component flowrate, Fprim, are zero. It is easy to see that for
the primary component flow to be zero, F3 = a,   F2 =  − 2a. If the flowrate F1 = a, we can
T
see that the net flowrate F = 0. Thus, the null space is given by x = ëéa -2a a ùû .
The unit vector in that direction is therefore

>> disp(null(C))
0.4082
-0.8165
0.4082

Case 2: For this case, let us consider that all the three streams have the same compo-
sition of the primary component, that is, ω1 = ω2 = ω3 = q. It should be clear that mixing
of these three streams will lead to the outlet stream with the same composition, q.
Thus, the net flowrate will be, F = F1 + F2 + F3, and the net flowrate of the primary com-
ponent, Fprim = qF. Thus, the image space will be 1D subspace of Y, such that

é1 ù
im ( C ) = ê ú F
ëq û

While it is possible to obtain any value of primary component flowrate, Fprim, the ratio
of this to the net flowrate (i.e., mass fraction) will always be q.
It can be verified using orth command in MATLAB that the image space is given by

ì é1/ 1 + q 2 ù ü
ï ú ïý
im ( C ) = span í ê
ïî êëq/ 1 + q úû ïþ
2

2.3 SINGULAR VALUE DECOMPOSITION

Singular value decomposition (SVD) and eigenvalue decomposition are very important
concepts that will be useful. Before discussing these, the following subsection presents a
few important definitions.

2.3.1 Orthonormal Vectors
Let x1 ∈ R n and x2 ∈ R n be two vectors in n-dimensional space. The dot product or the inner
product of the two vectors is

x 1, x 2 = x 1T x 2 = x T2 x 1 = x 2, x 1 (2.30)
42   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

A vector is a unit vector if its inner product with itself equals one. In the last example, the
basis for the image space was defined as

é1/ 1 + q 2 ù
ê ú
êq / 1 + q 2 ú
ë û

and one can easily verify that this is a unit vector.

Two vectors are said to be orthogonal vectors if their inner product is zero, that is, x 1T x 2 = 0.
Furthermore, if both the vectors are unit vectors as well, they are said to be orthonormal.
Orthonormality is a useful property. Recall that there were multiple possibilities for
defining the basis for image and null spaces. However, the commands orth and null
resulted in a specific type of basis vectors: They were all mutually orthonormal. Vectors
x1,  … , xk ∈ R n are said to be mutually orthonormal iff they satisfy the condition

ïì 1 if i = j
x Ti x j = í (2.31)
ïî0 otherwise

An orthogonal matrix is a square matrix whose column vectors are orthonormal to each
other. Thus, since

A = éë v 1  v n ùû , where v 1 ,¼, v n are mutually orthonormal vectors, (2.32)

from the definition (2.31) of orthonormal vectors, an orthogonal matrix satisfies

AAT = AT A = I (2.33)

Thus, for an orthogonal matrix

AT = A -1 (2.34)

The three properties, (2.32), (2.33), and (2.34), are key properties of orthogonal matrices.
Orthogonal Subspaces: Two subspaces are said to be orthogonal if any vector on one sub-
space is orthogonal to any other vector on the other subspace.
Remark: Since any vector in a subspace can be represented as a linear combination of its
basis vectors, it is sufficient to ensure that basis vectors of the two subspaces are orthogonal
to each other.

2.3.2 Singular Value Decomposition

Let us start this subsection with an example of linear transformation between input and out-
put vector spaces, which is represented as matrix multiplication. The change of basis through
transformation matrix was given in Equation 2.22. For the purpose of this discussion, let us
 Linear Algebra   ◾    43

restrict transformation to orthonormal basis set. The orthonormal basis set that spans the
input space forms the n columns of input transformation matrix:

Tx = éë v 1 v2  v n ùû (2.35)

and the basis set that spans the output space forms the m columns of the output transforma-
tion matrix:

Ty = éëu1 u2  um ùû (2.36)

Since the transformation matrices are chosen to be orthogonal

T -1 = T T

Recall that the relationship between the original vector x and the transformed vector (in the
new basis set in (2.35)) is

x = TxT x (2.37)

and

y = TyT y (2.38)

These can be substituted in the original linear operation y = Ax to get

y = TyT ATx x (2.39)



A

The above expression is valid for any appropriate set of orthonormal basis vectors. The
coordinate transformation is most effective for a “special” set of basis vectors.
Consider

é1 2ù
A=ê ú
ë2 4û

for which the geometric interpretation of null and image spaces was shown in Figure 2.2b.
{ }
The image space for this matrix was im ( A ) = span éë1 2 ùû . Let us choose this vector as
T

one of the basis, u1, for the output space. Since we want to choose orthonormal basis vector

é1 / 5 ù
u1 = ê ú (2.40)
êë2 / 5 úû

44   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

the other basis vector is the unit vector perpendicular to u1

é -2 / 5 ù
u2 = ê ú (2.41)
êë 1 / 5 úû

and the output transformation matrix is as given in Equation 2.36.

In the input space, let one of the basis vectors (v2) be the vector that spans the null space
and the other vector (v1) be orthogonal to the null space. Thus

é -2a/ 5a 2 ù é -2/ 5 ù
v2 = ê ú=ê ú (2.42)
ê a/ 5a 2 ú êë 1/ 5 úû
ë û

é1/ 5 ù
v1 = ê ú (2.43)
êë2/ 5 úû

and Tx is given by Equation 2.35:

é1/ 5 -2/ 5 ù
Tx = ê ú (2.44)
êë2/ 5 1/ 5 úû

With these defined, we may now compute

é5 0ù
 = TyT ATx = ê
A ú (2.45)
ë0 0û

The above matrix in the transformed input/output spaces implies

é y ù é5x 1 ù
ê 1ú = ê ú (2.46)
êë y2 úû êë 0 úû

The above equation makes the following rules quite clear: (i) Any point in the X space
gets mapped along y1 in the output space; (ii) y2 = 0 implies that no point in the X spaces
is mapped to this subspace; (iii) only the information in x 1 subspace is retained; whereas
(iv) the information along x 2 is lost. Thus, u1 is the image space and u2 is the subspace
orthogonal to it; and v2 is the null space and v1 is the subspace orthogonal to the null
space.
 Linear Algebra   ◾    45

We are now ready to generalize the above representation to any m × n matrix A through
the concept of SVD, which states that any matrix A can be represented as

A = U SV T (2.47)

where

U = éëu1 u2  um ùû (2.48)

and

V = éë v 1 v2  v n ùû (2.49)

are orthogonal matrices. The matrix Σ is an m × n matrix such that its diagonal elements
are nonnegative (i.e., positive or zero) and all the other elements are zero. The diagonal
elements of matrix Σ are called singular values. The singular values are ordered, that is,
σ1 ≥ σ2 ≥ ⋯. The number of singular values is exactly equal to m or n, whichever is lower.
Some of these singular values can be zero.
The MATLAB command for singular value decomposition is svd.
When A is a square matrix, the SVD may be written as

és1 ù
ê ú T
A = éëu1  un ùû ê  ú éë v 1  v n ùû (2.50)
 
ê sn úû
U
ë
V

where all the nondiagonal elements of Σ are zero.

When A is a tall matrix, that is, m > n,

és1 ù
ê ú
ê  ú T
A = éëu1  um ùû ê sn ú éë v 1  v n ùû (2.51)
 ê ú 
U ê 0  0 ú V
ê 0  0 ú
ë û

S

Likewise, when m < n, the matrix of singular values is given by

é s1 0 0 ù
ê ú
S=ê    ú (2.52)
ê sn 0 0 ú
ë û
46   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 2.1 Revisited:  Blending Operation Example

Previously, we had considered two different linear operator matrices for the blending
system example:

é1 1 1ù é1 1 1ù
C=ê ú , C¢ = ê ú
ë0 0. 5 1û ë 0. 5 0. 5 0. 5 û

(In the latter case, I have chosen q = 0.5.)

Recall that the image space of C was the entire R 2 space, whereas the null space was

é a ù
ê ú
x = ê -2a ú
ê a ú
ë û

Executing the SVD in MATLAB yields

T
é -0.4413 -0.7991 0.4082 ù
é -0.8671 -0.4981ù é1.9651 0 0 ùê ú
A=ê úê ú -0.5680 -0.1035 -0.8165ú
ë -0.4981 0.8671 û êë 0 0.6233 0 úû ê
ê -0.6947 0.5922 0.44082 úû
ë

Since both the singular values are nonzero, the image space is the complete R 2 space.
Since there can be at most two positive singular values, the null space will be non-
empty. As can be seen from the matrix V, the last column is the null space that we
obtained earlier.
A similar exercise can be done on the other matrix

é1 1 1ù
C¢ = ê ú
ë 0. 5 0. 5 0. 5 û

as well. The reader can verify that the following results agree with the discussion
regarding the image and null space of this matrix as well.

>> [U,S,V]=svd(A)
U =
-0.8944 -0.4472
-0.4472 0.8944
S =
1.9365 0 0
0 0 0
V =
-0.5774 -0.8165 -0.0000
-0.5774 0.4082 -0.7071
-0.5774 0.4082 0.7071
 Linear Algebra   ◾    47

2.3.3 Condition Number
2.3.3.1 Singular Values, Rank, and Condition Number
Let us summarize the results of the discussion on SVD. Let A := R n → R m be an m × n
matrix with ℓ singular values, {σ1,  …, σℓ}. Here, ℓ ≤ min(m, n). The two orthogonal matrices
may be written as

U = éëu1  u  | um ùû V = éë v 1  v  | v n ùû (2.53)

The first  column vectors of U span the image space and the remaining (m − ℓ) column vec-
tors form the subspace orthogonal to the image space. The latter subspace is “unreachable” on
linear operation through A. Similarly, the last (n − ℓ) column vectors of V span the null space.
The information along the null space is lost when data is operated upon by linear operator A.
The first ℓ column vectors of V span a subspace that is orthogonal to the null space of A.
Rank of a matrix is defined as the number of linearly independent rows of a matrix.
The concept of rank is introduced in introductory linear algebra courses while discussing
whether linear equation, Ax = b, has a unique solution. The concept of rank is useful for a
broader range of problems. In fact, row rank and column rank of a matrix are the number of
linearly independent rows and columns of a matrix, respectively. Thus, the column rank of
a matrix equals the number of linearly independent column vectors, which in turn, equals
the dimension of the image space of the matrix. It can be proved that row rank and column
rank of a matrix are equal (the proof is left as student exercise).
Since im(A) = span{u1,  …, uℓ}, rank is also equal to the number of nonzero singular val-
ues of A. Furthermore, if ℓ = m, the image space is the entire m-dimensional vector space of
outputs; else, it is an ℓ-dimensional subspace of the R m output space. Equivalently, if ℓ = n,
the null space of A is just the origin.
While rank is a useful criterion, it does not tell us much about the relative values of
σ1,  … , σℓ. Condition number is the ratio of the largest and smallest singular values, which is
an important parameter to analyze a linear system. Formally, condition number is defined
as the ratio of the two-norm of A to the two-norm of A−1, which simply means that condi-
tion number is the ratio of maximum singular values of A and A−1:

smax ( A ) smax ( A )
c ( A) = = (2.54)
( )
smax A -1 smin ( A )

Condition number is often invoked in the context of solving a set of linear equations.
It indicates how sensitive the solution will be to small errors in data. It is useful in linear
least squares problems (this will be dealt with in Chapter 10). It also indicates directionality
of the system. The implications of condition number in these scenarios will be discussed in
the remainder of this subsection.

2.3.3.2 Sensitivity of Solutions to Linear Equations

We will start with a “classical” example to motivate discussion in this section.
48   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 2.2  Condition Number and Solution of Linear Equations

Consider the linear equation, Ax = b. A “classical” example of ill-conditioned matrix is

é1 2 ù
A=ê ú
ë2 4.001û

This is a classic example that is used to demonstrate the importance of condition num-
ber. The condition number can be computed in MATLAB using

>> cond(A)
ans =
2.5008e+04

which indicates a highly “ill-conditioned” matrix. The reason for this would be clear
to the reader. If the element A(2, 2) = 4, we notice that the rank of the matrix will be
1, the matrix would not be invertible and a unique solution to linear equation would
not exist. However, with the A matrix given in this problem, the linear equation has a
unique solution for any value of b.
When b = [1  2]T, the solution of the linear equation is

>> x=inv(A)*b;
x =
1
0

The command inv(A)obtains A−1.

Let us say there was a 1% error in b vector. For

é1.01ù é 41.01ù
b=ê ú, x = ê ú
ë 2 û ë -20 û

The solution has changed significantly with a rather small change in b. Thus, condi-
tion number is an indicator of the sensitivity of the solution of linear equations to
errors in data. When faced with highly ill-conditioned matrix, one should reformulate
the problem to avoid this issue, instead of finding “improved” solution algorithms.
Condition number is a property of the system and not of the solution technique.

There is another part to the discussion of ill-conditioned matrices. The SVD of matrix A
from Example 2.2 gives

T
é -0.4471 -0.8945ù é5.0008 0 ù é -0.44471 -0.8945ù
A=ê úê úê ú (2.55)
ë -0.8945 0.4471 û ë 0 0.0002 û ë -0.8945 -0.4471û
 Linear Algebra   ◾    49

The value of solution was highly sensitive to initial conditions, when b = [1  2]T, that is,
when b was along or “close to” the vector u1. If instead

é1 ù é 4001.0 ù
b = ê ú, x = ê ú
ë0 û ë -2000.0 û

the solution x has a significantly larger magnitude than the right-hand side b. As one
moves the value of b2 from 2.0 to 0.0, the solution has moved from x1 = 1.0 to x1 = 4001. The
smallest singular value of A becomes the largest singular value of A−1. Hence, the resulting
solution becomes very large.
A large value of solution vector is not the hallmark of an ill-conditioned matrix. The hall-
mark of an ill-conditioned matrix is high sensitivity to errors. Consider the following matrix:

é1000 2000 ù
A=ê ú
ë2000 4001û

Note that if σi are singular values of A, (ασi) are singular values of [αA]. Thus, the condition
number of the above matrix remains the same as that in Example 2.2. The solution with this
matrix for different values of b (when b is in the column space of u1) is as follows:

é1 ù é0.001ù
b = ê ú, x = ê ú
ë2 û ë 0 û

é1.01ù é 0.041 ù
b=ê ú, x = ê ú
ë 2 û ë -0.020 û

The sensitivity of the solution to errors is the key factor. Note that again the value of x1 has
changed by a factor of 40, even though the values of x are very small.
We can use SVD to analyze this behavior. Transforming the coordinate systems to the
basis set represented by column vectors of V for the vector x and U for the vector b, we get
the following:

(U SV ) x = b (V
T
x ) = S (U b )
T


-1 T
(2.56)

x b

In the new basis set, this equation becomes

( ) ( )
x 1 = s1-1 b 1 x 2 = s2-1 b 2

(2.57)
50   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

In Example 2.2, the two values (see Equation 2.55) are

( s ) = 0.2, ( s ) = 5000.8
-1
1
-1
2

Let us consider the case when b ∈ span{u1}

é 1 ù  é -2.236 ù
b=ê úÞb=ê ú
ë2.0004 û ë 0 û

and the value of x 1 = -0.4471. In the original coordinate system, the solution is therefore

é 0. 2 ù
x = V x = ê ú (2.58)
ë 0. 4 û

When the value of b is moved slightly away,

 = é -2.236 ù
b ê ú
ë e û

T
yielding x 1 = -0.4471 and x 2 = 5000.8e. For example, when b = ëé1 2 ùû as in Example 2.2,
ε =  −1.789 × 10−4, which yields x 2 = -0.8945. Thus

é -0.4771ù é1 ù
x = ê ú Þ x=ê ú
ë -0.8495û ë0 û

Example 2.2 (Continued)  Summary of Linear Equation Solving Results

Let us summarize the above results in the context of solving linear equations:

é 1 ù -1
é 0. 2 ù
b=ê ú Þ x=A b=ê ú
ë2.0004 û ë 0. 4 û

é1 ù é1 ù
b = ê ú Þ x = A -1 b = ê ú
ë2 û ë0 û

The summary of the above results in modified coordinate spaces:

 = U T b = é -2.236 ù Þ x = S -1 b
b  = é -0.4471ù
ê ú ê ú
ë 0 û ë 0 û
 Linear Algebra   ◾    51

 = U T b = é -2.236 ù Þ x = S -1 b
b  = é -0.4471ù
ê ú ê ú
ë 0.0002 û ë -0.8495û

The last step above is the reason for the sensitivity of the solution to errors. A very
small change in b resulted in a significant change in x 2 from 0 to −0.8495 (which is
double the value of x 1). Therefore, the final solution changes significantly:

é 0. 2 ù
x = V x = ê ú
ë 0. 4 û

é1 ù
x = V x = ê ú
ë0 û

The above discussion would also make it clear that varying b along the u1 direction will
result in only a proportional change in the solution. For example

é 1. 1 ù -1
é0.22 ù
b=ê úÞx=A b=ê ú
ë2.2004 û ë0.44 û

A standard interpretation of the solution of linear equations with ill-conditioned matrix is

that of “intersection of two nearly parallel lines.” However, this geometric picture is limiting,
especially when one expands to higher dimensions. In contrast, the approach of expressing
the linear equation in context of SVD provides new and interesting insights into its solu-
tion, which are easily generalizable.
Consider a n × n matrix, whose singular values, (σ1,  …, σℓ) are of similar order of mag-
nitude, whereas σℓ/σℓ + 1 ≫ 1. When the matrix is inverted, si-1 will be comparatively low for
the first ℓ elements, whereas it would be high for the remaining (ℓ + 1) to n elements. Thus,
{ }
small values of b +1 , ¼, b n will map as large values in the solution x. If errors in b are in
the subspace spanned by the first ℓ column vectors of U, the change in the solution x will be
proportional to the change in vector b. However, errors in b in the subspace spanned by the
remaining vectors will result in larger effects on x.

2.3.4 Directionality
The above example possibly indicates some sort of directionality in a linear operator,
A : X ® Y when the singular values are significantly different from each other. For a linear
operator that relates input and output spaces, Equation 2.56 may be rewritten as

(
y = U åV T x )
(U
T
y ) = å (V x )

T (2.59)

y x
52   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

so that

yi = si x i (2.60)

When the basis vectors of the input and output spaces are changed to the singular vectors,
this results in simply stretching or shrinking along these vectors. We used Example 2.1 to
discuss image and null spaces of a matrix. The following example takes this concept further,
expanding on the discussion in Section 2.3.3 for linear operator.

Example 2.3  Significance of Singular Values for Linear Operator

Consider the linear transform

é -0.25 1. 5 ù
y=ê úx (2.61)
ë -2.25 4.25û

The condition number for the above matrix is 11. The condition number for this
matrix is quite good. We will choose this matrix because it is easier to visually demon-
strate the significance of singular values for linear operation.
An alternative, geometric interpretation of condition number is as follows. Let the
vector x be a unit vector. Let us choose x randomly in the X space. If we do this mul-
tiple times, the locus of x will form a unit circle in the X space. For each of the values
of x, we compute y using the above relation (2.61). The locus of y will map an ellipse in
the Y-space. The ratio of major and minor axes of the ellipse is the condition number.
The physical picture is shown in Figure 2.3. The circles denote conditions for major
axis of the ellipse, while the diamonds denote conditions for minor axis.
The following code was used to generate Figure 2.3:

% Specify A and its svd

A=[-0.2500 1.5000
-2.2500 4.2500];
[U,S,V]=svd(A);

(a) (b)

FIGURE 2.3  Interpretation of condition number. (a) A circle in the X -space maps to an ellipse on
Y-space. (b) Condition number is interpreted as the ratio of major and minor axes of the ellipse.
 Linear Algebra   ◾    53

% Generate x randomly on a unit circle

x1=[-1:0.01:1];
x2=sqrt(1-x1.^2);
x=[x1, x1; x2, -x2];
% Plot the original input data
subplot(1,2,1)
plot(x(1,:),x(2,:),'b.'); hold on

% Compute and the output

y=A*x;
subplot(1,2,2);
plot(y(1,:),y(2,:),'b.'); hold on

% Compute the "radius"

ySquare=y.*y;
r=sum(ySquare);
% Minor and major axis directions
% were computed and plotted manually

The two circles on the figure correspond to points (−0.44, 0.898) and (0.44, −0.898).
Using svd command, the direction of vector v1 is found to be

é -0.443ù
v1 = ê ú
ë 0.896 û

Recall that Equation 2.61 may be written as

(U
T
y ) = S (V x )
T


(2.59)
y x

T
The first point therefore corresponds to x = ëé1 0 ùû . Consequently, in the Y-space, the
corresponding output point is y1 = s1. When translated back to the natural basis, this
point is plotted as a circle at (1.457, 4.807). Likewise, the other circle on Figure 2.3 is
the point (−1.457, −4.807). Note that these points in the modified basis correspond to

és1 ù é -s1 ù
y » ê ú and y » ê ú
ë0û ë 0 û

respectively.

Generalizing the observations from Example 2.3, let us say that σℓ ≫ σℓ + 1. Then, span{v1,  …, vℓ}
corresponds to the direction in the X -space where the result will be stretched after linear trans-
formation through matrix A. On the other hand, the vectors that lie in the span{vℓ + 1,  …, vn}
54   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

get shrunk with this linear transformation through matrix A. A further discussion of the
effect of this directionality on system behavior will be presented in Section 5.2.3.

2.4 EIGENVALUES AND EIGENVECTORS

2.4.1 Orientation for This Section
Eigenvalues originated not in linear algebra but in the analysis of rigid-body dynamics,
while solving linear ODEs in the late eighteenth and early nineteenth centuries. First year
calculus course exposes us to this in the form of eigenvalue problems (or the so-called
“Sturm–Liouville problems” for second-order ODEs). The importance of eigenvalues and
eigenvectors will be discussed later, in Chapters 3 and 5 for discussing stability and dynam-
ics of ODEs, and in Chapter 8 to introduce stiff ODEs. Needless to say, singular values and
eigenvalues are important concepts that we will carry forward in later chapters of this book.
Some of the drawbacks of eigenvalues are that they are applicable to n × n square matrices
only, and eigenvalues of real matrices may be complex. Singular values came much later,
perhaps as a way of generalizing the concept of eigenvalues.
With this picture in mind, most linear algebra texts discuss eigenvalues before they dis-
cuss singular values. However, I deviate from this narrative because the concepts of singular
and eigenvalues need to be tackled on their own merits. I presume that readers are already
aware of the concept of eigenvalues. I therefore introduce singular values before eigenvalues
because the former presented a natural narrative for the linear operator.

2.4.2 Brief Recap of Definitions

Eigenvalues and eigenvectors were introduced in introductory courses for solving linear
ODEs:

d
y = Ay (2.62)
dt

where y is an n-dimensional vector. The form of solution to this problem is obtained by

comparing it with an equivalent problem in single variable:

dy
= ay (2.63)
dt

The solution for the above problem in single variable is

y = c0e at (2.64)

The ith row for Equation 2.62 is written as

yi¢ = Ai1 y1 + Ai 2 y2 +  + Ain yn

 Linear Algebra   ◾    55

where the right-hand side is linear and differentiation is a linear operator. By analogy, since
the superposition principle holds, a solution to Equation 2.62 is

y = e lt c (2.65)

where
c is an n-dimensional vector
λ is a scalar that is yet to be determined

Substituting this in Equation 2.62

d
y = Ae lt c (2.66)
dt

Differentiating Equation 2.65

d
y = l e lt c
dt

and substituting it in the above equation yields

le lt c = Ae lt c (2.67)

The scalar eλt is nonzero (except for λ =  −∞) and may be eliminated. This yields us the
­following relationship:

Ac = lc (2.68)

which is now a linear algebra problem. The above equation is rewritten as

( A - lI ) c = 0 (2.69)

where λ is known as eigenvalue and c is known as eigenvector. The scalar λ is chosen such
that the matrix (A − λI) becomes rank deficient (i.e., rank(A − λI) < n). This condition gives
us the so-called characteristic equation:

det ( A - lI ) = 0 (2.70)

The eigenvector c is in null space of (A − λI). Let us end this discussion with a summary of
key points.

Definition: For a matrix A : R n → R n , there exists scalar l Î C and vector c Î C n such that

Ac = lc

where λ is called the eigenvalue and c is the eigenvector.

56   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Characteristic equation: Equation 2.70 is known as the characteristic equation of matrix A.

The above characteristic equation is an nth-order polynomial in λ. Thus, an n × n
matrix will have n eigenvalues. Some of these eigenvalues may be repeated.
Complex eigenvalues: For a real matrix A, eigenvalues may be real or complex. If there are
complex eigenvalues, they occur in complex conjugate pairs.
The eigenvector c is in the null space of (A − λI). If the n eigenvalues are distinct, the cor-
responding n eigenvectors are linearly independent. Moreover, if these distinct eigen-
values are real, we have n linearly independent real eigenvectors. This is an important
result because n distinct eigenvectors can form basis for the Rn space. However, these
eigenvectors may not be orthonormal.

2.4.3 Eigenvalue Decomposition
Eigenvalues and eigenvectors were introduced for solving linear ODEs, y′ = Ay. The term
is reported to have origins in the German word “eigenwert,” which translates (according to
Google translate) to “intrinsic.” The term eigenvalue or eigenvector may therefore imply
“an intrinsic value/vector” that characterizes the matrix. The most important application of
eigenvalues and eigenvectors is in the analysis of situations where we need to map a linear
transformation of a vector space on itself.
In Section 2.3, physical interpretation of SVD was provided for a linear transformation
y = Ax. The mapping was A: R n → R m. The input and output vector spaces could be of
different dimensions (as seen in Example 2.1) or they could be of same dimension (when
m = n, such as Example 2.3). Naturally, SVD gave two different coordinate transformations:
The orthogonal matrix V as the input basis, the orthogonal matrix U as the output basis,
and the diagonal matrix Σ that maps x ÎX to y Î Y .
In contrast, eigenvalues are of interest when mapping the R n vector space on itself. For
the ease of this discussion, consider the case where the matrix A has n distinct eigenvalues
(this is often a more common case). It can be proved that if the eigenvalues are distinct, the
eigenvectors will be linearly independent (proof is left as an exercise). Thus, the eigenvec-
tors can form a basis for coordinate transformation*:

C = éëc1 c2  c n ùû (2.71)

Equivalent to Equation 2.37, change of coordinates to nonorthonormal† basis set is repre-

sented as

y = C -1 y (2.72)

*  Standard linear algebra texts often use Ax = λx to define eigenvalues and eigenvectors. Hence, they represent transformation
matrix for eigenvectors as the basis set as X = éë x 1 x 2  x n ùû . Note that this representation and Equation 2.54 are
equivalent. Since I have used x ÎX as input vectors in Section 2.3, I chose to use notation c as eigenvectors.
†  Recall that the eigenvectors may not be orthogonal.
 Linear Algebra   ◾    57

or equivalently

y = C y (2.73)

This can be expanded as

y = y1c1 + y2 c 2 +  + yn c n (2.74)

Premultiplying by matrix A gives us

(
Ay = A y1c1 + y2 c 2 +  + yn c n ) (2.75)

Using Equation 2.68, this becomes

Ay = ( l1c1 ) y1 + ( l 2 c 2 ) y2 +  + ( ln c n ) yn (2.76)

Simple algebraic manipulations yield

é y ù
ê 1ú
ê y ú
Ay = éël1c1 l2c 2  ln c n ùû ê 2 ú
ê ú
ê y ú (2.77)
ë nû
él1 ù é y1 ù
ê úê ú
l ú ê y2 ú
c 2  c n ùû ê
2
Ay = éëc1
ê  úê  ú
ê úê ú
êë l nú êy n úû
 û ë
CL
y

Note that the order of matrices C and Λ is important. The product ΛC implies that each
element λi multiplies the ith row of matrix C, whereas the product CΛ implies that each
element λi multiplies the ith column of matrix C. Thus, the equation cannot be written as
Ay = LC y .
Substituting (2.72), we get the following important result:

Ay = C LC -1 y
(2.78)
A = C LC -1

The above equation (2.78) is the key result of eigenvalue decomposition.

58   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Diagonalization of a matrix refers to eigenvalue decomposition of matrix A that has n

distinct eigenvalues, since the eigenvalue decomposition will result in a diagonal matrix Λ.
When the matrix A is rank deficient, one of its eigenvalues is zero. A zero eigenvalue
behaves like any other eigenvalue. There will be an eigenvector associated with the zero
eigenvalue. Note that since (A − λI) = A, the corresponding eigenvector, c, lies in the null
space of A. Consider the example

é1 2ù
A=ê ú
ë2 4û

which we had discussed as an example of rank-deficient matrix. The two eigenvalues are
λ1 = 0 and λ2 = 5. The corresponding eigenvectors are

é -2 ù é1 ù
c1 = ê ú , c 2 = ê ú
ë1û ë 2 û

where the first eigenvector, c1, which corresponds to λ1 = 0, is in the null space of A.
The above information can be obtained using eig command. The readers can verify that
the diagonal form
-1
é1 2 ù é -2 1 ù é0 0 ù é -2 1ù
ê ú=ê úê úê ú
ë2 4û ë 1 2 û ë0 5û ë 1 2û

is indeed valid.
The above results are also valid when eigenvalues exist in complex conjugate pair.

2.4.4 Applications
The eigenvalue decomposition is the cornerstone of the analysis of linear dynamical sys-
tems. It is used in both differential equations

y ¢ = Ay (2.62)

and difference equations

y k +1 = Ay k (2.79)

In both examples, the matrix A maps the R n vector space onto itself.*
First, let us perform a geometric interpretation of eigenvalue decomposition, like that in
Example 2.3, before moving to the applications.

*  Let me repeat the contrast of this case with the examples in Section 2.3. The n × n square linear operator matrix, for the linear
operation y = Ax, mapped a n-dimensional input space to another n-dimensional output space. In case of differential equa-
tion, y′ = Ay, the matrix A maps the n-dimensional space to itself.
 Linear Algebra   ◾    59

Example 2.4  Significance of Eigenvalues and Eigenvectors

Consider the matrix

é -0.25 1. 5 ù
A=ê ú
ë -2.25 4.25û

from Example 2.3. The eigenvalues and eigenvectors for this matrix can be found
using the command eig as

l1 = 3.299, l 2 = 0.701

é0.3893ù é0.8446 ù
c1 = ê ú , c2 = ê ú
ë 0.9211û ë0.5354 û

Figure 2.4 shows the geometric interpretation of eigenvalues and eigenvectors. The
dots, which form a unit circle, represent various values of vector y (as in Example 2.3,
each dot represents each of the 101 unit vectors). The plus signs represent corre-
sponding vectors Ay. Notice that the two circles are numerically the same as that in
Figure 2.3; they are plotted on the same axis because they lie on the same vector space.
However, the main geometric significance of eigenvalues and eigenvectors is shown as
the lines on the plot. The first solid line corresponds to the first eigenvector c1. When
operated by the matrix A, the result is that the vector gets simply stretched in the same
direction by a factor equal to λ1 = 3.299. This is shown by the dashed line in the figure.
Likewise, the second thick line is the vector c2, which gets shrunk in the same direc-
tion by a factor λ2 = 0.701 (this dashed line may not be visible because it is shorter and
thinner than c2).

y
Ay

FIGURE 2.4  Geometric interpretation of eigenvalues and eigenvectors. The dots represent y and
the plus symbols represent corresponding Ay. The thick solid lines are the eigenvectors c1 and c2,
whereas the dashed lines are Ac1 and Ac2, respectively.
60   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

[1 3 ; …
1

0.5 Ax
eig …
0 x
help

–0.5 close

–1

–1 0 1
Make A*x parallel to x

FIGURE 2.5  Demo window from eigshow interactive demonstrator in MATLAB®.

Thus, any vector in the direction of the eigenvector of a matrix gets stretched or
shrunk by a factor given by the eigenvalue. If an eigenvalue is negative, the result-
ing vector Aci will be a vector in opposite direction that gets stretched/shrunk by the
eigenvalue.

Thus, the physical interpretation is stretching and shrinking of the vector along the
direction of an eigenvector by a factor equal to the corresponding eigenvalue. There is an
excellent interactive tool in MATLAB called eigshow that can be used to exactly under-
stand these concepts. The direction of x can be changed using the mouse, and the vector Ax
responds to these changes. Figure 2.5 shows a screenshot of eigshow window. By interac-
tively moving the vector x and tracking how the vector Ax moves, one can understand the
concepts discussed in Examples 2.3 and 2.4.
While the above is useful in understanding eigenvalues and eigenvectors, the next exam-
ple focuses on concepts that will be useful for readers to use them.

Example 2.5  Eigenvalue Decomposition

We will continue with Example 2.4, where we saw that a vector in the direction of c1
and c2 is stretched or shrunk by a factor equal to the eigenvalue. This example gives
geometric interpretation of how eigenvalue decomposition may be used. Consider the
vector

é -0.6 ù é -1.05ù
y=ê ú Þ Ay = ê ú
ë -0.8 û ë -2.05û

These two vectors are represented by solid and dashed line in Figure 2.6, respec-
tively. As shown in the previous section, the two eigenvectors c1 and c2 are chosen as
 Linear Algebra   ◾    61

c2

c1

Ay

FIGURE 2.6  Significance of eigenvalue decomposition. The thick lines represent eigenvectors c1
and c2. The solid line represents the vector y and the dotted lines “complete the parallelogram.” The
dashed line represents the vector Ay.

basis vectors. The two dotted lines emanating from the point y complete the paral-
lelogram (e.g., Figure 2.1a). These two solid lines along (and opposite) the direction
of eigenvectors represent the projections along the eigenvectors. Since these lines are
along the eigenvectors, multiplying with matrix A results simply in expansion of the
element y1 and shrinking of the element y 2 . These two are represented by the two
thick dashed lines in the figure. These thick dashed lines are Ay1, the coordinate of
the solution along first eigenvector, and Ay 2 , the coordinate of the solution along the
second eigenvector. To get the final solution Ay in the original basis, the thick dotted
lines complete the parallelogram to yield the solution Ay displayed in the form of thin
dashed line.
This shows the practical application of eigenvalue decomposition. Since any vec-
tor that lies along an eigenvector stays along the same eigenvector, when acted upon
by the matrix A, the response of a linear system along eigenvectors can be analyzed
independently.
To summarize, the steps in computing Ay included the following:
Change of basis to eigenvectors to obtain

é -0.4236 ù
y = C -1 y = ê ú
ë -0.6223 û

is represented by thin solid lines in Figure 2.6.

Stretching/shrinking of y by a factor equal to the corresponding eigenvalue gives

é l1 ( -0.4236 ) ù é -0.2969 ù
ê ú=ê ú
êël 2 ( -0.6223 ) úû ë -2.053 û
62   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

where the first element (−0.2969) is the distance along c1 axis and the second (−2.053) is
the distance along c2 axis. These are represented as the two thick dashed lines in the figure.
Change of basis back to the natural basis

é -0.2969 ù é -1.05ù
Cê ú=ê ú
ë -2.053 û ë -2.05û

gives us the solution. Geometrically, the resulting vector, Ay, is obtained by “complet-
ing the parallelogram,” which is indicated by thick dotted lines.

The above example showed the case of distinct, real eigenvalues. However, these results
are applicable for other situations as well.

2.4.4.1 Similarity Transform
The transformation along the eigenvectors is an example of similarity transform. If S is any
invertible matrix, then the matrix B obtained as

B = S -1 AS (2.80)

is said to be similar to A and the transformation is known as similarity transform. The col-
umn vectors of matrix S form the new basis set. The above equation may be written as

A = SBS -1

Multiplying both sides with eigenvector, c, gives

lc = SBS -1c
(2.81)
lc = Bc , c = S -1c

The eigenvalues of similar matrices are equal, whereas eigenvectors are changed from c to
S−1c. The transformation along eigenvectors as basis set is a special type of similarity trans-
form, since it leads to diagonal (or nearly diagonal) matrix Λ.

2.4.4.1.1  Change of Basis  In systems where the matrix multiplication by A maps the vector space
on itself, change of basis is represented by similarity transform. This was seen in Example 2.5.
Change of basis therefore does not change the eigenvalues of the system.
Change of basis along the eigenvectors is an important practical method for analyzing
linear systems.

2.4.4.1.2  Power and Exponent of Similar Matrices  Two similar matrices, A and B are related as
A = SBS−1. We can therefore write A2 as

( )( )
A2 = SBS -1 SBS -1 = SB 2 S -1

 Linear Algebra   ◾    63

We can multiply the above with matrix A to get higher powers of A. Generalizing,

Ai = SBi S -1 (2.82)

in a similar manner.

2.4.4.1.3  Jordan Canonical Form  Jordan canonical form is a special type of similarity transform
closely related to eigenvalue decomposition. The idea behind Jordan canonical form is that any
matrix A can be written in the following form:

A = C LC -1 (2.83)

In case of n distinct eigenvalues, the matrix Λ is diagonal, as seen in Equation 2.78. When
there are repeated eigenvalues, the eigenvectors corresponding to the repeating eigenval-
ues may not be linearly independent. If that happens, full diagonalization is not possible.
However, it is still possible to decompose the matrix A in the above Jordan canonical form.
For example, consider a 3 × 3 matrix whose eigenvalues are {λ1, λ2, λ2}. It is possible to
decompose the matrix A in the following form:

él1 0 0ù
ê ú -1
A = éëc1 c2 c 3 ùû ê 0 l2 1 ú éëc1 c2 c 3 ùû
ê0 0 l 2 úû
ë

The above decomposition is nearly diagonal. The scalar “1” appears in the off-diagonal
element in each block corresponding to the repeated eigenvalue. The vector c3 is the “gen-
eralized eigenvector” of matrix A.

2.4.4.2 Linear Differential Equations

Let us assume that the matrix A is fully diagonalizable. Thus, in case of the differential
equation

y ¢ = C LC -1 y
(2.84)
(C y ) = A (C y )
-1 -1

Transforming the basis to eigenvectors, the above can be written as

y ¢ = L y (2.85)

Since Λ is diagonal, each row represents the ith differential equation

y i¢ = li y i
64   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The solution to this equation, therefore, is

ée l1t ù
ê ú
y = ê  ú y ( 0 ) (2.86)
ê e lnt úû
ë 
  
eL
Transforming it back to the original basis, the above solution is

 y (0)
Lt -1
y = Ce
 C
 (2.87)
e At
The analytical solution to the ODE (2.62) is given by the above equation. Standard text-
books on linear algebra discuss methods to compute matrix exponent. It is easy to compute
for small-size matrices. The MATLAB command expm may be used to compute the matrix
exponent numerically. Thus, the evolution of y at any time t from initial condition y0 may
be calculated in MATLAB as
>> yi = expm(A*ti)*y0;

where yi is the value yi(ti) calculated at time ti.

The diagonalization from Equation 2.86 also helps us qualitatively discuss the stabil-
ity of linear ODEs. If the eigenvalues are real and negative, the system is asymptotically
stable, implying that y(t) → 0 as t → ∞. If one or more of the eigenvalues is positive,
the system is unstable, whereas if an eigenvalue is zero, the system is marginally stable.
We will use this property in the discussion of linear stability analysis in Chapter 5 and
again in the analysis of nonlinear systems in Chapter 9.

2.4.4.3 Linear Difference Equations

As in the previous discussion on differential equations, let us assume that the matrix A is
diagonalizable. The difference equation

y k +1 = Ay k (2.79)
may be written as

y k +1 = C LC -1 y k (2.88)

Starting with k = 0, we can write

y 1 = C LC -1 y 0
(
y 2 = C LC -1 y 1 = C LC -1 C LC -1 y 0 )
= C L2C -1 y 1 (2.89)

k -1
yk = C

  y0
L C
Ak
 Linear Algebra   ◾    65

Since Λ is a diagonal matrix

él1k ù
ê ú -1
y =Cê  ú C y0 (2.90)
ê kú
ln û
ë

Just as the case of differential equation, the diagonalization from Equation 2.90 also helps us
qualitatively discuss the stability of linear difference equations. The difference equation (2.79)
results in an asymptotically stable behavior if all the eigenvalues are within the unit circle,
that is, |λi| < 1, ∀ i. If one or more of the eigenvalues are outside the unit circle, the system is
unstable; whereas eigenvalues on the unit circle implies that the system is marginally stable.
In chemical engineering, difference equations are often used in computer-based process
control and logistic maps. We will not discuss difference equations for the rest of this book.

2.5 EPILOGUE
Some of the key concepts in linear algebra were introduced in this chapter. The three types
of problems in linear systems of interest to engineers include the following.
First problem involves solving a set of linear equations of the type, Ax = b, given by

é a11 a12  a1n ù é b1 ù

ê ú é x1 ù ê ú
ê a21 a22  a2n ú ê ú ê b2 ú
x2
ê     úê ú = ê  ú (2.8)
ê úê  ú ê ú
ê     úê ú ê  ú
êam1 am2  amn ú  êë xn úû ê ú
ëû x bm û
ë
A b

The aim is to find the vector x given the right-hand side, b. The most common example is to
solve n linear equations in n unknowns, where the matrix A is an n × n matrix. However, there
are several examples where the number of equations exceeds the number of unknowns. Such
examples will be seen in linear least squares problems for parameter estimation (Chapter 10).
The MATLAB commands relevant to this type of problems are listed below.

Command Description Usage

rank Compute rank of a matrix r=rank(A);

inv Compute inverse of a matrix x = inv(A)*b;
will solve linear equation as x = A−1b if A is
full-rank
mldivide Left division to solve Ax = b (A is m × n x=A\b;or x=mldivide(A,b); solves the
matrix, and x is n × 1 and b is m × 1 linear equation Ax = b, even when A is
vectors) nonsquare.
lu LU decomposition of matrix A. Please see [L,U]=lu(A); and
Appendix C for details. [L,U,P]=lu(A); factorize A into a set of
lower/upper triangular matrices such that
A = LU or PA = LU.
66   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The linear equations problem was cast as a linear combination of column vectors of matrix A:

x1 v 1 + x2 v 2 +  + xn v n = b (2.91)

where v1, v2,  … , vn (see Section 2.2). The various properties of vectors, matrix, and asso-
ciated vector spaces were discussed. The relevant MATLAB commands are summarized
below.

Command Description Usage

null(A) Calculate null space V=null(A);

of A returns basis vectors of the null space as columns of matrix V.
orth(A) Computes image V=orth(A);
space of A returns basis vectors of the image space as columns of matrix V.
norm(b) Compute norm of a norm(b,i);
vector computes (∑i|bi|p)1/p
If i is not specified, two-norm is computed.
norm(A) Compute norm of a Computes norm of a matrix. The two-norm of a matrix is equal to its
matrix largest singular value.
cond Condition number cn=cond(A); computes the condition number, the ratio of highest
of a matrix to smallest singular values of A.

Example 2.1 used a simple model of blending process to highlight the concepts of null and
image spaces, as also to discuss the solution of linear equations. Example 2.2 showed the
sensitivity of solution to errors in the data. Condition number was introduced to quantify
this sensitivity.
The discussion on null and image spaces led us to SVD (Section 2.3). SVD was intro-
duced in the context of analyzing the second type of problems in linear algebra:

é b1 ù é a11 a12  a1n ù

ê ú ê ú é x1 ù
ê b2 ú ê a21 a22  a2n ú ê ú
x2
ê  ú=ê     úê ú (2.9)
ê ú ê ú ú
ê

ê ú ê     ú êx ú
êbm ú êam1 am2  amn ú  êë n úû
ëû  ë û x
y A

which represented linear mapping between n-dimensional input vector space X to

m-dimensional output vector space Y. Example 2.3 presented geometric interpretation of
SVD. With this, one can interpret null and image spaces in context of SVD. This was the
second practical context in this chapter: a linear map between an input and an output space.
The third practical context in this chapter is when matrix A represents a linear map
between a vector space to itself, most commonly observed in linear differential and dif-
ference equations. Section 2.4 and Example 2.5 presented eigenvalue decomposition of a
 Linear Algebra   ◾    67

linear system. The physical perspectives of singular value and eigenvalue decompositions

were also compared. The following table summarizes the relevant MATLAB commands for
the two decompositions and related functions.

Command Description Usage

svd(A) Singular value decomposition s=null(A);

returns ordered singular values of A.
[U,S,V]=svd(A);
performs SVD such that A = USVT.
eig(A) Eigenvalues (and l=eig(A);
eigenvectors) of matrix A returns eigenvalues of A.
[C,L]=eig(A);
returns eigenvectors and eigenvalues of A. Individual
columns of V contain the eigenvectors (c1, …, cn) and
the diagonal elements of L contain the corresponding
eigenvalues.
jordan(A) Perform Jordan [M,L]=jordan(A);
decomposition computes the Jordan decomposition, such that A = MLM−1.
Matrix L is nearly diagonal, with the diagonal elements
equal to the eigenvalues of A.
eigshow SVD and eigenvalue eigshow provides a GUI-based demonstrator for singular
decomposition demonstrator value and eigenvalue decompositions.

This concludes this practical introduction to linear algebra.

EXERCISES
Problem 2.1 (a) Show that linearly independent vectors v1, v2,  … , vn ∈ R n span the R n
space.
(b) Show that Equations 2.18 and 2.19 are equivalent.
Hint: Define the vector

é v 1,i ù
ê ú
v 2 ,i
vi = ê ú
ê  ú
ê ú
êë v n,i úû

to prove the equivalence.

Problem 2.2 Show that ℛn can have at most n linearly independent vectors. In other words,
show that vectors v1, v2,  … , vn, vn + 1 ∈ R n are linearly dependent.
Problem 2.3 Show that the row rank and column rank of a matrix are equal.
68   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Problem 2.4 Repeat the steps of Section 2.3.3 (Example 2.2) for solving Ax = b, with

é1 3 ù é1.37 1 ù
A=ê ú and A = ê ú
ë3 6.001û ë 0. 5 0.37 û

Specifically, find the value of b at which the solution is highly sensitive.

Change the vector b slightly and observe its effect on the solution x.
Hint: If you are unable to solve the problem, choose (up to) four different
b vectors: (i) b ∈ span{u1}, (ii) b ∈ span{u2}, (iii) b ∈ span{v1}, (iv) b ∈ span{v2}.
Problem 2.5 Show that for an n × n matrix with distinct eigenvalues, λi, the corresponding
eigenvectors ci are linearly independent.
Problem 2.6 Consider the following three matrices:

é -1.3 0. 1 ù é -8.05 -3.95 ù é 4. 8 -6.0 ù

A=ê ú, B = ê ú, C = ê ú
ë 0. 2 -1.4 û ë -7.90 -4.10 û ë 6. 3 -7.5 û

Consider the three systems

y = Ax , y = Bx , y = Cx

Randomly generate 250 data points in domain space, X, using randn. Plot
the corresponding output in Y-space. Justify the difference in observed
response.
Relate the qualitative results to the singular values of the three matrices.
Problem 2.7 For the same three matrices in Problem 2.6, choose y0=[0.7071;
0.7071]. The solution of the ODE

y ¢ = Ay , y ( 0 ) = y0

is given by y = y0eAt. This can be computed using y=y0.*expm(A*t). For

a range of time values [0:tMax], compute y. Hence, plot y vs. t.
Repeat this for y′ = By,   y(0) = y0.
Also repeat for y′ = Cy,   y(0) = y0.
What are the qualitative observations for A, B, and C matrices? Justify the
­difference in the observed response.
Relate the qualitative results to the eigenvalues and eigenvectors of the
three matrices.
 Chapter 3

Ordinary Differential
Equations
Explicit Methods

3.1 GENERAL SETUP
A general ordinary differential equation (ODE), introduced in Chapter 1, is of the form

dy
= f ( t ,y )
dt (3.1)
y (t0 ) = y 0

The initial condition at time t = t0 is specified as y0. In general, y ∈ R n is an n-dimensional
solution variable of interest, and f(t, y) : R n → R n is a vector-valued function. In this chapter,
I first cover numerical techniques to solve an ODE initial value problem (IVP), followed by
the application of ODE solution techniques to Process Engineering problems. As discussed
in Chapter 2, the convention followed throughout this text is that y is a n × 1 column vector
and f(⋅) is n × 1 function vector. The independent variable, t, is a scalar.

3.1.1 Some Examples
Examples of systems described by ODEs abound in engineering. For example, the reaction
of a species along the length of a plug flow reactor (PFR) is given by an ODE:

d
u C A = -kC An (3.2)
dz

69
70   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Since this is a first-order ODE, a single initial condition is required, CA(z = 0) = CA, in. Change
of temperature of liquid in a well-stirred vessel that is electrically heated is also given by an
ODE of the form

dT
V rc p = Qrc p (Tin - T ) + Qh Ah (3.3)
dt

where
Qh is the heat flux from the electric heater
Ah is the heater surface area

The temperature at the start, T(t = 0) = T0 forms the initial condition for this system.
More commonly, we encounter situations where multiple ODEs have to be solved, for
example, when there are multiple species in a reactor or a nonisothermal reactor, where
energy balance equation models the temperature variation in the reactor. Likewise, there
may be multiple heated tanks that need to be modeled, or the height of liquid in the tank
may vary.
Equation 3.2 is written in the standard form by dividing throughout by u. If there are
multiple species, the mass balance is written for each individual species to obtain

d
C A = f1 ( C A ,CB ,¼)
dz
d
CB = f 2 ( C A ,CB ,¼) (3.4)
dz


while the energy balance (for nonisothermal case) may be written as

dT
= fn+1 ( C A ,CB ,¼) (3.5)
dz

Equations 3.4 and 3.5 may be combined to obtain the set of ODEs:

éC A ù é f1 ( C A ,CB ,¼) ù
ê ú ê ú
d êCB ú ê f 2 ( C A ,CB ,¼) ú (3.6)
=
dz ê  ú ê  ú
ê ú ê ú
+1 ( C A ,C B , ¼) ú
ë T úû êëfn
ê
 û
y f (y)

which is in the standard form (3.1). Since the concentrations and temperature are all speci-
fied at the inlet, y(z = 0) = yin, we have a set of (n + 1) ODE-IVP.
 Ordinary Differential Equations   ◾    71

Another type of example involves conversion of higher-order ODEs into a set of first-
order ODEs. The classical example of this is the mass-spring-damper system. The motion
of a body with mass m attached to a spring is given by

mx ¢¢ = -cx ¢ - kx (3.7)

where
x″ is the acceleration
v = x′ is the velocity

The initial condition involves displacing the mass by a certain distance and releasing it. This
is an example of “damped oscillator.” The second-order ODE may be written as

x¢ = v
c k (3.8)
v¢ = - v- x
m m

Defining vector y = [x v]T, the above ODE will be written in the standard form*:

é v ù é x0 ù
y¢ = ê ú , y (0) = ê ú (3.9)
ë - cv - kx û ë0 û

The solutions of problems of the type (3.6) and (3.9), which give rise to ODE-IVP, are dis-
cussed in this chapter.
ODE-BVPs (boundary value problems): These form another type of ODEs, where the
conditions for various state variables are specified at different points in the domain. A clas-
sic example is that of heat conduction in a rod:

d 2T
= -b (T - Ta ) (3.10)
dz 2

with Ta as the temperature of the ambient. Since this is a second-order ODE, two condi-
tions are required to solve iy. If both the conditions are specified at the same location (e.g.,
T(0) = T0 and T′(0) = ϑ0), we can convert the second-order ODE into the standard ODE-IVP
form (3.1). However, more commonly, the two conditions are specified at either ends of the
domain, such as

T ( 0 ) = T0 , T ¢ ( L ) = J (3.11)

é0 1ù
*  In fact, this is an example of linear system of ODEs: y′ = Ay, with A = ê ú.
ëê -k - c úû
72   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

This leads to ODE-BVP. ODE-BVP cannot directly be solved using methods described
in this chapter. They are converted using finite difference approximation to a set of linear
or nonlinear equations and are solved. This procedure results in a special structure of the
problem. Methods for solving ODE-BVP (as well as other problems that result in similar
numerical structure) will be discussed in Chapter 7.
Thus, this chapter focuses on one family of numerical methods to solve ODE-IVP. An
introduction to numerical solution of ODE-IVP and a comparison with numerical integra-
tion will be first presented in the remainder of this section. Thereafter, an important family
of numerical methods, called Runge-Kutta (RK) methods, will be discussed. A majority of
discussions in this section will focus on a single-variable problem; extension to multivari-
able case will be considered thereafter.

3.1.2 Geometric Interpretation
Before proceeding further, I will draw parallels with numerical integration for a problem
in a single variable, that is, y is a scalar and f is a scalar function. Numerical integration is
covered in Appendix E. If the function f(⋅) is a function of t only and is independent of y,
then numerical integration may be used to “solve” Equation 3.1:

y (b ) b

ò( ) ò
y a
dy = f ( t ) dt
a
(3.12)

b
If the integral on the right-hand side is represented by I =
ò
a
f ( t ) dt , then it is clear that

I = y (b ) - y ( a ) (3.13)

Thus, y(b) may be considered as simply the integral I, if the initial condition y(a) = 0.
In contrast, if f(t, y) is a function of the dependent variable y as well, an ODE-IVP is
solved.
The geometric interpretation of integration, discussed in Appendix E, is typically well
known through the first course in high-school calculus. Integral, if we recall, is the area
under a curve: When the function f(t) is plotted against t, the area under the curve between
t = a and t = b is the integral I. It bears repeating that in understanding the meaning of inte-
gral, the function f(t) is plotted on the Y-axis.
In contrast, when solving ODE-IVP, the solution variable y is plotted on the Y-axis. The
initial condition, (a, ya), forms the starting point and f(a) is the slope at this point. The infor-
mation about the slope is used to determine the next point, y(a + h). Thus, the geometric
interpretation of solving ODE-IVP is to use the information about the slope f(t) to deter-
mine how the solution will propagate along the y–t plot.
The next question is, what if the function in Equation 3.1 is a function of both t and y?
Typically, this is when the phrase “solving an ODE-IVP” is invoked. One way of looking at
 Ordinary Differential Equations   ◾    73

ODE-IVP is to consider it as a generalization when f(⋅) can be a function of both t and y.

However, I like to consider ODE-IVP as a more general concept than this.
Consider the following example of ODE-IVP:

dy
= -t 2 y , y ( 0 ) = 1 (3.14)
dt

The above equation can be solved analytically, and the initial condition used to obtain

-t 3/3
y =e (3.15)

Note that depending on the initial condition, one gets a family of curves when one plots y(t)
vs. t. In contrast to integration, ODE-IVP is best understood when the solution, y(t) (and
not f(⋅)) is plotted on the Y-axis, as shown in Figure 3.1.
The solution for the above ODE is plotted in Figure 3.1. Unlike integration, we are inter-
ested in “tracking” how the solution y(t) evolves with time t, starting at the point (t0, y0). The
final solution y(t) depends on the initial condition, y0. For different initial conditions y0, a
-t 3 /3
family of curves y = ce is obtained in the y vs. t space. The solution in the figure is for
the initial condition of Equation 3.14.
At t = 0.5, the dependent solution variable is y(0.5) = 0.9592. The slope of the curve y(t)
equals the function value −t2y, that is, −0.240. Thus, the right-hand side of the ODE (3.14)
is nothing but the slope of the curve y(t) at any point on the curve. Solution technique for
ODE therefore involves retracing the solid line in Figure 3.1, given the slope f(t, y) at any
point in the t – y space. The family of numerical methods discussed in this chapter attempts
to use the information of the slope f(t, y) and the projected slopes to predict how y(t) will
behave in the future. Another family of numerical methods use information from the past
to predict the future y(t).

–0.240
0.8

0.6
y

0.4

0.2

0
0 0.5 1 1.5 2
t

FIGURE 3.1  Solution to the ODE (3.14). The arrow indicates slope of the tangent at t = 0.5.
74   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

3.1.3 Euler’s Explicit Method

The simplest numerical method for evaluating the ODE is Euler’s method. Applying the
forward difference approximation to y′ on the right-hand side of Equation 3.1 yields

yi +1 - yi
= f ( t i ,y i ) (3.16)
h

Rearranging the above equation yields Euler’s explicit method:

yi +1 = yi + hf ( t i ,yi ) (3.17)

In the above, h is the step-size in the independent variable t. The step-size is chosen by users
or internally by the algorithm to ensure stability and accuracy of the numerical technique.
Starting with the initial values, (t0, y0), the above expression (3.17) is used recursively to
obtain new values yi + 1 and step forward in time. The code below shows implementation of
Euler’s explicit method for the ODE-IVP given in (3.14).

Example 3.1  Euler’s Explicit Method

Problem: Solve the ODE-IVP given in Equation 3.14 using step-sizes of h = 0.1, 0.05,
0.01 to obtain y(2). Also compare the results with true solution.
Solution: The code below uses Euler’s method with step-size of h = 0.01.

%% Problem Setup
t0=0; tN=0.5;
y0=1;
h=0.01; N=(tN-t0)/h;
%% Initialize and Solve
t=[0:h:tN]'; % Initialize time vector
y=zeros(N+1,1);
y(1)=y0; % Initialize solution
for i=1:N
y(i+1)=y(i)+h*(-t(i)^2*y(i));
end
%% Output and Error
plot(t,y); hold on;
yTrue=exp(-tN^3/3);
err=abs(yTrue-y(end));

The result of the above code is shown in Figure 3.2.

As can be observed from the above figure, the symbols get closer to the true solu-
tion as the step-size is decreased. The errors in computing y(0.5) are e0.1 = 0.011,
e0.05 = 0.0057, and e0.01 = 0.0012.
 Ordinary Differential Equations   ◾    75

0.99

0.98

y
0.97

0.96

0.95
0 0.1 0.2 0.3 0.4
t

FIGURE 3.2  Comparison of the true solution to ODE-IVP of Equation 3.14 with numerical solu-
tions using Euler’s method with h = 0.1 (diamonds), h = 0.05 (squares), and h = 0.01 (circles).

Euler’s explicit method can be easily derived from Taylor’s series expansion of y(t).
Specifically, the expansion of y(ti + h) around y(ti) is given by

h2 h3
y ( t i +1 ) = y ( t i ) + hy ¢ ( t i ) + y ¢¢ ( ti ) + y ¢¢¢ ( ti ) +  (3.18)
2! 3!

Since y′(t) = f(t, y), the above equation may be written as

h2
y ( t i +1 ) = y ( t i ) + hf ( t i ,yi ) +
2!
(
f ¢ x,y ( x ) ) (3.19)

where ξ ∈ [ti, ti + 1]. The first two terms form Euler’s explicit method (3.17), whereas the last
term gives the local truncation error (LTE) of Euler’s explicit method:

h2
Elte =
2
(
f ¢ x,y ( x ) ) (3.20)

where ξ is some point between ti and ti + 1.

The LTE is the error incurred in going from yi to yi + 1 numerically, assuming the value of
yi was known accurately. However, as shown in the previous example, multiple steps were
taken, starting at t = 0 and using different step-sizes h to compute the solution y(t) numeri-
cally. Any numerical method starting from t0 and taking multiple steps to reach yi + 1 will
incur errors due to two reasons: error in the value of yi itself and the error in going from
yi → yi + 1. The net error in using multiple steps of ODE-IVP is known as the global truncation
error (GTE). The interrelationship between LTE and GTE was introduced in Chapter 1.
76   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The derivation of GTE of Euler’s method will be skipped* for brevity. It can be shown that
the GTE for Euler’s method is
M Kt
E£
2K
(
e -1 × h )
(3.21)
ìï ¶f ( t ,y ) üï ìï df ( t ,y ) üï
K = max í ý , M = max í ý
îï ¶t þï îï dt þï

The practical significance of Equation 3.21 is that the Euler’s explicit method has accuracy
( )
of the order h to the power 1, represented in shorthand as E ~ O h1 . This was observed in
Example 3.1: The error reduced by half when the step-size was halved (from ε = 0.011 for
h = 0.1 to 0.0057 h = 0.05), while the error fell by one order of magnitude (from 0.011 to
0.0012) when the step-size was reduced by one order of magnitude.
( ) ( )
The GTE of Euler’s method is ~ O h1 , while its LTE is ~ O h2 . In fact, this is a com-
mon trend that will be observed for all ODE solution techniques discussed in this book.
( )
If the LTE of the ODE solving method is ~ O hn+1 , its GTE will be ~ O hn . We will call ( )
such a method, with GTE ~ O h ( ) , as an nth order method.
n

3.1.4 Euler’s Implicit Method

Euler’s explicit method was obtained in Equation 3.16 using the definition of y′ as a forward
difference formula. Instead, if a backward difference formula is used, then

yi - yi -1
= f ( t i ,y i ) (3.22)
h

This can be rewritten as

yi - yi -1 - hf ( t i ,yi ) = 0 (3.23)

This equation needs to be solved at each time ti to obtain the value of yi. Since the solution
yi is implicitly known by solving (nonlinear) equation (3.23). The next example will demon-
strate the use of Euler’s implicit method.

Example 3.2  Euler’s Implicit Method

Problem: Solve the ODE-IVP in Example 3.1 using Euler’s implicit method.
Solution: In order to solve the ODE-IVP using Euler’s implicit method, the first step
is to substitute f(⋅) in Equation 3.23 to yield

( )
yi - yi -1 - h t i2 yi = 0

* Refer to any standard numerical ODE techniques book for the derivation. The derivation of GTE for integration, which is
pedagogically simpler, is presented in Appendix E for an interested reader.
 Ordinary Differential Equations   ◾    77

Rearranging the above equation yields

1
yi = yi -1 (3.24)
1 + ht i2

Knowing the value yi − 1 and time ti at which the solution value yi is desired, the above
expression can be used to solve the ODE-IVP using the following code.

%% Problem Setup
t0=0; tN=0.5;
y0=1;
h=0.1; N=(tN-t0)/h;
%% Initialize and Solve
y=zeros(N+1,1);
t=[0:h:tN]'; % Initialize time vector
y(1)=y0; % Initialize solution
for i=2:N+1
y(i)=y(i-1)/(1+h*t(i)^2);
end
%% Error calculation
yTrue=exp(-tN^3/3);
err=abs(yTrue-y(end));

The error in Euler’s implicit method follows the same pattern as Euler’s explicit
method. The figure using Euler’s implicit method is similar to that of Figure 3.2
and is skipped. The errors in computing y(0.5) are e0.1 = 0.012, e0.05 = 0.006, and
e0.01 = 0.0012.

Like the explicit method, Euler’s implicit method also has LTE ~ O hn+1 ( ) and GTE
~O h .( )
n

Before moving further, one point of implementation detail needs to be mentioned.

Since Euler’s method is rather simple, a comparison of codes in Examples 3.1 and 3.2 will
be useful. One of the common errors among beginners with computational methods is
related to “bookkeeping.” Comparing with the two Euler’s codes, the for loop is executed
starting at i=2 (which corresponds to t = 1. h). Note that according to Equation 3.23 for
the implicit method, past information is used to determine the current value, yi. Thus,
y(i) is computed using y(i-1) in Example 3.2. On the other hand, in the explicit
method, current information (i.e., ti and yi) is used to determine the future value yi + 1.
Thus, the for loop starts at i=1, and the current information y(i) is used to generate the
future values y(i+1).
Although Euler’s implicit method code could very well be written for i=1:N, I will
try to keep the MATLAB® codes consistent with the equations shown in the overall
derivation.
78   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

3.1.5 Stability and Step-Size

Convergence is an important property of a numerical technique. An ODE solution tech-
nique is said to be convergent if the numerical solution approaches the true solution value
as the step-size h → 0. In other words, lim yn - y ( t n ) = 0.
h ®0
Stability is another important property. A numerical solution is said to be stable if the
numerical solution yn remains bounded as n → ∞. Typically, there is a range of step-sizes, h,
for which the numerical method for solving ODE is stable.*

3.1.5.1 Stability of Euler’s Explicit Method

Euler’s explicit method has a limit on the maximum value of step-size h that can be used;
choosing a step-size larger than this value will result in an unstable solution. Consider the
recursive expression (3.17) used in Euler’s method
For the problem in Example 3.1, substituting the value of initial conditions in f(t0, y0)
yields

(
y1 = 1 - ht 02 y0 )

Further

( ) (
y2 = 1 - ht12 y1 = 1 - ht12 1 - ht 02 y0 )( )

n -1

yn = Õ (1 - ht ) y
i =0
2
i 0

The above equation is guaranteed to be stable if the following condition is satisfied:

1 - ht 2 £ 1

Since both h and t are positive, the above condition implies

2
h£ (3.25)
t2

With the end-time in Example 3.1 chosen as 10 s, run the code again. With h = 0.1, the value
of y(10) is obtained as ∼1017 because Euler’s method is unstable. On the other hand, Euler’s
method correctly gives the value of y(10) = 0 with step-size of h = 0.01.

( )
* Since all the numerical methods for solving ODE have their errors ~ O hn , n ³ 1, these numerical techniques will be
­convergent if they are stable. Hence, there is a concept of zero-stability, which implies stability of the numerical technique
when h → 0.
 Ordinary Differential Equations   ◾    79

The stability analysis can be formalized when f(⋅) is an explicit function of y only. As
seen in case studies in Section 3.5 and other chapters, this is true of a majority of chemical
engineering problems of interest. Before proceeding to the general case, consider the case
when f(y) is linear, that is, the ODE-IVP is

y ¢ = -l y (3.26)

The analytical solution for this ODE is y(t) = y0e−λt, which is stable because y(t) is bounded
as t → ∞. Substituting f(y) in Equation 3.17

yi = yi - hlyi -1 = (1 - hl ) yi -1
= -hl ( -hlyi -2 )
(3.27)

\ yi = ( -hl ) y0
i

Using the above equation, the relation for yi − 1 can be substituted as

yi = (1 - hl ) éë (1 - hl ) yi -2 ùû
= (1 - hl ) yi -2
2
(3.28)

Continuing this, it is easy to see that

yi = (1 - hl ) y0
i
(3.29)

This is a convergent series if the term (1 − hλ) lies between −1 and 1. In other words, Euler’s
method is stable if

1 - lh £ 1 (3.30)

Analogous to Equation 3.25, the condition for stability is given by

2
h£ (3.31)
l

3.1.5.2 Error and Stability of Euler’s Implicit Method

While a detailed analysis of error and stability will be skipped in this section, I draw your
attention to the fact that the error in Euler’s implicit method was similar to that obtained in
the explicit method. Both implicit and explicit Euler’s methods have a GTE ~ O h1 . ( )
80   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Consider the stability of Euler’s implicit scheme. Since both h and ti are positive, the term
(1 + ht )
-1
2
i from Equation 3.24 is positive and less than 1. Therefore, Euler’s implicit method
is stable for any choice of h. Indeed, when Example 3.2 is run for h = 0.1 and tN = 10, the
implicit method is still stable. When the step-size is further increased to h = 1, the implicit
method is still stable. Same results for stability of Euler’s implicit method are obtained for
the linear ODE case, y′ =  − λy as well. Any positive value of the step-size h will result in
stable solution.
In contrast to the explicit methods, implicit methods are often “globally stable” for any
range of values of step-size h. Even when the numerical methods are not globally stable,
their stability margins are significantly broader than the corresponding explicit methods of
equivalent accuracy. This shall be discussed further in Section II of this book. Specifically,
Chapter 8 is devoted to implicit ODE solving techniques for a variety of problems.
In addition to determining the step-size, stability analysis has significant practical rami-
fications on the choice of numerical method for solving ODEs. This will be demonstrated
toward the end of this chapter, in Section 3.5.4 (please see Example 3.15 as well). In case of
ODEs in multiple variables, if the values of λi determine the step-size. The “speed” of evolu-
tion of the ODE is governed by the smallest eigenvalue (slowest mode), whereas the step-
size is limited by the largest eigenvalue. If the ratio of the two is very large, an explicit ODE
solver may not converge. For such systems, an implicit ODE solver is required to ensure
good speed of convergence.

3.1.6 Multivariable ODE
Next, a multivariable case is considered, with y ∈ R n as an n-dimensional vector. The
reader is reminded that for the entire book, an n-dimensional vector will be a column vec-
tor (unless specified otherwise), that is, it will be an n × 1 vector. Recall the discussion in
Chapter 2, f : R n → R n, because it maps the Y -space onto itself. Thus, f(t, y) is an n × 1 vector
of nonlinear functions of t and y. With these definitions, extension to a multivariate case is
straightforward:

y i +1 = y i + f ( t i ,y i ) (3.32)

For a linear case, the ODE-IVP may be written as

y ¢ = - Ay (3.33)

Hereafter, the boldface will be dropped for convenience.* Euler’s method is written as

yi = yi -1 - hAyi -1 = ( I - Ah ) yi -1 (3.34)

* With some notable exceptions such as interpolation and integration, most of the methods discussed in this book are, in
general, applicable to multivariable cases. The derivations will be done for single-variable case. Extension to multivariable
cases will be clear from the context.
 Ordinary Differential Equations   ◾    81

where I is an n × n identity matrix. Note that in a multivariable case, the order of multiplica-
tion is important. Continuing on the same lines

yi = ( I - Ah ) y0
i

From Chapter 2, we know that the above equation is stable if eigenvalues of the matrix
(I − Ah) are in the unit circle. If eigenvalues of A are {λ1,  …, λn}, then the eigenvalues of
(I − Ah) are {(1 − λ1h),  …, (1 − λnh)}. Thus, following same arguments as before, the choice of
h should be such that all eigenvalues of Ah are positive and less than 2, which is equivalent
to saying that the step-size h should be chosen such that

2
0£h£ , "i (3.35)
li

3.1.6.1 Nonlinear Case
For a nonlinear ODE, it is possible to estimate the step-size required for stability by linear-
izing the system at the current point. Thus, defining

¶f
l=- (3.36)
¶y t , y
i i

the original ODE (3.1) can be written as

d
y » -ly
dt
Thus, the choice of h for stability is given by
2
h£ (3.37)
æ ¶f ö
ç- ÷
ç ¶y t , y ÷
è i i ø

Likewise, in a multivariable case, the matrix A is replaced by the Jacobian

é ¶f1 ¶f1 ¶f1 ù


ê ¶y ¶y2 ¶yn ú
ê 1 ú
ê ¶f 2 ¶f 2 ¶f 2 ú

J = ê ¶y1 ¶y2 ¶yn ú (3.38)
ê ú
ê     ú
ê ¶f ¶fn ¶fn ú
ê n  ú
êë ¶y1 ¶y2 ¶yn ûú

and the eigenvalues of [J] are of interest in determining the step-size.

This concludes our rather long introduction to ODE-IVP.
82   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

3.2 SECOND-ORDER METHODS: A JOURNEY THROUGH THE WOODS

Euler’s method is the simplest numerical technique to solve an ODE-IVP. The order of
( )
accuracy, given by the GTE, is of the order O h1 . This makes Euler’s method fairly inac-
curate. As we witnessed in the example in the previous section, reducing the step-size by a
factor improved the accuracy linearly by the same factor. This section introduces higher-
order ODE methods for solving ODEs, which are more accurate than Euler’s methods.

3.2.1 Some History
Euler’s method was described by Leonhard Euler in ca. 1770s. An improvement to Euler’s
method was proposed by Karl Heun in late nineteenth century. The idea draws inspira-
tion from the trapezoidal rule in integration. To compute yi + 1, Euler’s explicit method uses
the slope at the ith point, f(ti, yi); Euler’s implicit method uses the slope at (i + 1)th point,
f(ti + 1, yi + 1). The accuracy can be improved if the average of the two slopes is used. Heun
proposed that instead of using an average of the slopes at the two points, one could use the
slope at i and the “projected slope” at (i + 1). The projected point at (i + 1) is

yi + hf ( t i ,yi ) (3.39)

the slope at this point is

(
f t i +1 ,yi + hf ( t i ,yi ) ) (3.40)

and the improved Euler’s method is given by

yi +1 = yi +
h
2
( ( ))
f ( t i ,yi ) + f t i +1 ,yi + hf ( t i ,yi )

(3.41)

This Heun’s method is more accurate than Euler’s method. Specifically, its GTE is ~ O h2 , ( )
that is, it is a second-order accurate method. This shows that it is possible to use more
information to improve the accuracy of numerical ODE solution methods. Due to the
importance of differential equations in engineering and science, ODE solution techniques
have received a lot of attention in the twentieth century. Various families of methods have
been developed. This chapter will focus on explicit RK family of methods. RK methods
use multiple points between i and (i + 1) for projecting the slopes and use an average of
slopes at these projected points. These methods are of varying degrees of accuracy and
are abbreviated as RK-n, where n represents the order of GTE ~ O hn . Second-order RK ( )
( )
methods (i.e., methods with GTE ~ O h2 ) are considered in this section for pedagogical
purposes. Thereafter, extension to higher-order methods is discussed in Section 3.3.3.
Analysis of the improved Euler’s method and interpretation in context of RK-2 method
will be discussed in Section 3.2.2, whereas interpreting the improved Euler’s method in the
context of other methods is presented in Section 3.2.5.
 Ordinary Differential Equations   ◾    83

3.2.2 Runge-Kutta (RK-2) Methods

The solution using RK-2 method marches forward using the following equation:

yi +1 = yi + h ( w1k1 + w2 k2 ) (3.42)

where

k1 = f ( t i ,yi )
(3.43)
k2 = f ( t i + ph,yi + qh × k1 )

Notice that the slope f(ti, yi) from Equation 3.17 is replaced by a weighted sum, S = w1k1 + w2k2,
where the values k1 and k2 may be interpreted as slopes calculated at two different points.
RK-2 methods involve function evaluations with (at least) two intermediate points. These
function evaluations are represented as k1 and k2 in Equation 3.42.
Comparing with Equation 3.41, one can see that the improved Euler’s method uses
p = q = 1. As we will see presently, RK-2 is not a single method but a family of methods. The
derivation of the formula and error analysis is discussed next.

3.2.2.1 Derivation for RK-2 Methods

Let yi represent the current value of the dependent variable at time ti. Starting with this
value as initial condition, let y ( t i+1 ) represent the true solution. Using the Taylor’s series
expansion for the true solution around the current value yi

dy h2 d 2 y h3 d 3 y
yi +1 = yi + h + + + (3.44)
dt i 2 ! dt 2 i 3 ! dt 3 i

In the above equation, note that

dy d 2 y df ¶f ¶f dy
= f ( t ,y ) and = = +
dt dt 2 dt ¶t ¶y dt

Using this, Equation 3.44 may be written as

(i )

yi +1 = yi + hf (i )
+
2
(
h2 (i )
ft + f y( ) f ( ) +
i i h3 d 3 y
6 dt 3
) +

(3.45)

Here, we have used the shorthand notation:

¶ ¶
f ( )  f ( t i ,y i ) , f t( )  f ( t i ,y i ) , f y( )  f ( t i ,y i )
i i i

¶t ¶y
84   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Likewise, we will use Taylor’s series expansion for Equation 3.43:

¶ ¶
k2 = f ( t i , yi ) + ph f ( t i ,yi ) + qh × k1 f ( t i , yi ) + h2T (3.46)
¶t ¶y

In the above expression, we have represented the terms in (h2) and higher as T. Rearranging
the above and substituting in Equation 3.42, we get

yi +1 = yi + hw1 f ( ) + hw2 é f ( ) + phft( ) + qhf ( ) f y( ) + h2T ù

i i i i i
(3.47)
ë û

yi +1 = yi + h ( w1 + w2 ) f ( ) + h2 ( w2 p ) ft( ) + h2 ( w2q ) f y( ) + h3w2T

i i i
(3.48)

Comparing Equations 3.45 and 3.48, we get the following relations:

w1 + w2 = 1
1 (3.49)
w2 p = w2 q =
2

é1 (i ) ù
yi +1 - yi +1 = h3 ê ( y ¢¢¢ ) - w2T ú (3.50)
ë6 û

Equation 3.49 gives the relationship for choosing p, q, w1, and w2, whereas (3.50) shows that
( )
the LTE of RK-2 method is ~O h3 . Specifically, using the mean value theorem, it can be
shown that the error in RK-2 methods is

-h3

eRK 2 =
12
( )
y ¢¢¢ x, y ( x ) , x Î éët i , t i +1 ùû

(3.51)

3.2.2.2 Heun’s Method
There are four unknowns and three equations in (3.49). Thus, one of the parameters can
be chosen independently. As discussed earlier, RK-2 Heun’s method uses p = 1. This gives
q = 1, w1 = 0.5, w2 = 0.5. Thus, Heun’s method may be written as

h
yi +1 = yi +
2
( k1 + k2 )
k1 = f ( t i ,yi ) (3.52)

k2 = f ( (t i )
+ h ) , ( yi + hk1 )

( )
The GTE of an RK-2 method, such as Heun’s, is O h2 . Thus, when the step-size, h, is reduced
by a factor of 10, the error reduces approximately by a factor of 100. Consequently, RK-2
methods are more accurate than Euler’s explicit method, as demonstrated in the next example.
 Ordinary Differential Equations   ◾    85

Example 3.3  RK-2 Heun’s Method

Problem: Solve the problem of Example 3.1 using Heun’s method in MATLAB.
Solution: The code for RK-2 Heun’s method is given below. We make one
improvement in our code compared to Example 3.1. We define a function myFun,
which is used into Heun’s solver to compute f(t, y). MATLAB’s anonymous function
is used in this example (see Appendix A for a brief on MATLAB functions and
scripts).

% ODE-IVP Using RK-2 Heun's Method

% Solve ODE of the type: y' = f(t,y)
%% Problem Setup
t0=0; tN=0.5;
y0=1;
h=0.01; N=(tN-t0)/h;
myFun=@(t,y) –t^2*y;
%% Initialize and Solve
t=[0:h:tN]'; % Initialize time vector
y=zeros(N+1,1);
y(1)=y0; % Initialize solution
for i=1:N
k1=myFun(t(i),y(i));
y2=y(i)+h*k1;
k2=myFun(t(i)+h,y2);
y(i+1)=y(i) + h/2*(k1+k2);
end

The underlined command above defines the function myFun as an anonymous

function. The two inputs, t and y, are defined by the function handle @(t,y): The
function has two input arguments t and y and returns a single output –t2y. Note that
while t is a scalar, it is possible to have y as a vector (although in this example, y is
scalar as well).
The above code is written for single-variable Heun’s method with step-size h = 0.5.
We can change the first line of the code and execute it again for a different step-size.
Figure 3.3 compares the results obtained using two step-sizes: h = 0.5 and h = 0.1. It is
clear from the figure that there are errors in the numerical solution of the ODE and
that these errors are greater for the larger step-size of h = 0.5. The errors in computing
y(0.5) using the two step-sizes are e0.5 = 0.022 and e0.1 = 8.2 × 10−4.

Each step of Heun’s method requires function f(t, y) to be evaluated twice. Thus, with
h = 0.1, there are 10 function evaluations required for obtaining y(0.5). On the other hand,
Euler’s explicit method requires one function evaluation per step, so the same number
of function evaluations are required when step-size of h = 0.05 is used in Euler’s method.
The corresponding error computed in Example 3.1 was 5.7 × 10−3. Comparing with the
86   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

0.8

0.6

y
0.4

True solution
0.2 h = 0.5
h = 0.1
0
0 0.5 1 1.5 2
t

FIGURE 3.3  Comparison of Heun’s method using h = 0.5 (circles) and h = 0.1 (squares) with the true
solution (solid line). Smaller value of h results in higher accuracy.

error in Heun’s method for h = 0.1 (Example 3.2) shows the power of using a higher-order
method: The error is nearly one order of magnitude lower for the same number of function
­evaluations.
The geometric interpretation of Heun’s method is as follows. The slope at (ti, yi) of
Euler’s method is replaced by a weighted sum: h(k1 + k2)/2, geometrically, an average of
slopes k1 and k2. The former is nothing but the slope at (ti, yi). This slope is used to project
a point at ti + 1. The value k2 is the slope calculated at this projected point. Thus, Heun’s
method progresses using an average of the slope at (ti, yi) and a projection at ti + 1 using
the slope k1.

3.2.2.3 Other RK-2 Methods

The derivation in Section 3.2.2.1 shows that a family of RK-2 methods can be obtained by
choosing one of the parameters, such as the parameter p in the formulation. Another exam-
ple of RK-2 methods include the midpoint method (p = 0.5), which is given by

y i +1 = y ( ) + hk2
i

(
k1 = f t ( ) ,y ( )
i i
) (3.53)

ææ i h ö æ i h öö
k2 = f ç ç t ( ) + ÷ , ç y ( ) + k1 ÷ ÷
èè 2ø è 2 ø ø

Here, k2 is the slope at the projected “midpoint” between t(i) and t(i + 1). Projected value of y
at that point is (y(i) + h/2 k1).
Likewise, the so-called Ralston’s method is derived to minimize truncation error. In this
method

p = q = 3/4, w1 = 1/3 and w2 = 2/3 (3.54)

 Ordinary Differential Equations   ◾    87

John Butcher designed a convenient way to represent the coefficients of an RK method, now
called the Butcher tableau. A simplified tableau for RK-2 is represented as shown below:

p q

w1 w2

The bottom-most row contains weights of the (two) slopes, whereas the left-most row con-
tains the parameter p. The Butcher’s tableau will be revisited later in this section for general
RK methods.

3.2.3 Step-Size Halving: Error Estimate for RK-2

The LTE for RK-2 methods was derived in the previous section and is shown in Equation
3.51. It is usually not possible to compute error, ε, mainly because the value of f ‴(ξ, y(ξ))
cannot be calculated easily. Since the true solution is not known, calculating ε does not
seem to be straightforward. Hence, one needs to estimate what the truncation error is likely
to be. This section is devoted to discussing ways to estimate the truncation error and use
this information to improve the numerical ODE-IVP scheme. Although the information in
this section is discussed for RK-2 methods, the principles are more general and applicable
to other numerical schemes as well.
Consider again the second-order RK method for the ODE-IVP:

y ¢ = f ( t ,y ) , y ( t i ) = y i (3.55)

starting at the point (ti, yi). LTE implies the error in numerically computing yi + 1, starting
from this point, without accounting for the error accumulated in computing yi itself. As
before, if yi+1 represents the true solution of the ODE_IVP (3.55), then

yi +1 = yi +1 + ch3 (3.56)

where, c ∼  − f ‴(ξ)/12 is the factor representing the error as per Equation 3.51. The error,
ch3, can be estimated if there is an alternate way to compute yi + 1. The first way to do so is to
compute yi + 1 with a smaller step-size. Alternatively, yi + 1 may be computed using a method
with different level of accuracy (such as RK-3 method, which has LTE of O(h 4 )).
Consider the case where yi + 1 is also calculated in two steps with step-size of h/2. The
same RK-2 method is employed. The first application of RK-2 method yields

3
æhö
y 1 =y 1 + c1 ç ÷ (3.57)

i+
2
i+
2 è2ø
88   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

In the second application, y 1 is not known. Thus, the net error includes the LTE in the
i+
2
second application, as well as the effect of the first error:

3 3
æhö æhö
yi +1 » yi +1 + c1 ç ÷ + c2 ç ÷ (3.58)
2
è ø è2ø

Note the use of approximation sign above. If the function f(t, y) in Equation 3.55 is
independent of y, then the above relationship is exact. Subtracting Equation 3.56 from
Equation 3.58 and representing the difference between the solutions using two steps and a
 i +1
single step as D

 i +1 + h3 æ c1 + c2 - c ö , D
0=D  i +1 = yi +1 é h ù - yi +1 éh ù (3.59)
ç 3 3 ÷ ê2ú ë û
è2 2 ø ë û

In the above, while c ∼  − f  ‴(ξ)/12

æ é ùö æ é ùö
c1 ~ - f ¢¢¢ ( x1 ) / 12 ç with x1 Î êt i ,t 1 ú ÷ and c2 ~ - f ¢¢¢ ( x2 ) /12 ç with x2 Î êt 1 ,t i +1 ú ÷
ç i+ ÷ ç i+ ÷
è ë 2 ûø è ë 2 û ø

If the step-size is reasonably small, then we can assume c ≈ c1 ≈ c2. Thus

 i +1 - ch3 æ 1 - 1 ö
0»D (3.60)
ç 2 ÷
è 2 ø

 i +1 æç 2 ö÷
2
Ei +1 ~ ch3 » D 2
(3.61)
è 2 - 1 ø

This result can be generalized to any numerical scheme. Although the LTE was used in the
above derivation for ease of explanation, the result is more appropriately defined in terms
( )
of GTE. If the GTE of a numerical scheme is ~ O hn , then the error may be estimated as

 i æç 2 ö÷ , D
n
Ei ~ D  i = yi +1 é h ù - yi +1 éh ù (3.62)
n ê2ú ë û
è 2 -1 ø ë û

Example 3.4  Error Estimation for Heun’s Method

Problem: Estimate the error in using Heun’s method for the problem in Example 3.3
and compare it with the actual error.
Solution: In this problem, the code from Example 3.3 will be used to estimate the
error using Equation 3.62 for h = 0.1.
 Ordinary Differential Equations   ◾    89

First, the code is executed with the values of h=0.1; tN=0.1. This gives the solu-
tion y0.1[h]. The result is stored in variable yOneStep. The code is executed again
with the value of h=0.05, keeping tN the same. The solution obtained at t = 0.1 using
éh ù
this method is the value y0.1 ê ú ºyTwoStep. Next, the difference between the val-
ë2û
 0.1:
ues calculated using two steps and a single step gives D

>> Delta=yTwoStep-yOneStep;
>> errEstimate=4*Delta/3
errEstimate =z
1.6673e-04

Recall that the true value of y(t) = e−t3/3. Thus, the actual error in computing y0.1[h] is

y true ( 0.1) - y0.1 éëh ùû = 1.6672 ´ 10-4

Notice that the error estimated in the above example is close to the true error. It should be
remembered that the difference D  i, as per Equation 3.83, estimates the error in the single-
step implementation of RK-2 method. The next example demonstrates how the value of D i
can be used to obtain a more accurate approximation of the ODE solution.

3.2.4 Richardson’s Extrapolation
Let me use the following example to demonstrate Richardson’s extrapolation method to
improve the accuracy of a numerical technique.

Example 3.5  Richardson’s Extrapolation for Heun’s Method

éh ù  0.1 to get an improved solution for

Problem: Use the values of y0.1 éëh ùû , y0.1 ê ú , and D
2
ë û
the ODE-IVP from Example 3.4.
4
Solution: According to Equation 3.61, ch3 ~ D 0.1. Substituting this in Equation
3
3.56, an improved approximation of the ODE-IVP solution can be obtained as

4
y0.1 » y0.1 éëh ùû + D 0. 1
3

Continuing where we left off in Example 3.4, an improved solution can be obtained as

>> yImproved=yOneStep+4*Delta/3
yImproved =
0.9997
>> errNew=abs(yTrue-yImproved)
errNew =
1.2156e-08
90   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Note that the error in calculating y0.1 decreased significantly. This method of com-
bining results from different step-sizes to obtain an improved numerical method is
known as Richardson’s extrapolation.

So, does using Richardson’s extrapolation mean that there is no error in the improved
numerical solution? As one might guess it, the answer to that question is no. It is important
to notice that in Equation 3.61, we wrote that the error was approximately proportional to
 i +1. Richardson’s extrapolation will serve to improve the order of accuracy, not eliminate
D
the error.
( )
Consider a numerical technique has GTE ~ O hn . As earlier, yt[h] will be used to repre-
sent the numerical solution obtained using step-size h at time t. Note that in addition to the
leading error term, there are higher-order terms that have to be considered as well:

yt = yt éëh ùû + chn + dhn+1 (3.63)

h
Likewise, a similar expression can be written with step-size :
2
n n +1
éh ù æ h ö æhö (3.64)
yt = yt ê ú + c ç ÷ + d ç ÷
ë2û è 2 ø è2ø

Multiplying the above equation by 2n and subtracting

éh ù d

(2 - 1) y
n
t = 2n yt ê ú - yt éëh ùû - hn+1
ë2û 2
(3.65)

éh ù
2n yt ê ú - yt éëh ùû
ë2û d (3.66)
yt = - hn+1
2n
-1
yimproved
n
2 2 -1
 
( )
( )
E ~O hn +1

Consider application of the above formula to Heun’s method. Since n = 2 for Heun’s method

éh ù
4 yt ê ú - yt éëh ùû
yimproved = ë2û
3
4 æ éh ù ö
= ç yt ê ú - yt éëh ùû ÷ + yt éëh ùû
3 è ë2û ø
4
= yt éëh ùû + Dt
3
 Ordinary Differential Equations   ◾    91

This is the same formula that was used in Example 3.5. Richardson’s extrapolation improves
the accuracy of the numerical method to the next remaining term in the truncated series.

NOTE: RICHARDSON’S EXTRAPOLATION AND ERROR ESTIMATION

Consider the effort required in calculating y0.1 using Richardson’s extrapolation in
Example 3.5. The function f(t, y) is evaluated twice in computing y0.1[h] and four times in
éhù
computing y0.1 ê ú. Thus, six function evaluations are required for obtaining a GTE of O h3 .
ë 2û
( )
In contrast, the best RK-3 method gives the same GTE with only three function evaluations.
Thus Richardson’s extrapolation is useful only in those cases where both error estimation
and improvement in numerical scheme are simultaneously needed. It finds use in numerical
differentiation and numerical integration.
Embedded RK method, discussed in the next section, is a preferred method for online
error estimation for ODE-IVP in most commercial solvers.

Richardson’s extrapolation is not just limited to ODE solution techniques. It may be used
for any numerical method. In Problem 3.2, you’ll use Richardson’s extrapolation for trape-
zoidal rule in numerical integration and for numerical differentiation in Problem 3.3. Using
( )
a numerical method with accuracy ~ O hn , let χh be the numerical solution using step-size
h and χh/2 be the numerical solution using step-size h/2. The Richardson’s extrapolation
formula gives

2n c h / 2 - c h d
c true = - hn+1 (3.67)
2n
-1
cimproved
(n
2 2 -1
 
)
( )
E ~O hn +1

A final note is that if the numerical technique has error terms given by

c = cnum + chn + dhn+2

then the error from Richardson’s extrapolation improves to O hn+2 . ( )

3.2.5 Other Second-Order Methods (*)
Note: This section is included for completion and may be skipped without affecting the
continuity of the discussion.

3.2.5.1 Trapezoidal Rule: An Implicit Second-Order Method

The improved Euler’s method takes an average between slopes at ith point and projected
slope at (i + 1)th point. Instead, if the actual slope at the endpoint were used, we will get an
implicit trapezoidal rule:
h

yi +1 = yi +
2
( )
f ( t i ,yi ) + f ( t i +1 ,yi +1 )

(3.68)
92   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

This is an implicit, second-order method. It will be discussed again in Chapter 8, where

implicit ODE methods and methods for solving differential algebraic equations (DAEs) are
presented. More generally, it falls in the Adams-Moulton family of methods and may be said
to be second-order AM-2 method. In RK methods, the projections on the “future” points
are used; the previously computed points, yi − 1, yi − 2, …, are ignored. The Adams-Moulton
method fits a polynomial on the past points to compute

(
yi +1 = yi + h afi +1 + ( b1 fi + b2 fi -1 +  + bn fi -n+1 ) )
Since the right-hand side depends on yi + 1, this is an implicit family of methods

3.2.5.2 Second-Order Adams-Bashforth Methods

The idea of Adams-Bashforth methods is like the Adams-Moulton method, except that they
are explicit. Thus, a = 0 and Adams-Bashforth method is given by

yi +1 = yi + h ( b1 fi + b2 fi -1 +  + bn fi -n+1 )

The second-order AB-2 method is given by

3h h (3.69)
yi +1 = yi + fi - fi -1
2 2

Note that AB-1 method is nothing but Euler’s method.

3.2.5.3 Predictor-Corrector Methods
The improved Euler’s method was originally proposed by Wilhelm Heun as a “predictor-
corrector” method. The explicit Euler’s method

+1 = yi + hf ( t i ,yi )
yipred

is used to predict the next point, and a higher-order method

yi +1 = yi +
h
2
( (
f ( t i ,yi ) + f t i +1 ,yipred
+1 ))
is used to improve this prediction. In general, ABn − 1 is used as a predictor and AMn is used
as a corrector. This is done not merely to improve the accuracy of the numerical method
(ABn can instead be used if accuracy was the only concern); the predictor-corrector meth-
ods have improved stability properties than explicit AB methods but are still explicit, unlike
AM methods.
MATLAB solver ode115 uses Adam’s predictor-corrector methods of varying orders,
( ) ( )
from O h1 to O h15 . This is an explicit solver.
 Ordinary Differential Equations   ◾    93

3.2.5.4 Backward Differentiation Formulae

The idea of backward differentiation formulae (BDFs) is to use the past information much
the same way as AM methods. However, instead of fitting polynomial to past values of fi − j,
the past values of the solution are used instead to improve the order of accuracy:

yi +1 = ( c1 yi + c2 yi -1 +  + cn yi -n+1 ) + ahf ( t i +1 ,yi +1 )

The second-order BDF formula is written as

4 1 2h
yi +1 = yi - yi -1 + f ( t i +1 ,yi +1 ) (3.70)
3 3 3

MATLAB solver ode15s uses first- to fifth-order BDF method. It is the second most pop-
ular solver in MATLAB and is useful for solving stiff ODE-IVP problems, as well as some
types of DAE problems. The need for a stiff solver like ode15s is introduced in a case study
in Section 3.5.4 and the implicit methods are discussed in more detail in Chapter 8.

3.3 HIGHER-ORDER RUNGE-KUTTA METHODS

The previous section focused on second-order methods. The RK methods are popular for
solving ODE-IVP because higher-order methods with better accuracy are available; they
are relatively easy to code being explicit methods; and they allow adaptive step-sizing,
where the step-size h is varied to meet the error tolerances. Higher-order RK methods will
be discussed in this section.

3.3.1 Explicit Runge-Kutta Methods: Generalization

The key idea behind RK methods is to replace f(t, y) for computation of yi + 1 with a weighted
slope calculated at multiple points, that is

yi +1 = yi + h × S ( t i ,yi ) (3.71)

where S(.) is a term that can be explicitly calculated from known quantities ti and yi. Higher-
order RK methods include more terms based on the projection of f(t, y). A generic RK
method that involves m-terms may be written as

yi +1 = yi + ( w1k1 + w2 k2 +  + wm km ) (3.72)

where

k1 = f ( t i ,yi )
k2 = f ( (t i + p2h ) , ( yi + q21hk1 ) ) (3.73)
k3 = f ( (t i + p3h ) , ( yi + q31hk1 + q32 hk2 ) )

94   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The first term, k1, is just the slope at ith point; the second term, k2, involves coefficients
p2 and q21. Thus, k2 is a slope computed at some projected point between i and (i + 1). The
terms in subsequent stages use the slopes, kj, computed so far. A compact way of represent-
ing an RK method with m terms is
m

yi +1 = yi + åw k
j =1
j j (3.74)

æ æ j -1 öö
ç å
k j = f ç ( t i + p j h ) , y i + ç h q j k ÷ ÷
ç
è  =1
÷÷
øø
(3.75)
è
The Butcher’s tableau is a convenient way of representing all the weights for RK and similar
family of methods. The general Butcher’s tableau is written as
p1 q11

p2 q21 q22

pm qm1 qm2 qm,m–1 qm,m

w1 w2 wm–2 wm

or the shorthand notation

p Q

Note that in RK family of methods, the first row is zero, since the first term k1 is simply
the slope f(ti, yi). For explicit methods, all the diagonal elements and superdiagonal ele-
ments in Q are zero. This is because, as seen in Equation 3.75, the summation is only up to
(j − 1). Thus, k2 depends on h, ti, yi, k1 but not on itself and subsequent terms; k3 depends on
h, ti, yi, k1, k2 but not on itself and subsequent terms; and so on.
The Butcher’s Tableau for explicit RK methods using m terms is given by
0

p2 q21

pm qm1 qm2 qm,m–1

w w wm–1 wm
 Ordinary Differential Equations   ◾    95

Note that all the diagonal elements, q11, q22, … are zero, making these explicit ODE methods.

NOTE: SOME INTERESTING INFORMATION

The Butcher tableau became a standard way of representing coefficients of numerical ODE
solvers in the last few decades, after John Butcher published his book on differential equa-
tions. The Butcher tableau for explicit RK methods has a strictly lower triangular structure,
with diagonal and superdiagonal elements as zero.
However, there exists a class of implicit RK methods that have the diagonal elements in
the matrix Q as nonzero. Methods that have nonzero superdiagonal elements may not be
categorized as RK methods.
The so-called Lobatto and Radau methods are fully implicit methods, where the entire
Q matrix may contain nonzero elements. These are not RK-type methods but instead have
roots in quadrature and collocation formulae. Interestingly, these methods were proposed
before RK methods. In fact, Reheul Lobatto died in 1866, 1 year before Martin Kutta was
born! It is only recently that Lobatto and Radau methods are expressed in terms of the
Butcher tableau.

The explicit RK methods with m stages are of the form of Equations 3.74 and 3.75. The number
of stages m is nothing but the number of terms ki that are used in solving the ODE-IVP. The
Butcher’s tableau for explicit RK methods is such that its first row is zero (p1 = 0, q1ℓ = 0) and
that Q matrix is strictly lower triangular (i.e., all the diagonal elements q and superdiagonal
elements are zero). On the other hand, the order of an RK method is the order of GTE; thus,
( )
the nth order RK method has GTE ~ O hn . One interesting result for all explicit RK methods
is that the order of the RK method does not exceed the number of stages, that is, n ≤ m. This
( )
means that the RK method with four terms can at most be O h 4 accurate. There is an upper
limit on the order of the RK method with m terms. However, it is possible to choose the weights
p, Q, and w such that the order of accuracy is lower. The standard RK-3 method is written as
h
yi +1 = yi +
6
( k1 + 4k2 + k3 ) (3.76)

where
æ h hk ö
k1 = f ( t i ,yi ) , k2 = f ç t i + ,yi + 1 ÷ , k3 = f ( t i + h,yi - hk1 + 2hk2 )
è 2 2 ø
The Butcher tableau for this RK-3 method is
0

0.5 0.5

1 −1 2

1 4 1
6 6 6
96   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

( ) ( )
This method has LTE of ~ O h 4 and a GTE of ~ O h3 . Just as we had seen in RK-2 meth-
ods, it is possible to choose different values of weights p, Q, and w to obtain various RK-3
methods involving three stages. The following example presents a MATLAB code for using
standard RK-3 for solving ODE-IVP.

Example 3.6  Standard RK-3 Method

Problem: Use the standard RK-3 method of Equation 3.76 to solve the ODE of
Example 3.3.
Solution: The code for Heun’s method from Example 3.3 is modified as below to
implement the standard RK-3 method. As before, the anonymous function is used in
the code below.

% ODE-IVP Using Standard RK-3 Method

% Solve ODE of the type: y' = f(t,y)
%% Problem Setup
t0=0; tN=0.5;
h=0.01; N=(t3.t0)/h;
y0=1;
myFun=@(t,y) -t^2*y;
%% Initialize and Solve
t=[0:h:tN]'; % Initialize time vector
y=zeros(N+1,1);
y(1)=y0; % Initialize solution
for i=1:N
k1=myFun(t(i),y(i));
t2=t(i)+h/2;
y2=y(i)+h/2*k1;
k2=myFun(t2,y2);
t3=t(i)+h;
y3=y(i)-h*k1+2*h*k2;
k3=myFun(t3,y3);
y(i+1)=y(i) + h/6*(k1+4*k2+k3);
end
%% True solution and error
yTrue=exp(-t.^3/3);
err=abs(yTrue-y);
disp([h,err(end)]);

The above code uses RK-3 method to solve the ODE-IVP. The following results are
obtained when the code is run with various step-sizes.

h err
0.1 6.6908e-06
0.05 8.3830e-07
0.01 6.6685e-09
 Ordinary Differential Equations   ◾    97

When the step-size is halved from 0.1 to 0.05, the error reduces by a factor of 8;
whereas, when the step-size is reduced by one order of magnitude, the error reduces
by three orders of magnitude. This is because RK-3 is a O h3 method. ( )
It should be noted that the actual error will also depend on f ⁗(ξ) terms. So, the
actual change in error may not be exactly (h1/h2)n; this is just an indicator of how the
numerical method behaves in a qualitative (and semiquantitative) way.

Similarly, higher-order RK methods have also been derived. Fourth-order RK methods will
be discussed in a separate Section 3.3.3 due to their popularity in ODE solving.

3.3.2 Error Estimation and Embedded RK Methods

I mentioned in the previous section that two ways of estimating errors in RK methods are
to use step-size halving (Section 3.2.3) or to use two different RK methods of differing accu-
racy. The latter method is discussed here.
Let us consider the RK-2 midpoint method

yiRK 2
+1 = yi + hk2
(3.77)

æ h h ö
k1 = f ( t i ,yi ) , k2 = f ç t i + ,yi + k1 ÷
è 2 2 ø

is used to solve the ODE-IVP. The solution is related to the true value as

yi +1 = yiRK 2
+1 é
3
ëh ùû + ch (3.56)

( )
since the LTE of RK-2 method is ~ O h3 . Third-order RK-3 methods have a greater
­accuracy than RK-2 methods. The solution using RK-3 method (employing three function
evaluations*) was represented as

+1 = yi + h ( w1k1 + w2 k2 + w3 k3 )
yiRK 3

and the numerical solution of the RK-3 method is related to the true solution as

yi +1 = yiRK 3
+1 é
4
ëh ùû + dh (3.78)

Note that unlike Examples 3.3 and 3.6, we are considering LTE in the above equations. The
difference between the two is given by

0 = yiRK 3
+1 é ùû - yiRK
ëh
2
+1 é h ùû + dh 4 - ch3
ë
 
Di +1

* An RK-3 method requires at least three function evaluations. It is possible to derive RK-3 methods with more than three
function evaluations as well. I have kept this discussion simple with three function evaluations only, though the arguments
are generalized to any higher-order method.
98   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Thus, noting that the leading error term is ch3, the above equation is approximated as

ch3 » Di +1 º Ei +1 (3.79)

Thus, the difference between the single application of RK-3 and RK-2 methods provides an
estimate of the error for the RK-2 method. This is demonstrated in the next example, where
the error in using RK-2 midpoint method will be estimated. We will use the standard RK-3
method of Example 3.6:

h
yiRK 3
+1 = yi +
6
( k1 + 4k2 + k3 ) (3.76)

where

æ h hk ö
k1 = f ( t i ,yi ) , k2 = f ç t i + ,yi + 1 ÷ , k3 = f ( t i + h,yi - hk1 + 2hk2 )
è 2 2 ø

The following example uses the RK-2 and RK-3 methods together to estimate the LTE
in RK-2.

Example 3.7  Error Estimation for RK-2

Problem: To estimate the error in RK-2 method using single implementation of RK-3.
Solution: The code for Heun’s method from Example 3.3 is modified as below.
The term yMP calculates yi + 1 using RK-2 midpoint method, whereas the term z cal-
RK 3
culates yi+1 using Equation 3.88. The difference is captured in the variable delta.
The code for single use of RK-2 midpoint method along with error estimate is given
below.

% Define problem conditions

h = 0.1;
t0 = 0;
y0 = 1;
% Calculate intermediate points
k1 = -t0*t0*y0;
t2 = t0+h/2;
y2 = y0+h/2*k1;
k2 = -t2*t2*y2;
t3 = t0+h;
y3 = y0-h*k1+2*h*k2;
k3 = -t3*t3*y3;
% Midpoint method solution
yMP = y0+h*k2;
% Error estimate
 Ordinary Differential Equations   ◾    99

z = y0 + h/6*(k1+4*k2+k3);
del = abs(z-yMP);
err = abs(exp(-h^3/3) – yMP);

The above code is executed for various values of h and the results are tabulated below:

h del err
0.02 6.667e-7 6.667e-7
0.1 8.325e-5 8.328e-5
0.5 9.115e-3 9.561e-3

It is clear from the above table that Δ1 is a reasonable approximation of local error E1.

Thus, using RK methods of different orders to estimate the numerical error is the first key
idea. Notice an important factor in the above example: The terms ki used in the RK-2 and
RK-3 methods are the same. In fact, we could write the RK-2 method as

+1 = yi + h ( 0k1 + 1k2 + 0k3 )

yiRK 2

to represent that the two methods use the same terms with different weights. The extended
Butcher tableau is written as
0

0.5 0.5

1 −1 2

0 1 1
1 4 1
6 6 6

Generalizing this, we can write it as

p Q

wRKn
wRK(n + 1)

The above is the second key idea behind embedded RK methods.

The third key idea is that error is proportional to the nth power of h for an RK-n method. If
the RK-n method is used with two different step-sizes, h and hnew, then as per Equation 3.61

Enew ( hnew )
n +1

= (3.80)
(h )
n +1
E

100   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

( )
where the LTE of the method is O hn+1 . Recall that in Equation 3.79, the RK-2 method has
( ) ( )
LTE ~ O h3 , the RK-3 method has LTE ~ O h 4 and their difference, Δ ∼ ch3. This differ-
ence, Δ, between the solutions from two different RK methods is approximately equal to the
error E of the lower order RK method, as seen in Equation 3.79.
Let us say that the desired accuracy of the numerical method was Enew = εtol. Then, from
Equation 3.80

1/n
æe ö (3.81)
hnew ~ h ç tol ÷
è D ø

is designed to give the error tolerance desired from the ODE solver.

Example 3.8  Step-Size Adaptation in RK-2 Method

Here, let us combine the results from Example 3.7 to improve the error performance
of RK-2 midpoint method using Equation 3.81.
The value of yMP, z and their difference Δ was computed in Example 3.7 for h = 0.5
as yMP = 0.9688, z = 0.9596, |Δ| = 9.115e − 3. Let us say that the desired error toler-
ance was εtol = 10−5. From Example 3.7, we also know that the error for h = 0.02 was
6.7 × 10−7 and that using h = 0.1 was 8.3 × 10−5. So, the step-size that gives error of 10−5
would lie somewhere between these two values of step-sizes. Using Equation 3.81,
we get

1/3
æ 10-5 ö
hnew = 0. 5 ç -3 ÷
è 9.115 ´ 10 ø

which yields us hnew = 0.0516. Let us now run RK-2 midpoint method with this step-
size. To do so, the code in Example 3.7 was executed again with h=0.0516. With no
other change in the code:

err =
1.1448e-05

This indicates that Equation 3.81 may be used to determine the step-size that gives
approximately the desired error.

3.3.2.1 MATLAB® Solver ode23

MATLAB has a variety of solvers in their ODE suite. MATLAB has a solver ode23 that
uses a combination of second- and third-order RK methods with adaptive step-sizing.
 Ordinary Differential Equations   ◾    101

It is an explicit RK solver with four stages. The Butcher tableau for this Bogacki-Shampine
method is
0

0.5 0.5

0.75 0 0.75

(3.82)
1 2/9 1/3 4/9

2/9 1/3 4/9

7/24 1/4 1/3 1/8

The interested reader is referred to the paper by Shampine and coworkers for more infor-
mation on this and other solvers in MATLAB. The ode23 solver has another interesting
property called “first same as last” (FSAL for short). The coefficients used for calculation of
k4 are the same as the weights wRKn. In other words, the projected value of k4(ti, yi) calculated
at the ith step is the same as f(ti + 1, yi + 1). Thus, one does not need to calculate k1 at each step;
k1 at the (i + 1)th step equals the value of k4 calculated at the previous step.
The adaptive step-size RK solvers work in a similar manner as described in this section.
The step-size that was determined from the previous step is used to compute the solution
yi + 1 at the next step using the first RK method (from extended Butcher’s tableau). Using the
second RK method from the extended Butcher’s tableau, the value Δ (which is Δ = z − yi + 1) is
computed. The new step-size is computed using Equation 3.81. This forms the step-size for
the next step. The same procedure is repeated at each point in computing the trajectory of y(t).
The procedure is slightly different for the first step. The method starts with some
(­possibly arbitrary) estimate of the step-size and uses Equation 3.81 to iteratively determine
an appropriate step-size. Once determined, this step-size is used in computing y1; thereafter
the method proceeds as explained before.
Writing a code for adaptive step-size RK method will be skipped in this chapter.

3.3.3 The Workhorse: Fourth-Order Runge-Kutta

In this chapter, I have presented first-, second-, and third-order RK methods. The Bogacki-
Shampine method was a four-stage RK method. With different values of weights, RK-2 and
RK-3 methods were obtained. The best order of accuracy for a four-stage RK method is
( )
~ O h 4 . The overall equation for a single step using four intermediate points is given by

yi +1 = yi + h ( w1k1 + w2 k2 + w3 k3 + w 4 k4 ) (3.83)

102   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

where

æ æ m -1 öö
ç
ç
ç
ç
è
å
k1 = f ( t i ,yi ) , km = f ( t i + pmh ) , yi + h qmj k j ÷ ÷
÷÷
ø ø
(3.84)
è j =1

For all explicit RK methods, the order of the RK method does not exceed the number of
stages. The highest order of accuracy possible for m = 2 stages is n = 2; for m = 3 stages is
n = 3; and for m = 4 stages is n = 4. This means that RK method with four terms can at most
( ) ( )
be O h 4 accurate; it is not possible to have O h5 or higher accuracy with four stages.
However, the interesting fact is that the highest order of accuracy possible for any m = 5
( )
stage RK method is still O h 4 ; the minimum number of terms required for O h5 RK-5 ( )
method is m = 6. This is an interesting result; it also happens to be the reason for popularity
of RK-4 methods. The popularity of RK-4 methods is because including the fifth term k5
does not improve the order of accuracy of RK method compared to the best four-stage RK
method.

3.3.3.1 Classical RK-4 Method(s)

The classical RK-4 method is given by the following formula:

h

yi +1 = yi +
6
( )
( k1 + 2k2 + 2k3 + k4 ) + O h5

(3.85)

where

æ h h ö æ h h ö
k2 = f ç t i + ,yi + k1 ÷ , k3 = f ç t i + ,yi + k2 ÷ , k4 = f ( t i + h,yi + hk3 )
è 2 2 ø è 2 2 ø

Thus, the Butcher tableau for RK-4 classical method is given by

1/ 1/
2 2

1/ 0 1/
2 2

1 0 0 1

1/ 1/ 1/ 1/
6 3 3 6
 Ordinary Differential Equations   ◾    103

The classical RK-4 method uses four intermediate stages and yields a method that has a
( )
global accuracy of O h 4 .

3.3.3.2 Kutta’s 3/8th Rule RK-4 Method

Several other RK-4 methods can also be derived. Another popular method is that from
Kutta, proposed in the same paper as the classical RK-4 method. This method is similar to
Simpson’s 3/8th rule for integration (see Appendix E for discussion on integration formu-
lae), if the function f is function of t only. The formula is given by

h

yi +1 = yi +
8
( )
( k1 + 3k2 + 3k3 + k4 ) + O h5

(3.86)

The Butcher’s tableau for this method is

1/ 1/
3 3

2/ −1/ 1
3 3

1 1 −1 1

1/ 3/ 3/ 1/
8 8 8 8

Since the previous method is called classical RK-4, this RK-4 method is often called 3/8th
rule RK-4 method.
The classical RK-4 method was described originally in their seminal work by Carl Runge
and Martin Kutta. The method is rather elegant and easy to implement. When numeri-
cal computing started becoming popular in the first half of the twentieth century, RK-4
became an ODE-IVP method of choice. An additional term did not give any advantage
( )
because the best accuracy from a five-stage RK method still remains O h 4 . Later, when
( )
computational speeds improved, the O h 4 method with adaptive step-sizing provided suf-
ficiently high accuracy that RK-4 remained the most popular explicit ODE-IVP technique.

3.4 MATLAB® ODE45 SOLVER: OPTIONS AND PARAMETERIZATION

MATLAB’s default ODE-IVP solver is ode45, which uses Dormand Prince (RK-DP)
method. This uses a combination of fifth- and fourth-order methods. The fifth-order
method gives the value of the differential variable, yi + 1, at the next time ti + 1. Based on
the discussion in the previous section, it is clear that the minimum number of interme-
diate stages required for a fifth-order RK method is six. Since this is an embedded RK
method, the same function evaluations will be used by the fourth-order RK method as well.
104   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The fourth-order method is used for error control. The extended Butcher tableau for this
method is given by

1/5 1/5

3/10 3/40 9/40

4/5 44/45 –56/15 32/9

8/9 19372/6561 –25360/2187 64448/6561 –212/729

1 9017/3168 –355/33 46732/5247 49/176 –5103/18656

1 35/384 0 500/1113 125/192 –2187/6784 11/84

35/384 0 500/1113 125/192 –2187/6784 11/84

5179/57600 0 7571/16695 393/640 –92097/33920 187/2100 1/40

The first set of weights give the fifth-order method. Thus, the next value of yi + 1 is given by

æ 35 500 125 2187 11 ö

yi +1 = yi + h ç k1 + k3 + k4 - k5 + k6 ÷ (3.87)
è 384 1113 192 6784 84 ø

Since this is an embedded RK method, the same function evaluations are used in calcula-
tion of the fourth-order solution. Additionally, since k7 is not used in computing yi + 1 as per
Equation 3.87, it is computed as follows:

æ 35 500 125 2187 11 ö

zi(+1) = yi + h ç
7
k1 + k3 + k4 - k5 + k6 ÷
è 384 1113 192 6784 84 ø (3.88)

( (7 )
k7 = f t i +1 ,zi +1 )

The fourth-order embedded method gives

æ 5179 7571 393 92097 187 1 ö

yi(+1 ) = yi + h ç
RK 4
k1 + k3 + k4 - k5 + k6 + k7 ÷ (3.89)
è 57600 16695 640 339200 2100 40 ø

The difference

D = yi +1 - yi(+1 ) (3.90)
RK 4

provides error estimate.
 Ordinary Differential Equations   ◾    105

Additionally, RK-DP method is a first same as last (FSAL) method. Notice that the
coefficients for computing k7 on the last row of q weights are the same as the coefficients
used in Equation 3.87. In other words, since the coefficients used in Equation 3.87 to com-
pute yi + 1 are the same as the coefficients used for computing k7 as per Equation 3.88, the
function value k7 computed in the current step is the same as the first function evaluation
to compute k1 in the next step. Thus, one additional function evaluation is avoided due to
the FSAL property. Thus, at each step, because k1 is nothing, but k7 of the previous step, six
function evaluations (to compute k2,  … , k7) are required for each step of RK-DP method.
The case study Section 3.5 will extensively use ode45 solver for solving ODE-IVP.
Before that, we end this section with the following brief example that shows application of
ode45. All the ODE methods in MATLAB follow the same format. They require a func-
tion that takes scalar-valued t and vector y as input argument and return f(t, y) as the out-
put. Function f should be of the same dimension as the vector y. The syntax for ode45 is

[tSol,ySol]=ode45(@(t,y) myFun(t,y), tSpan, y0);

where tSol is the time vector at which the solutions are obtained, ySol are the solutions
y(t), tSpan gives the time span for which the solution is desired, and y0 is the initial
condition at time tSpan(1). The matrix ySol has as many rows as the number of time-
points in tSol and as many columns as the dimension of vector y.
The next example demonstrates use of ode45 for a 1D problem.

Example 3.9  Using ode45 for Solving Example 3.3

The initial condition and function was already defined in earlier examples as

% Conditions for solving the ODE

t0=0; tN=0.5;
y0=1;
myFun=@(t,y) -t^2*y;

Note that since the solution is desired in the range [t0, tN], this forms the vector
tSpan. Thus, the remainder of the code consists of the following single line (and
comment):

% Solving the ODE

[tSol,ySol]=ode45(@(t,y) myFun(t,y), [t0,tN], y0);

This is all that is required to solve the ODE-IVP using ode45 solver. The solver takes
step-size of approximately ~0.0125 to meet the desired tolerance.

3.5 CASE STUDIES AND EXAMPLES

The concepts presented in this chapter will now be applied for solving practical problems of
interest to chemical engineers.
106   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

3.5.1 An Ideal PFR

A PFR is an idealized reactor, which is used to carry out the following general reaction:

A ® Products

The inlet consists of the reactant introduced at a concentration CA0. If the inlet volumetric
flowrate is Q, the velocity is given by u = Q/Acs, where Acs is the area of cross-section of the
PFR. The molar flowrate is FA = QCA. The model for a PFR at steady state is given by

d
dz
( uCA ) = RA (3.91)

Consider the case where the reaction rate is given by the Langmuir-Hinshelwood model.
If there is no change in volume due to reaction, u is constant and the overall model for the
system is written as

dC A kC A (3.92)
u =- , C A0 = 1 mol/m3
dz 2
1 + K r CA

The kinetic parameters for the system are

k = 2 s -1 , K r = 1 mol 2 /m6

First, this problem will be solved using ode45 solver. Thereafter, the problem will be recast
as a design problem for the PFR and solved using numerical integration. This example
will thus also be used to illustrate the relationship between integration and ODE-IVP. In
Chapter 5, extensions of the PFR will be undertaken as case studies.

3.5.1.1 Simulation of PFR as ODE-IVP

It is necessary to espouse good MATLAB programming practices right at the outset.
Toward this goal, the code will be written in a modular fashion, keeping it flexible for fur-
ther extensions and utilization of MATLAB’s functionalities to maintain a consistent coding
structure. An important aspect of good programming practices that I evangelize includes
separation of problem definition and solution. I will define a single “driver” script (which is
executed by the user) that provides problem definitions and handles overall project execu-
tion and uses separate function(s) as required. The function file, insofar as possible, may
avoid defining parameters of the problem. The parameters are defined in a separate file
(for larger projects) or in the driver script (smaller problems such as the current example).
These parameters are passed to the solver function through use of parameterized anony-
mous functions in MATLAB. The following example illustrates this method as well.
 Ordinary Differential Equations   ◾    107

Example 3.10  Conversion in PFR

Problem: For the PFR described above, use ode45 to obtain concentration CA along
the length of a 0.5 m long PFR. Also compute the conversion XA. The inlet flowrate is
Q = 0.1 m3/s and cross-sectional area is Acs = 0.25 m2.
Solution: The first task is to consider making the function file that will be passed
to ode45; this function will take z and Ca as inputs and returns dC. The computa-
tion of dC is as per Equation 3.92. The values of rate parameters, k and K, as well
as inlet velocity u, form the parameters for the PFR. This function will be named
pfrModelFun.
The inlet concentration CA0 forms the initial condition. It is, in general, not a
model parameter. The model parameters, initial conditions, and solution parameters
will be defined in the driver script. In earlier versions of MATLAB, due to the lack of
other options, model parameters were passed to the function using global variables.
This practice is discouraged; a parameter structure will be passed to the function
instead.
Once the ODE is solved, a separate section computes and plots the final results. The
conversion is defined as follows:

FA0 - FA Q ( C A0 - C A )
XA = =
FA0 Q C A0

The core of the function pfrModelFun consists of the following lines:

rxnRate=k*Ca/sqrt(1+Kr*Ca^2); % Reaction rate

dC=-1/u*rxnRate; % Overall model equation

In addition to the above, the parameters, k, Kr, and u need to be obtained

from modelParam structure. This structure will be defined in the driver script
pfrLHDriver and passed using anonymous function definition: @(z,Ca)
pfrModelFun(z,Ca,modelParam).
The resulting model function pfrModelFun.m is given below:

function dC=pfrModelFun(z,Ca)
% To compute dC/dz for a PFR for a
% single Langmuir-Hinshelwood rate
% Model Parameters
k=modelParam.k;
Kr=modelParam.Kr;
u=modelParam.u0;
% Calculation of PFR model equation
rxnRate=k*Ca/sqrt(1+Kr*Ca^2);
dC=-1/u*rxnRate;
108   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The following is the driver script pfrLHDriver.m:

% Driver script for simulation of a PFR

% with single reaction using LH kinetics
%% Model Parameters
modelParam.k =2;
modelParam.Kr=1;
% Reactor conditions
Acs=0.25;
L=0.5;
modelParam.u0=0.1/Acs;
modelParam.C0=1;
%% Simulating the PFR
[Z,CA]=ode45(@(z,Ca) pfrModelFun(z,Ca,modelParam), ...
[0 L],modelParam.C0);
%% Computing and plotting results
XA=(modelParam.C0-CA)/modelParam.C0;
plot(Z,XA);
xlabel('Length (m)'); ylabel('conversion');

Figure 3.4 is a plot of conversion vs. length of the PFR. The conversion increases with the
length of the PFR. Conversion of 75% is attained at PFR length of 0.32 m. Conversely, PFR
volume of 0.08 m3 is required for attaining 75% conversion.

3.5.1.2 Numerical Integration for PFR Design

The model equation of PFR (Equation 3.92) can be rewritten in the form of design equation
that is familiar to chemical engineers:

d ( Q /Acs ) C A dFA kC A
º =- (3.93)
dz dV 1 + K r C A2

0.8
Conversion

0.6

0.4

0.2

0
0 0.1 0.2 0.3 0.4 0.5
Length (m)

FIGURE 3.4  Conversion as a function of PFR length.

 Ordinary Differential Equations   ◾    109

From the definition of conversion

FA = FA0 (1 - X A ) , C A = C A0 (1 - X A )

Thus, the design equation is written as

æ dX ö kC A0 (1 - X A )
FA0 ç - ÷=-
è dV ø 1 + K r C A2 0 (1 - X A )
2

Rearranging, the PFR design equation is given by

X pfr æ 2 ö
FA0 ç 1 + K r (1 - X A ) ÷
¢

V=
ò
0
k ¢ çè (

1 - XA )
ø
÷
dX , k ¢ = kC A0 , K r¢ = K r C A2 0 (3.94)

fval

This integration can be solved using trapezoidal rule (MATLAB command trapz), as
described in Appendix E.

Example 3.11  Design of a PFR

Problem: Solve the PFR design equation to obtain reactor volume for 75% conversion.
Solution: The following code was used for PFR design. The initial part of the code
remains similar to the PFR driver. The remainder of the code is given below.

%% Design Parameters
kPrime=modelParam.k*CA0;
KrPrime=modelParam.Kr*CA0^2;
FA0=(u0*Acs)*CA0;
%% Design of PFR
Xpfr=0.75;
XALL=[0:0.01:Xpfr];
RALL=kPrime*(1-XALL)./sqrt(1+KrPrime*(1-XALL).^2);
fval=FA0./RALL;
% PFR Volume
V=trapz(XALL,fval);

The resulting value of volume is given below:

>> V =
0.0798
110   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Numerical integration requires splitting of the integration domain into several intervals.
In this example, I chose the interval width as h = 0.01. The function value fval can be
1
calculated as ( FA0 ) . This can be conveniently done using the powerful vector opera-
R ( XA )
tions of MATLAB (see Appendix A for a primer). The function trapz uses the trapezoidal
rule (also see Appendix E) to compute the PFR volume. The result of 0.0798 m3 is close to
the approximate value of 0.07 m3 obtained in the previous section.

3.5.1.3 Comparison of ODE-IVP with Integration

The PFR example was intended to illustrate a couple of points regarding ODE-IVP and inte-
gration. When the function f(⋅) depends only on the independent variable, the two can be
said to be equivalent. However, the example above demonstrates the relationship between
the two very well.
First, when we asked the question: “what is the conversion achieved at a given length
(volume) of PFR,” I chose ODE-IVP. This was because ODE-IVP naturally tracks how the
dependent variable (CA or conversion) varies with PFR volume (or length). On the other
hand, when we asked the design question: “what volume (or length) is required to achieve
certain conversion,” I could use Figure 3.4 to obtain PFR volume that yielded 75% conversion.
dV 1
Alternatively, it was convenient to rearrange the ODE in the form of = ( FA0 )
dX A R ( XA ),
making the desired value of PFR volume as a target variable needed to achieve desired Xpfr.
1
The geometric interpretation of this design procedure becomes clear when ( FA0 )
R ( XA )
is plotted against XA in Figure 3.5. The PFR design volume is nothing but the area under
this curve. Note that in case of ODE-IVP, the evolution of solution XA vs. volume is plot-
1
ted; whereas in numerical integration, function value fval= ( FA0 ) is plotted vs. XA
R ( XA )
(Figure 3.5), with the volume given by the shaded area under the fval curve.

0.25

0.2

0.15
FA0/R(XA)

0.1

0.05

0
0 0.25 0.5 0.75
Conversion

FIGURE 3.5  Plot of fval vs. conversion required for design of a PFR volume.
 Ordinary Differential Equations   ◾    111

CA0, T0

Tj0

CA, T
Tj

FIGURE 3.6  Schematic of a jacketed CSTR.

3.5.2 Multiple Steady States: Nonisothermal CSTR

Another standard problem in chemical engineering is that of a continuous stirred tank
reactor (CSTR) with exothermic reaction. The heat generated on reaction is removed from
the system using a cooling jacket. The system is shown in Figure 3.6.

3.5.2.1 Model and Problem Setup

The overall model for the CSTR includes mass balance and energy balances for the reactor
and cooling jacket. The resulting model equations are given below:

dC A F
= ( C A0 - C A ) - rA
dt V
dT
V rc p = F rc p (T0 - T ) + ( -DH ) rAV - UA (T - Tj ) (3.95)
dt
dTj
Vj r j c j = Fj r j c j (Tj 0 - Tj ) + UA (T - Tj )
dt

æ E ö
with the reaction rate given by rA = k0 exp ç - ÷ C A. The values of various parameters are
given in Table 3.1. è RT ø
This problem is solved in the following example.

TABLE 3.1  Model Parameters and Operating Conditions for Jacketed CSTR
CSTR Inlet Cooling Jacket Other Parameters
F = 25 L/s Fj = 5 L/s CA0 = 4 mol/L
V = 250 L Vj = 40 L k0 = 800 s−1
ρ = 1000 kg/m3 ρj = 800 kg/m3 E/R = 4500 K
cp = 2500 J/kg · K cp = 5000 J/kg · K (−ΔH) = 250 kJ/mol
T0 = 350 K Tj0 = 25°C UA = 20 kW/K
112   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 3.12  Jacketed CSTR

Problem: Solve the transient nonlinear CSTR problem for inlet temperature 350 K.
Initially, at t = 0, the concentration within the CSTR is 0.1 mol/L, the CSTR tempera-
ture is 600 K and cooling jacket temperature is 500 K. Plot how the three variables
change with time.
Solution: In order to solve the above problem, the solution vector is defined as

éC A ù
ê ú
y=êT ú
ê Tj ú
ë û

The model equations are written in the standard form y′ = f(t, y), where both y and
dy are column vectors* of size 3 × 1. All the parameters need to be converted to SI
units.
The core part of the code consists of the following model description:

dy(1,1)=F/V*(C0-Ca)-rxnRate;
dy(2,1)=F/V*(T0-T)+DH*rxnRate/(rhoCp)-hXfer/(V*rhoCp);
dy(3,1)=Fj/Vj*(Tj0-Tj)+hXfer/(VRhoC_j);

Prior to this, the following terms need to be defined: rxnRate (rate of reaction),
hXfer (heat transfer term UA(T − Tj)), rhoCp (ρcp), and VRhoC_j (Vjρjcj). This
example continues after a brief interlude.
First, I will describe a “traditional” way of writing the MATLAB function that
is passed to the ode45 solver. In earlier versions of MATLAB, if one needed to
pass a large number of parameters (such as the parameters in Table 3.1), doing so
through function arguments was inconvenient and error-prone. Hence, the model
parameters required in a specific function were defined within the same func-
tion, whereas the parameters required in multiple functions were shared using
global variables. The function, cstrFunOld.m exemplifies this traditional
method.

function dy = cstrFunOld(t,y)
global C0 T0 Tj0
%% Parameters
F=25/1000; % m^3/s
V=0.25; % m^3
<other parameters also defined here>

* Keeping with the convention followed throughout this book, unless otherwise stated, all vectors are defined as n × 1 column
vectors.
 Ordinary Differential Equations   ◾    113

%% Key variables
Ca=y(1); T=y(2); Tj=y(3);
rxnRate=k0*exp(-E/T)*Ca;
hXfer=UA*(T-Tj);
rhoCp=rho*Cp;
VRhoC_j=Vj*rhoj*cj;
%% Model equations
dy(1,1)=F/V*(C0-Ca)-rxnRate;
dy(2,1)=F/V*(T0-T)+DH*rxnRate/(rhoCp)-hXfer/(V*rhoCp);
dy(3,1)=Fj/Vj*(Tj0-Tj)+hXfer/(VRhoC_j);

The above code maintains separation of parameter definition and model execution func-
tions: The main part of the code starts at the second section (demarcated by %% Key
variables), prior to which all the parameters are defined. The inlet conditions are
shared with the driver function using global variables. However, a few years ago (perhaps
around 2010), anonymous functions and structure arrays were introduced in MATLAB.
My experience working with cross-functional teams in the industry has led me to embrace
these as powerful tools for writing better MATLAB programs. I personally evangelize this
“modern” method of programming, as shown below.

3.5.2.2 Simulation of Transient CSTR

With their recent introduction in MATLAB, structure arrays form a more convenient
means to pass the model parameters to a function. The function argument variables have a
local scope within the function. This is a recommended programming practice followed in
all programming languages.
The core of the code remains nearly unchanged; the model parameters are now accessed
through structure fields. For example, calculation of reaction rate is modified as

rxnRate=par.k0 * exp(-par.E/T)*Ca;

Here, par is a structure that is passed to the function, cstrFun, as an argument. The
fields of the variable, par.k0 and par.E represent the preexponential factor and activa-
tion energy of the reaction, respectively. Similarly, the next line is rewritten as

hXfer=par.UA*(T-Tj);

The overall function file cstrFun.m is written as below:

Example 3.12  (Continued)

function dy = cstrFun(t,y,par)
%% Inlet and current conditions
C0=par.C0; T0=par.T0; Tj0=par.Tj0;
Ca=y(1); T=y(2); Tj=y(3);
114   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

%% Key Variables
rxnRate=par.k0 * exp(-par.E/T)*Ca;
hXfer=par.UA*(T-Tj);
rhoCp=par.rho*par.cp;
VRhoC_j=par.Vj*par.rhoj*par.cj;
tau=par.V/par.F; % Residence time
tauJ=par.Vj/par.Fj;
%% Model Equations
dy(1,1)=(C0-Ca)/tau-rxnRate;
dy(2,1)=(T0-T)/tau+par.DH*rxnRate/rhoCp-hXfer/(par.V*rhoCp);
dy(3,1)=(Tj0-Tj)/tauJ+hXfer/(VRhoC_j);

Comparing with the earlier code (cstrFunOld), the parameters are not defined
within the function. Instead, they will be defined in the driver script (cstrDriver.m)
and passed to the function through par structure. cstrDriver script is given
below:

% Simulation of a jacketed CSTR with

% exothermic first-order reaction
%% Define model parameters (SI units)
modelPar.F=25/1000; % CSTR parameters
modelPar.V=0.25;
modelPar.rho=1000;
modelPar.cp=2500;
modelPar.Fj=5/1000; % Cooling jacket
modelPar.Vj=40/1000;
modelPar.rhoj=800;
modelPar.cj=5000;
modelPar.k0=800; % Rate constants
modelPar.E=4500;
modelPar.DH=250000;
modelPar.UA=20000;
%% Define inlet and initial conditions
modelPar.C0=4000;
modelPar.T0=350;
modelPar.Tj0=298;
y0 = [100; 600; 500];
tSpan = [0 50];
%% Solving and plotting
[T,Y]=ode15s(@(t,y) cstrFun(t,y,modelPar),tSpan,y0);
subplot(2,1,1);
plot(T,Y(:,1));
xlabel('time (s)'); ylabel('C_A (mol/m^3)')
subplot(2,1,2);
plot(T,Y(:,2:3));
xlabel('time (s)'); ylabel('T, T_j (K)')
 Ordinary Differential Equations   ◾    115

1000

CA (mol/m3)
500

0
0 10 20 30 40 50
700

600
T, Tj (K)

500

400
0 10 20 30 40 50
Time (s)

FIGURE 3.7  Transient simulations of jacketed CSTR.

The transient simulation results are shown in Figure 3.7. This example illustrates
­simulation of a jacketed CSTR. At the end of 50 s, the three modeled variables have
the values, CA = 461.0, T = 647.6, Tj = 472.6.

3.5.2.3 Step Change in Inlet Temperature

At t = 50 s, the inlet temperature of the CSTR is changed to 298 K. The following example
shows the simulation of CSTR from 50 to 100 s.

Example 3.13  Step Change in Inlet Temperature

Problem: Starting with the conditions of Example 3.12 at the end of 50 s, simulate the
system with step change in T0 to 298 K.
Solution: After the last line of the previous code, the following is added:

%% Simulation for next 500s with step change in T0

tSpan=[50, 200];
y50=Y(end,:);
modelPar.T0=298;
[T2,Y2]=ode15s(@(t,y) cstrFun(t,y,modelPar),tSpan,y50);
subplot(2,1,1);
plot(T2,Y2(:,1));
ylabel('C_A (mol/m^3)')
subplot(2,1,2);
plot(T2,Y2(:,2:3));
xlabel('time (s)'); ylabel('T, T_j (K)')
116   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

4000

CA (mol/m3)
2000

0
50 100 150 200
800

600
T, Tj (K)

400

200
50 100 150 200
Time (s)

FIGURE 3.8  Transient CSTR response after T0 is reduced to 298 K.

Figure 3.8 shows the time evolution of the modeled variables for 150 s after step-
down in the inlet temperature. The outlet concentration increases and the tempera-
tures drop rapidly after the step change. The outlet concentration is now close to the
inlet concentration of 4 mol/L, and almost no reaction is taking place in the system.
At the end of 200 s, the values of the corresponding variables are CA = 3991, T = 298.8,
Tj = 298.4.

This example shows steady state multiplicity. When the inlet temperature was T0 = 350 K,
the system was in a steady state with high conversion. When the inlet temperature was
reduced to T0 = 298  K, the system transitioned to another steady state with low conver-
sion. This issue of steady state multiplicity will be discussed in more detail in Section II of
this book.

3.5.3 Hybrid System: Two-Tank with Heater

Consider the system consisting of two heated tanks in series, as shown in Figure 3.9.
The two tanks are connected with tubes at the bottom and at a certain height H. Electric
heaters are used to heat up the fluid in the tanks. This is an example of so-called hybrid
system, which consists of continuous variables as well as switching behavior. In this
example, there is a switching on/off of the flow in the intermediate connecting tube.
If the height of liquid in a tank is greater than H, then the fluid flows through this
­connecting tube. When the liquid levels are below H, fluids flow through the bottom
pipe only.
 Ordinary Differential Equations   ◾    117

F0

F1t

h1
H
h2

F1b F2

FIGURE 3.9  Schematic of two tanks in series.

The model for the system is given below:

d
A1 h1 = F0 - F1t - F1b
dt
d
A2 h2 = F1t + F1b - F2
dt
(3.96)
d F Q1
T1 = 0 (T0 - T1 ) +
dt A1h1 A1h1rc p
d Q2
T2 = ( F1t + F1b ) (T1 - T2 ) +
dt A2h2rc p

The first two equations are material balance on the two tanks. The last two equations come
from energy balance. These equations are obtained after rearranging the original energy bal-
ance equation, where the term on the left-hand side is A h rc T ¢ = rc A h × T ¢ + T × h¢ .
( i i p i ) p i ( i i i i )
The last term is simplified using the appropriate material balance to obtain the equations
given above.
The flowrates in the above equations are given by

F1b = c1 h1 - h2 , F2 = c2 h2 (3.97)

and

ì0 h1 £ H
ïï
F1t = íc1 h1 - H h1 > H , h2 £ H (3.98)
ï
ïîc1 h1 - h2 h2 > H

The parameters are as follows:

Areas of the tanks: A1 = A2 = 0.25 m3

Inlet conditions: F0 = 0.4 m3/min, T0 = 25°C
118   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Valve coefficients: c1 = c2 = 0.6 m2.5/min

Other conditions: ρcp = 1 cal/cm3, Q1 = Q2 = 100 kW
Height of intermediate pipe: H = 0.5 m

The condition for calculation of F1t can be handled in a couple of ways. One way is to use
if-then statements. Another, more elegant method is to note that first expression in
Equation 3.98 (i.e., when h1 ≤ H) can be written as F1t = c1 H - H :

ìc1 H - H h1 £ H
ïï
F1t = íc1 h1 - H h1 > H , h2 £ H (3.98)
ï
ïîc1 h1 - h2 h2 > H

When h2 > H, the second value inside the square root is h2; else it is H. Likewise, the first
value inside the square root is H when h1 ≤ H and equal to h1 otherwise. Thus, the above
equation may be written as

F1t = c1 h1 - h2 , hi = max ( hi , H ) (3.99)

The forthcoming example illustrates the use of this conditional statement to evaluate the
flowrate and hence solve the model of two-tank heater system. Unlike previous example
that used SI units, I will use minutes as the unit for time and KJ for energy for convenience.

Example 3.14  Hybrid Two-Tank Heater System

Problem: Solve the two-tank heater system described above. Initially, both the tanks
contain 100 liters of water at 25 °C.
Solution: First, all the quantities are converted to consistent units. Height will be in
meters and temperature in °C. The parameters requiring unit conversion are

rc p = 4180 kJ/kg, Q1 = Q2 = 100 kJ/s ´ 60 s/min = 6000 kJ/min

The computation of F1t will be done using Equation 3.99 as

del=max(H,h1)-max(H,h2);
F1t=par.c1*sqrt(del);

The first line defines del as the term within the square root, which is then used in
computing F1t in the next line. The MATLAB function heated2TankFun.m is

function dy=heated2TankFun(t,y,par)
% Model for hybrid two-tank system with heater
 Ordinary Differential Equations   ◾    119

%% Getting variables and computing terms

h1=y(1); h2=y(2); T1=y(3); T2=y(4);
% Flow rates
F1b=par.c1*sqrt(h1-h2);
F2=par.c2*sqrt(h2);
del=max(par.H,h1)-max(par.H,h2);
F1t=par.c1*sqrt(del);
% Heating rate
heater1=par.Q1/(par.A1*h1*par.rhoCp);
heater2=par.Q2/(par.A2*h2*par.rhoCp);
%% Model equations
dy=zeros(4,1);
dy(1)=(par.F0-F1b-F1t)/par.A1;
dy(2)=(F1b+F1t-F2)/par.A2;
dy(3)=par.F0/(par.A1*h1)*(par.T0-T1)+heater1;
dy(4)=(F1b+F1t)*(T1-T2)+heater2;

The corresponding driver script heated2TankDriver.m is given below:

% Drive script: heated2TankDriver.m

% Simulation of hybrid two-tank system with heater
%% Model parameters
modelPar.A1=0.25; modelPar.A2=0.25;
modelPar.F0=0.4; modelPar.T0=25;
modelPar.c1=0.6; modelPar.c2=0.6;
modelPar.Q1=6000; modelPar.Q2=6000;
modelPar.rhoCp=4180;
modelPar.H=0.5;
%% Initial conditions
h1init=0.4;
h2init=0.35;
y0=[h1init; h2init; 25; 25];
tSpan=[0 10];
%% Solving and plotting
[T,Y]=ode45(@(t,y) heated2TankFun(t,y,modelPar),...
tSpan, y0);
subplot(2,1,1);
plot(T,Y(:,1:2));
ylabel('height (m)')
subplot(2,1,2);
plot(T,Y(:,3:4));
xlabel('time (s)'); ylabel('T (deg C)')

The results are shown in Figure 3.10. Since the two liquid heights are fairly close to each
other initially, the net flow out of the second tank is greater than the flow in. Hence, the level
first falls, before increasing again.
120   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

0.6

Height (m)
0.4

0.2
0 5 10
80

60
T (°C)

40

20
0 5 10
Time (s)

FIGURE 3.10  Transient results in terms of height and temperature of water in the two tanks.

The next figure (Figure 3.11) shows the behavior of the system at higher flowrate of
0.48 m3/min. At this higher flowrate, water levels in both the tanks increase above the inter-
mediate pipe. Note that at steady state, F0 = (F1b + F1t) = F2 so that the volume of water in the
two tanks does not change.

3.5.4 Chemostat: Preview into “Stiff” System

A chemostat is a continuous stirred biological reactor, where a growth medium is con-
tinuously added to the reactor containing unconverted substrates, metabolic products,
and microorganisms. The inlet to the chemostat usually contains only the substrate(s); it
typically does not contain microorganisms. The microorganisms consume the substrate
to grow, and in the process, make useful products. Since the chemostat is essentially a
CSTR, the product stream from the reactor consists of the same components as the che-
mostat itself. The concentrations of all the important species: substrate(s), intermediates
(if any), metabolites and products, and biomass are modeled as a transient ODE system.
The growth rate of the microorganisms can often be complex. The simplest model that
captures the essential features of microorganism grown is given by Monod. The growth
rate is given by

æ éS ù ö
rg = ç m max ë û ÷ éë X ùû (3.100)
ç
è K S + éëS ùû ÷ø

 Ordinary Differential Equations   ◾    121

Height (m)
0.5

0
0 5 10
50

40
T (°C)

30

20
0 5 10
Time (s)

FIGURE 3.11  Transient results for a higher inlet flowrate of 480 L/min.

where [S] and [X] are substrate and biomass concentrations, respectively. The rate con-
stant μmax is the maximum growth rate and KS is the saturation constant. At large substrate
concentration, when [S] ≫ KS, the growth rate is zero-order in substrate concentration;
whereas when [S] falls substantially, the growth rate becomes first-order in substrate
concentration.
The model equations are given by the following ODEs:

dS
= D ( S f - S ) - rg
dt
dX
= -DX + rg Yxs (3.101)
dt
dP
= -DP + rg Yps
dt

The rate constants are given as μmax = 0.5, KS = 0.25, Yxs = 0.75, and Yps = 0.65.
The next example demonstrates simulation of chemostat.

Example 3.15  Chemostat: Bioreactor with Monod Kinetics Model

Problem: Solve the chemostat model given by Equation 3.101 for feed concentration
of Sf = 5 g/mL and dilution rate of D = 0.1 h−1. The chemostat initially has 5 g/mL of the
substrate, and inoculant is added to that initial [X] = 0.02 g/mL.
122   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Solution: This is a straightforward implementation in ode45, similar to the earlier

examples. The solution consists of the following driver script:

% driverMonod: Modeling a Chemostat with Monod kinetics

%% Reactor parameters
monodParam.mu=0.5;
monodParam.K=0.25;
monodParam.Yxs=0.75;
monodParam.Yps=0.65;
monodParam.Sf=5;
monodParam.D=0.1;
% Initial conditions
Y0=[5.0; 0.02; 0];
%% Solving and plotting
[tS,YS]=ode45(@(t,y) funMonod(t,y,monodParam),[0 30],Y0);
plot(tS,YS);

The second-last line uses ode45 to calculate the solutions tS and YS. The function,
funMonod, passed to the ODE solver is given below:

function dy=funMonod(t,y,monodParam)
mu=monodParam.mu; K=monodParam.K;
Yxs=monodParam.Yxs; Yps=monodParam.Yps;
D=monodParam.D; Sf=monodParam.Sf;
%% Variables to solve for
S=y(1); X=y(2); P=y(3);
%% Model equations
rg= mu*S/(K+S)*X;
dy(1,1)=D*(Sf-S) - rg;
dy(2,1)=-D*X + Yxs*rg;
dy(3,1)=-D*P + Yps*rg;
end

The solver takes more than a hundred steps to reach the solution. On MATLAB 2016a
version, tS is a 109-length vector, whereas the size of YS is 109 × 3. Figure 3.12 shows
the transient response of the chemostat for this problem.

This example also follows the same pattern as the previous ones. It is a good programming
practice to declare all the model parameters at one location. As the code grows more com-
plex for large projects, this way of modularizing the codes proves very useful. As a good
coding practice in the industry, we often went a step further. The parameters related to the
microbial growth kinetics would be located in one structure (say monodParam), which
include μmax, KS, Yxs, Yps. On the other hand, the chemostat operating parameters—that is, D
and Sf—would be included in another structure (say reactorParam). While this demar-
cation would be an “overkill” for this problem, it becomes useful in large projects where
modularity is a key.
 Ordinary Differential Equations   ◾    123

Concentrations
3

0
0 10 20 30
Time

FIGURE 3.12  Transient response of a chemostat.

For the parameter values of Example 3.15, the chemostat response is smooth. Initially, at
low biomass concentrations, the substrate concentration falls gradually. After around 10 h,
there is a significant reduction in substrate concentration as the higher biomass concentra-
tion results in faster consumption of the substrate. As substrate concentration falls, the
system behavior would transition from an initial zero-order response in [S] to eventually
first-order in [S]. Finally, the system reaches steady state.
Now consider the case when the saturation constant, KS, in Equation 3.100 is reduced to
a value of 0.005 g/mL. The fourth line in driverMonod.m is changed, and the code is run
again. For this value of saturation constant, the ode45 solver becomes unstable. The results
are shown in Figure 3.13. The initial “zero-order response” is similar to that seen earlier, in
Figure 3.12. However, when the substrate concentration drops, the reaction rate becomes
first-order in [S], resulting in a rapid decrease in reaction rate that the explicit ode45
solver is unable to capture. This instability of the explicit solver is not very different from the

100

50
Concentrations

–50

–100
0 10 20 30
Time

FIGURE 3.13  Transient chemostat response for KS = 0.005 g/mL using ode45. The solver becomes
unstable due to the stiff nature of the ODE.
124   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Concentrations
3

0
0 10 20 30
Time

FIGURE 3.14  Transient chemostat response for KS = 0.005 g/mL using ode15s. A stable solution is
obtained as ode15s is a stiff solver.

one discussed in Section 3.1.5, where the stability of Euler’s explicit and implicit methods
were compared.

STIFF SYSTEM
A stiff system refers to a system of ODEs where one or more components of the system have
a significantly different time scale of response compared to other components.

In the case of the chemostat, at low values of substrate concentration, the growth rate is
significantly lower when the reaction is first-order in [S] compared to the reaction rate
being independent of [S] (i.e., zero-order in [S]). The transition from zero- to first-order
happens when the substrate concentration is of the same order of magnitude as KS. When
the value of KS is very low, the system undergoes a very rapid reduction in the growth rate,
rg. Consequently, the rate at which substrate concentration decays falls precipitously. This
can be seen in Figure 3.14.
Figure 3.14 is obtained using ode15s, which is a stiff ODE solver provided in MATLAB.
The solver ode15s uses an implicit backward difference formula to solve the ODE. As can
be seen from this example, ode15s is the solver of choice if the system of ODEs is stiff, or
when ode45 does not work.
Comparing Figures 3.12 and 3.14, one can see that the former results in smoother curves
for [S], [X], and [P] than ode15s. This is because ode45 is a higher-order solver and is a
better solver that gives an excellent trade-off between accuracy and speed of computation.
As described in Section 3.4, it uses an embedded RK4 method. As a rule of thumb, which
is suggested by MATLAB and corroborated by experience of several expert users, ode45
should be the first solver of choice for a generic ODE problem. If the problem is stiff and
ode45 does not work, ode15s usually provides the next best option.
A further discussion on ode15s will be provided in Chapter 8 when discussing implicit
ODE solver and solution of DAEs. With this note, we end the discussion in this chapter.
 Ordinary Differential Equations   ◾    125

3.6 EPILOGUE
The problem of solving ODE-IVP was introduced in Section 3.1. Several types of example
problems can be solved as ODE-IVP. Higher-order ODEs can be converted to a set of first-
order ODEs, or the problem to solve may consist of multiple simultaneous ODEs. For ODE-
IVP, the initial conditions are specified at a single point in the solution domain. All the
components are written together as a solution vector, y. The strategies to obtain ODE-IVP
in the standard form

dy
= f ( t ,y )
dt (3.1)
y (t0 ) = y 0

were discussed briefly in Section 3.1.1 and case studies provided in Section 3.5.
Second-order ODE-IVP methods were discussed in Section 3.2. This chapter focuses
on explicit RK family of methods, which are discussed at length. The stability problems with
explicit RK methods were discussed, and Section 3.5.4 demonstrated the practical implica-
tions on a simulation problem. Section 3.2.5 provided a brief peek into some other important
ODE-IVP methods. These classes of methods are available in the ODE suite of MATLAB.
Section 3.3 extended the discussion to higher-order RK methods. Adaptive step-size
methods were then discussed. All the methods in MATLAB ODE suite are adaptive step-
size methods. These methods were referred to at various points in the chapter, most specifi-
cally in Sections 3.2.5 and 3.4.
The practical aspect of solving ODE-IVP in MATLAB is summarized now. For many
problems of interest to chemical engineers, explicit ODE-IVP methods will prove suffi-
cient. The MATLAB solver ode45 is the primary go-to solver for these cases. While other
explicit solvers (such as ode23 and ode115) are available, ode45 provides very high
accuracy at good computational speed.
There are several other ODE-IVP problems that are difficult to solve. Such stiff ODEs
will be discussed in Chapter 8. If ode45 fails to converge, the stiff solver ode15s would
be the next choice. This variable-order solver is typically less accurate and may not be used
as the first solver in MATLAB. The MATLAB help documentation is an excellent resource
on implementing an ODE solver. However, choosing which ODE solver is suitable requires
some understanding of how the ODE-IVP are solved, as discussed in this book.
If your problem requires you to use a different solver than ode45 and ode15s,
­reading Chapter 8 after this chapter will provide a better background to make an informed
choice.

EXERCISES
Problem 3.1 Solve Example 3.1 using RK-2 midpoint method from Equation 3.53 and
RK-2 Ralston’s method from Equation 3.54.
Problem 3.2 Use Richardson’s extrapolation for numerical integration.
126   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Problem 3.3 Use Richardson’s extrapolation for numerical differentiation.

Problem 3.4 Solve Example 3.3 using the classical RK-4 method from Section 3.3.3.
Problem 3.5 Solve the mass-spring-damper problem, mx″ =  − cx′ − kx, using ode45.
Choose appropriate values of c and k. The initial condition is that the system
is moved to a location x = 0.2 and released without any velocity x′(0) = 0. Plot
how location and velocity vary with time.
Problem 3.6 Repeat the above Problem 3.5 using your own RK-2 Heun’s method code.
For this purpose, you may write your own code from scratch or build upon
Heun’s code from Example 3.3.
Problem 3.7 Repeat the above problem using RK-3 and RK-4 methods.
 CHAPTER 4

Partial Differential
Equations in Time

4.1 GENERAL SETUP
Chapter 3 covered systems defined by ordinary differential equations, where the dependent
variable varied either in time or in a single spatial dimension. There are several examples
where the dependent variables vary in time and space or in multiple spatial dimensions.
Such models are represented by partial differential equations (PDEs). A general first-order
PDE in two independent variables is given by

æ ¶f ¶f ö
ç f, ¶x , ¶x , x1 , x2 ÷ = 0 (4.1)
è 1 2 ø

where
ϕ is the dependent variable
x1 and x2 are the two independent variables (e.g., x1 could be time t, and x2 could be axial
coordinate z; or x1 and x2 could be axial and radial coordinates z and r)

If the above function is nonlinear in the dependent variable or its derivatives, then the
overall PDE is nonlinear.
A generic second-order PDE contains one or more of the second-order terms, ¶ 2 f/¶x12,
¶ 2 f/¶x22, and/or ∂2ϕ/∂x1∂x2 as well.
We usually encounter either first-order or second-order PDEs in (chemical) engineer-
ing. Higher-order PDEs are not common. These PDEs are further of a specific type called
quasilinear PDEs. These may be written in general as

¶2f ¶2f ¶2f ¶f ¶f

A 2
+ B + C 2
+ D +E +F =0 (4.2)
¶x1 ¶x1¶x2 ¶x2 ¶x1 ¶x2

127
128   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The coefficients A to F may themselves be functions of x1, x2, and/or ϕ. It would be clear
from the description above that the PDE (4.2) is second-order PDE if one or more of A, B,
and C are nonzero. If A, B, and C are all zero, this is a first-order PDE. Thus, the order of PDE
is the highest order of differentiation of ϕ in the overall equation.
The above PDE needs to have initial or boundary conditions. The number of boundary
conditions required in a particular dimension depends on the order of the PDE in that
dimension. For example, if A is nonzero, two boundary conditions are required in x1; if A is
zero, then single initial condition is sufficient in x1.

4.1.1 Classification of PDEs
Homogeneous PDE: The PDE is said to be homogeneous if F = 0.
Linear vs. Nonlinear PDE: The above PDE is linear if A to E are all functions of indepen-
dent variables only, whereas F is a linear function of ϕ (i.e., F = F0 + F1ϕ). The coefficients A
to F1 should not depend on ϕ. For example, the PDE

¶f 2 ¶f
+t = sin ( t ) (4.3)
¶t ¶x

is linear, because the coefficient E = t2 and the source term F = sin(t) are not a function of the
dependent variable, ϕ. On the other hand

¶f ¶f
+ f = sin ( t ) (4.4)
¶t ¶x

is nonlinear, because the coefficient E = ϕ depends on the dependent variable, ϕ. Additionally,
the following PDE
2
¶f æ ¶f ö
+ = G ( t ,x ) (4.5)
¶t çè ¶x ÷ø

is also nonlinear. It should be noted that Equation 4.5 is a first-order PDE since the highest
order of differentiation with respect to t and x is first order. While Equations 4.3 and 4.4 are
quasilinear PDEs, Equation 4.5 is not.

4.1.2 Brief History of Second-Order PDEs

We are going to concern ourselves with PDEs of the type given in Equation 4.2 only, since
these are the most common types of PDEs in chemical engineering. Partial differentiation
was used in calculus even before PDEs were identified as key mathematical tools. Leibnitz
and l’Hospital used partial differentiation in the late seventeenth century. Following
Leonhard Euler’s formalization of “infinitesimal calculus,” the role of PDEs in describ-
ing physical laws for balance of mass, energy, momentum, etc., started getting discovered.
In 1752, d’Alembert introduced the 1D wave equation:

ftt = v 2 fxx
 Partial Differential Equations in Time   ◾    129

to model vibrating strings.* A decade later, Euler generalized this to 2D and 3D wave equa-
tion. The Laplace equation

Ñ2 f = fxx + f yy = 0

was introduced to model Newton’s gravitational potential. Siméon Poisson modified the
Laplace equation to model Gauss’s law for gravity in differential form. This equation is now
well known as the Poisson equation and is written in a general form as ∇2ϕ = ρ. Finally, in
1822, Fourier introduced the transient heat equation:

ft = kfxx

for modeling heat flow.

The wave equation, Laplace/Poisson equations, and heat equation are considered proto-
typical examples of three main types of PDEs of importance to engineers, namely, hyper-
bolic PDEs, elliptic PDEs, and parabolic PDEs, respectively. The next section discusses
classification of first- and second-order PDEs and their implication for numerical solutions.

4.1.3 Classification of Second-Order PDEs and Practical Implications

This classification of PDEs will prove important for the selection of appropriate numerical
techniques. The classification of PDEs as elliptic, hyperbolic, or parabolic is based on the
value of

D = B 2 - 4 AC (4.6)

The PDE is said to be elliptic if D < 0, hyperbolic if D > 0, and parabolic if D = 0. More impor-
tant than the definition is the physical significance of the terms. These terms are perhaps
motivated from the equivalence with corresponding curves in conics: ellipse, hyperbola, and
parabola. The implication of these characteristics for solving the PDEs is discussed here.

4.1.3.1 Elliptic PDE
Elliptic PDEs describe systems that have reached a steady state and where diffusion is a
dominant phenomenon (or at least where diffusion significantly affects the independent
variable). Just as ellipse is a smooth curve, elliptic PDEs describe dependent variables
that vary smoothly over space. If the conditions at the boundaries undergo an abrupt step
change, the diffusive terms will tend to smoothen out its effect in the domain. For example,
the following elliptic PDE describes temperature distribution at steady state with heat con-
duction as the dominant phenomenon:

0 = kÑ2T + S (T ) (4.7)

¶2f
*  Here I have used shorthand notation ϕtt to represent , and so on.
¶t 2
130   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

which for Cartesian coordinate in 2D is represented as

æ ¶ 2T ¶ 2T ö
0 = k ç 2 + 2 ÷ + S (T ) (4.8)
è ¶x ¶y ø

In the above equation, B = 0, A = C = k; thus D < 0 and the PDE is classified as elliptic. Thus,
an elliptic PDE in two dimensions has the diffusive term dominant in both the dimensions.
Since the differential equations are second order, two boundary conditions are needed in
both X- and Y-coordinates. For example, if Equation 4.8 governs temperature in a rectan-
gular plate, boundary conditions are specified for each of the four edges of the plate. The key
feature of elliptic PDEs is that the temperature at any point in the domain will be governed
by the conditions at all the four boundaries of the plate.
Elliptic PDEs will not be covered in this chapter. The reader may refer to Chapter 7 for
discussion on solving elliptic PDEs.

4.1.3.2 Hyperbolic PDE
Hyperbolic PDEs are used to describe propagation of waves or convection of material or
energy in transport problem. In conics, a hyperbola is an open curve with two disconnected
branches. By analogy, hyperbolic PDEs can be used to model those systems that are char-
acterized by propagation of an abrupt or step change at boundary along the domain; they
also model systems where this propagation or convection results in discontinuities, such as
in shock waves.
The 1D wave equation introduced earlier is an example of hyperbolic PDE widely stud-
ied in introductory engineering math courses:

ftt = v 2 fxx (4.9)

Writing this equation in standard form shows D > 0, classifying it as a hyperbolic PDE.
Let us introduce the following coordinate transformation:

x = x + vt , h = x - vt (4.10)

With this transformation, one can verify that Equation 4.9 reduces to

¶2f
=0 (4.11)
¶x¶h

and the solution to the wave equation is given by

f = f1 ( x ) + f 2 ( h) (4.12)

f ( x ,t ) = f1 ( x + vt ) + f 2 ( x - vt ) (4.13)
 Partial Differential Equations in Time   ◾    131

The curves x + vt = c1 and x − vt = c2 are called characteristic curves. What does this physi-
cally mean? Consider a curve x − vt = 1. The second term in Equation 4.13 becomes f2(1)
and thus is a constant. Thus, the value of f2 is constant along the second characteristic.
Likewise, the value of f1(⋅) is constant along the first characteristic.
The key behavior of a hyperbolic PDE relevant to numerical solution techniques is that
the information at the boundary is propagated along the two characteristic curves.
A similar quantitative response is observed in some types of first-order PDEs, as dis-
cussed next.

4.1.3.3 First-Order Hyperbolic PDEs

Let us consider another analysis of the 1D wave equation described above. Let us define two
new variables:

¶f ¶f
q= , y=v (4.14)
¶t ¶x

Clearly, one can see that taking partial differentiation ψt yields

¶y ¶q
=v (4.15)
¶t ¶x

Likewise, partial differential θt = ϕtt, which using Equation 4.9 can be written as

¶q ¶y
=v (4.16)
¶t ¶x

Thus, the wave equation (4.9) can be converted into the following matrix form:

¶ é q ù é0 vù ¶ é q ù
ê ú - ê ú ê ú =0 (4.17)
¶t ëy û ëv 0 û ¶x ëy û

This equation is in the form Φt − AΦx = 0. Using the concepts of eigenvalues discussed in
Chapter 2, it is easy to diagonalize the above equation. Noting that the eigenvalues of the
T T
above matrix are ±v and the eigenvectors are v 1 = é1/ 2 1/ 2 ù and v 2 = é -1/ 2 1/ 2 ù ,
ë û ë û
we can change to coordinate axes to ( v 1 v 2 ). Indeed, it is easy to do this coordinate trans-
formation. Recall from Chapter 2 that the physical interpretation of transforming to
( v1 v 2 ) implies that we define the following:
1 1
J= (q + y ), v= (q - y) (4.18)
2 2
132   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

It is easy to verify that Equations 4.15 and 4.16 get converted to the following decoupled set
of first-order PDEs:

¶J ¶J
-v =0 (4.19)
¶t ¶x

¶v ¶v
+v =0 (4.20)
¶t ¶x

The second-order PDE is converted into a set of two first-order ODEs. One would recog-
nize that the first term is the time derivative term, whereas the second is a convection term.
Thus, balance equations involving convection form a set of hyperbolic PDEs.
The curves (x + vt) and (x − vt) form the characteristic curves for PDEs (4.19) and (4.20),
respectively. The key numerical feature of hyperbolic PDEs is the convection or propagation
along the characteristics influences the solution at any point in the domain.

4.1.3.4 Parabolic PDE
Parabolic PDEs are used to solve initial value problems (IVPs) where the system is diffusion
dominated in one spatial dimension. Parabola is a smooth open curve, which represents
transition between an ellipse (closed smooth curve) and hyperbola (disconnected open
curves). In the same manner, a parabolic PDE is used to describe systems that propagate in
one direction, while the dependent variable has a smooth behavior due to a diffusive com-
ponent along the other dimension. A transient heat equation

¶T ¶ 2T
= a 2 + S (T ) (4.21)
¶t ¶z

is a prototypical example of parabolic PDE. This is an IVP in one dimension (t) and a
boundary value problem in the other dimension (z).
The key numerical feature of parabolic PDEs is the propagation of the solution along one
direction, whereas the solution at any point in the domain is influenced by both boundaries
in the other (z) direction.

4.1.4 Initial and Boundary Conditions

Initial conditions: They are most often specified in the form of the value of the variable ϕ
defined at a certain initial time for the entire domain in other independent variables.
In case of first-order hyperbolic PDE, one boundary condition is required for each of the
dependent variables, whereas two boundary conditions are required for parabolic PDEs.
There are three general types of boundary conditions as follows.

Dirichlet condition: The value of independent variable itself is specified at one boundary:

f ( t ,z = z 0 ) = f0 (4.22)
 Partial Differential Equations in Time   ◾    133

For example, temperature at one end or concentration entering a reactor may be specified.
Neumann condition: Here, the derivative of independent variable is specified at one
boundary:

¶f
=b (4.23)
¶z t , z1

For example, heat flux is zero at insulated boundary or the mass flux may be specified.
Mixed condition: Here, the boundary condition includes both the value of the variable
and its derivative at a boundary:

æ ¶f ö
g ç f ( t ,z1 ) , ÷÷ = 0 (4.24)
ç ¶z
è t , z1 ø
Danckwerts boundary condition is an example of mixed boundary condition. Another
example of mixed boundary condition is when the heat flux at boundary equals the rate
of heat exchange with the surroundings by convection. The mixed boundary condition
often reduces to the form

¶f
k
¶z t , z1
(
= g f ( t ,z1 ) ) (4.25)

4.2 A BRIEF OVERVIEW OF NUMERICAL METHODS

Various methods have been developed for solving PDEs. This section provides a brief over-
view of some important classes of methods. The methods discussed here are only indicative;
this is not intended to be a comprehensive or accurate review of numerical PDE-solving
techniques. I will use the example of a plug flow reactor (PFR) to motivate the idea.

4.2.1 Finite Difference
The first class of methods for solving PDEs is finite difference techniques. The domain is
divided into multiple intervals. The differentiation formulae (see Appendix B) are used to
approximate numerical derivatives. Thus, the spatial derivative at any location, i, is written
using backward difference formula as

¶C C - Ci -1
u = ui i
¶z i h

or using the central difference formula as

¶C C - Ci -1
u = ui i +1
¶z i 2h
134   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The solutions are obtained at the individual discrete points in the domain. In a transient
PFR, the concentration will also vary with time. The time derivative may be written as

¶C C p,i - C p -1,i
=
¶t Dt

giving rise to implicit methods.

Explicit in time finite difference method is obtained if the time derivative is written as

¶C C p +1,i - C p,i
=
¶t Dt

4.2.2 Method of Lines
Method of lines (MoL) is like that method described above, except that finite difference is
used only for the spatial domain. The finite difference in space

¶C C - Ci -1 ¶C C - Ci -1
= ui i , or u = ui i +1
¶z i h ¶z i 2h

converts the original PDE into a set of ODEs. The solution vector then consists of the prob-
lem variable at discrete points in the spatial domain:
T
f = éëC1 C2  Cn+1 ùû

and the ODEs are written in the standard for ϕ′ = f(ϕ). These may then be solved using
ODE solution techniques mentioned in Chapter 3.

The finite difference and MoL techniques will be discussed in detail in this book. This chap-
ter will use MoL to solve parabolic and hyperbolic PDEs by converting them into a set of
ODEs. Hence, the title of this chapter indicates the solution of transient PDEs.

4.2.3 Finite Volume Methods

Finite volume methods (FVM) are a different class of PDE solution techniques. Instead of
discretizing the domain into various intervals and writing the differential equation in terms
of variables at the nodes, the domain is discretized in finite volumes. The original equation
is written in the so-called conservative form. Each finite volume behaves as a physical mate-
rial volume in the domain, with the balance equation applicable to the volume.
The PFR also consists of multiple finite volumes in series. The flux term was derived after
letting the finite volume shrink to δz → 0 as

¶ ( uC )out - ( uC )in
¶z
( uC ) = lim
dz
dz ®0
 Partial Differential Equations in Time   ◾    135

The idea of FVM is to model instead the finite volume itself; the flux terms give inlet and
outlet from the boundaries of the volume and the transient and reaction source terms per-
tain to the reacting material in the volume itself.
Thus, in principle, FVM applied to a PFR may be considered as multiple CSTRs in series.
FVM are commonly used in computational fluid dynamics (CFD) software. FVM will not
be discussed further in the rest of this book.

4.2.4 Finite Element Methods

Finite element methods (FEM) use a slightly different approach for approximating the solu-
tion after discretizing the domain. Instead of expressing the differential term as a finite
difference or solving the equation over a finite volume, the solution is expressed as a com-
bination of basis functions:

C = å ci yi

where
ψi denote basis functions
ci denote the coefficients

One of the common methods to choose the basis functions is that the functions ψi have
value 1 at the ith node and zero at all other nodes. The solution C is the linear combination
of the basis functions over the entire domain. Once the basis functions are chosen and dis-
cretization is fixed, solution of a PDE using FEM mainly involves finding the coefficients ci.
FEM became popular in solid mechanics. However, applications of FEM have now been
found in a wide variety of problems. FEM continue to be popular in solid mechanics and
structural problems; they are also finding growing use in multiphysics problems where vari-
ous types of physics are involved in solving a single problem.
Again, FEM are beyond the scope of this book. It is also mentioned briefly to contrast it
with our method of choice: finite difference in space.

4.3 HYPERBOLIC PDE: CONVECTIVE SYSTEMS

Hyperbolic PDEs are most commonly encountered in chemical engineering for transient
simulations of convective systems. The conservation equations are of the form

¶f ¶
+ ff = S ( f) (4.26)
¶t ¶x

The above equation is first-order hyperbolic PDE when the term fϕ is the convective flux.
The convective or advective component is given by

f f = uf (4.27)

where u is the velocity. For example, in continuity equation, which is an overall mass bal-
ance, ϕ = ρ, the average density and S ( f ) = 0 (except for nuclear reactions). Furthermore,
136   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

for the sake of initial discussion, we will assume that u is constant. Thus, we are initially
interested in hyperbolic PDEs of the type

¶f ¶f
+u = S ( f) (4.28)
¶t ¶x

At a later stage, we will relax this condition and allow u to vary.

The example that we will use in this discussion is that of a PFR. Species conservation
equation for a PFR involves conservation of moles or mass of a species. In case of the for-
mer, ϕ = CA where CA is the concentration of reacting species, A. The source term S captures
creation or disappearance of the species due to reaction. Thus, the species balance for a PFR
yields the following (set of) first-order hyperbolic PDEs:

¶C A ¶
+ ( uC A ) = rA ( C ) (4.29)
¶t ¶x

In several cases, the velocity u is constant* (or nearly constant). In such cases, the PFR is
governed by the following PDE:
¶C A ¶C
+ u A = rA ( C ) (4.30)
¶t ¶x

We will now discuss various numerical methods for solving hyperbolic PDE (4.28).

4.3.1 Finite Differences in Space and Time†

The simplest procedure to solve a first-order hyperbolic PDE is to use finite difference in
time and space. Let us choose Δt as the step-size in the t-direction and Δx as the step-size
in the x-direction. The spatial domain is of a finite length L so that the number of spatial
divisions is n = L/Δx. The discretization procedure will convert the PDE into a set of alge-
braic equations or expressions, which will be used to march forward in time. As described
in Chapter 2, we may use either explicit or implicit method in time for marching forward.

4.3.1.1 Upwind Difference in Space

An explicit O ( Dt ) finite difference in time is the simplest choice for discretizing the PDE.
We start with initial conditions at t = 0 and march forward in time. We are nominally free to
choose the finite difference scheme in space. Let us choose first-order backward difference
formula for discretizing in space. The convective term is then written as

é ¶f ù f p,i - f p,i -1
ê ¶x ú = Dx
(4.31)
ë û p ,i

*  This is true for liquid-phase reactions and isothermal gas-phase reactions. The velocity changes in nonisothermal gas-phase
reactions, and/or in gas-phase reactions with significant change in the number of moles due to reaction.
†  The methods discussed in this section are useful for understanding some numerical basis behind finite difference techniques

for solving hyperbolic PDEs. A reader interested in numerical methods may continue reading this section, whereas a reader
interested in process simulation may skip this section without loss of continuity.
 Partial Differential Equations in Time   ◾    137

where p is the time index such that t = pΔt and i is the spatial index such that x = iΔx. The
source term is calculated at time pΔt and location iΔx and is represented as Sp,i  S ( pDt ,iD x ).
( )
Forward difference in time yields the following O D1t accurate approximation:

¶f f p +1,i - f p,i
= (4.32)
¶t Dt

Substituting in Equation 4.28, the difference equation is given by

uD t
f p +1,i = f p,i - éf p,i - f p,i -1 ùû + Dt Sp,i (4.33)
Dx ë
which is an explicit expression to calculate ϕp+1, i and march forward in time.
The local stability of the above equation can be analyzed using the so-called von Neumann
stability analysis. It is local because it ignores the effect of boundary conditions and is
derived for homogeneous equation (i.e., without the source term). The derivation of stabil-
ity conditions is relatively straightforward, but will be skipped since it is beyond the scope
of this book. The backward difference formula is stable if velocity u is positive and the fol-
lowing Courant condition is satisfied:

Dt
u £1 (4.34)
Dx

When the flow is from right to left, that is, when the velocity is negative, backward differ-
ence formula is unstable and the forward difference formula should be used.
Thus, the upwind difference formula is given by
ì uD t
ïïf p,i - D éëf p,i - f p,i -1 ùû + Dt Sp,i , if u > 0
x
f p +1,i =í (4.35)
u
ï f p ,i - tD
éëf p,i +1 - f p,i ùû + Dt Sp,i , if u < 0
ïî Dx

Figure 4.1 shows the stencil of dependence for the upwind difference scheme. The square
represents the point (p + 1, i) in the T–X space where the solution needs to be found. The
solid line and arrow connect points used to compute the spatial and temporal derivatives,
respectively. The filled circles denote points where the values are known. The stencil is
shown for all methods discussed in this section.
Let us consider the physical interpretation of the Courant condition. When u > 0, the mate-
rial flows from left to right. The conditions at any spatial location are therefore influenced
by the node that is upstream of itself. Thus, using a backward difference formula retains this
physical condition that ϕi is influenced by preceding nodes ϕi − 1. Same can be observed for
opposite flow direction also. Furthermore, the Courant condition can be written as

Dx
u£
Dt
138   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

FTCS (hyperbolic) FTCS (parabolic)

t t

Δt
Z Z
Δz
Upwind Crank-Nicolson

t t

Z Z

FIGURE 4.1  Schematic diagram of various finite difference schemes. Thin lines represent the com-
puting grid, with the thin dashed line indicating points in the future. Solid circles are known points
at current time and empty diamonds represent unknown points to be calculated. The thick solid
lines link points connected by finite difference in space; arrows link points connected by finite dif-
ference in time.

Since u is the physical speed of propagation, the numerical rate unum = Δx/Δt should be
greater than the speed u to stably capture the effects of convection. Thus, the spatial differ-
encing should maintain direction of information propagation and the grid in time domain
(i.e., Δt) should be brought closer than the rate at which information convects.
The forward in time, first-order upwind differencing method discussed here is not accu-
rate enough to be useful for practical examples. The discussion here, however, will serve as
a useful reminder for future analysis.

4.3.1.2 Forward in Time Central in Space (FTCS) Differencing

The accuracy of the numerical technique may be improved using a central difference for-
mula for the spatial derivative:

é ¶f ù f p,i +1 - f p,i -1
ê ¶x ú = 2D x
(4.36)
ë û p ,i

Substituting this in Equation 4.28 yields the following formula:

uD t
f p +1,i = f p,i - éf p,i +1 - f p,i -1 ùû + Dt Sp,i (4.37)
2D x ë
 Partial Differential Equations in Time   ◾    139

The above is an explicit relation. Unfortunately, the FTCS method is unstable for any choice
of Δt. The proof can be arrived at using the von Neumann stability analysis. This implies that
any error in the numerical solution of ϕp,i will grow unbounded and the FTCS method may
not be used for first-order hyperbolic PDEs.

4.3.1.3 Lax-Friedrichs Scheme
Lax and Friedrichs proposed a simple way to make the FTCS method stable. They replaced
the term ϕp,i on the right-hand side of Equation 4.37 with an average of the values at its
neighboring nodes: ϕp,i → (ϕp,i +1 + ϕp,i −1)/2. Thus, the updated equation using Lax-Friedrichs
method is

f p +1,i =
1
2
( f p,i +1 + f p,i -1 ) - 2uDDt éëf p,i +1 - f p,i -1 ùû + Dt Sp,i (4.38)
x

The von Neumann stability analysis results in the same Courant stability condition:

Dt
u £1 (4.34)
Dx

Let us analyze Lax-Friedrichs scheme further by rearranging Equation 4.38 as

f p +1,i - f p,i =
1
2
( f p,i +1 - 2f p,i + f p,i -1 ) - 2uDDt éëf p,i +1 - f p,i -1 ùû + Dt Sp,i (4.39)
x

Dividing by Δt

f p +1,i - f p,i D 2x ( f p,i +1 - 2f p,i + f p,i -1 ) uDt

= - éf p,i +1 - f p,i -1 ùû + Sp,i (4.40)
Dt 2D t D 2x 2D x ë

Clearly, the first term above is an additional term, which is a finite difference approximation of

D 2x ( f p,i +1 - 2f p,i + f p,i -1 ) D 2x é ¶2f ù

º ê 2ú (4.41)
2D t D 2x 2D t ë ¶x û p,i

Thus, Lax-Friedrichs scheme makes the FTCS method stable by introducing a numerical
diffusion term, described in Equation 4.41.

4.3.1.4 Higher-Order Methods
Accuracy in time can be improved using higher-order differencing in time.
The leapfrogging method uses central difference formula to approximate the time derivative
as well. Recall that the central difference formula is f¢p = ( f p +1 - f p -1 ) /Dt . The update equation
can be derived in a straightforward manner and is left as an exercise. The leapfrogging method
140   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

is stable for a range of Δt values given by the Courant condition. However, the problem is that
the time derivative does not include values at time instance p. Thus, the alternate mesh points
are decoupled, due to which the errors at even- and odd-numbered nodes evolve indepen-
dently of each other. Consequently, this method often does not give acceptable results.
Lax-Wendroff method, which is a combination of Lax-Friedrichs and leapfrogging meth-
( )
ods, is another alternative that is O Dt2 accurate in time. It uses the Lax-Friedrichs scheme
with a half step to determine values ϕp + 0.5 , i ± 0.5. These two values are then used in leapfrog-
ging method, which is again implemented with half-steps. Consequently, this is a two-step
explicit formula. While the method is good in theory, it faces several issues when handling
stiff systems or systems with highly nonlinear source term, S ( f ).
Higher-order upwind method: While the above two methods provided higher-order dif-
ferencing in time, it sometimes also becomes necessary to use higher-order differencing in
space. For example, three-point upwind difference equation can be used to improve spatial
accuracy of upwind method. This will be considered in Section 4.3.3 for “method of lines.”
The derivation of forward-in-time three-point upwind method is also left as an exercise.
In summary, I have discussed several methods for using finite differences in time and
space. I have personally found explicit-in-time finite differences inadequate (poor accuracy
and stability). Crank-Nicolson (Section 4.3.2) and MoL (Section 4.3.3) are my preferred
numerical methods for solving practical problems involving PDEs.

4.3.2 Crank-Nicolson: Second-Order Implicit Method

Chapter 3 discussed implicit and explicit methods for solving ODEs, where it was shown
that implicit (Euler’s) method is globally stable. The same principle works for hyperbolic
PDEs as well. Using finite difference in time, Equation 4.28 is written as

f p +1,i - f p,i é ¶f ù
= -u ê ú + S ( f p +1,i ) (4.42)
Dt ë ¶x û p +1,i

Note that both ∂ϕ/∂x and S ( f ) are computed at time location (p + 1). A central difference
formula may be used for ∂ϕ/∂x and the first-order fully implicit formula may be derived.
The derivation is left as an exercise.
The above first-order implicit method is not very useful due to its low accuracy. Crank and
Nicolson, in the 1940s, derived a second-order implicit formula. Although they derived it for
a general parabolic PDE, it is applicable to hyperbolic PDEs as well. The time differencing is
based on the trapezoidal rule (see Appendix D for numerical integration and Chapter 8 for
ODEs). The idea is similar to the one discussed with Heun’s method in Chapter 3: A higher-
order accurate method is obtained by taking the average of function values at t = pΔt and
t = (p + 1)Δt. Specifically, the right-hand side of Equation 4.42 is replaced by an average at the
two points. This results in the following implicit formula for Crank-Nicolson method:

f p +1,i - f p,i u æ é ¶f ù é ¶f ù ö 1
= - çê ú +ê ú ÷ + ( Sp,i + Sp +1,i ) (4.43)
Dt 2 çè ë ¶x û p,i ë ¶x û p +1,i ÷ø 2

 Partial Differential Equations in Time   ◾    141

f p +1,i - f p,i u æ f p,i +1 - f p,i -1 f p +1,i +1 - f p +1,i -1 ö 1

+ ç + ÷ - ( Sp,i + Sp +1,i ) = 0 (4.44)
Dt 2è 2D x 2D x ø 2

The above is a nonlinear equation, which is written for each spatial location, 1 ≤ i ≤ n. All
the quantities at time-coordinate p are known and the quantities at p+1 are to be computed.
The above is a set of nonlinear equations. I have not yet discussed methods for solving non-
linear equations. Hence, I will defer numerical solution of Crank-Nicolson method until
later.

4.3.2.1 Preview of Numerical Solution

Equation 4.44 does not represent a single equation, but rather a set of nonlinear equations
for all spatial locations at the next time, (p + 1). We define a vector of solution variables

T
F p +1 = ëéf p +1,1 f p +1,2  f p +1,n ùû (4.45)

with the convention followed in this book of using column vectors. The above set of equa-
tions (4.44) is written in standard vector form as

G ( F p+1 ) = 0 (4.46)

where G is a vector of functions, with Equation 4.44 representing the ith row. Various meth-
ods for nonlinear algebraic equations are discussed in Chapter 6. An example demonstrating
the use of Crank-Nicolson method is deferred to Chapter 8 in Section II of this book.

4.3.3 Solution Using Method of Lines

Since the spatial domain is finite, the discretization in space discussed in Sections 4.3.1 and
4.3.2 are of sufficient accuracy. In the previous chapter, methods for solving transient ODEs
with high accuracy were discussed. MoL combines spatial discretization with higher-order
transient ODE solvers to solve transient PDEs. The core idea behind MoL is to convert the
PDE into a set of ODE-IVP by discretizing in space.
As discussed in Section 4.3.1, the spatial domain is discretized* in n intervals, with
h = L/n. If the central difference formula is used in space, the PDE (4.28) get converted to a
set of n coupled ODE-IVP:

dfi f -f
= -u i +1 i -1 + S ( fi ) (4.47)
dt 2D x

*  I use h to represent step-size in discretization. In the previous section, since discretization in both space and time was dis-
cussed, I had used Δx instead. I have used the symbols h and Δx replaceably to represent step-size. The notations will be clear
from the context they are used.
142   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Here, we have only retained index for space and dropped the time-index since the equation
is now converted to an ODE in time. If we define the vector

T
F = éëf1 f2  fn ùû (4.45)

then we will get a set of n ODE-IVP in the standard form. As before, we are not limited to
central difference in space; any appropriate finite difference approximation (see Appendix B
for details on numerical differentiation) may be used as well.
In the remainder of this section, we will use the example of an isothermal PFR to com-
pare central difference, first-order upwind and second-order upwind methods.

4.3.3.1 MoL with Central Difference in Space

The transient mass balance on a PFR results in a first-order hyperbolic PDE. The PFR model
with a first-order irreversible reaction without volume change is

¶C A ¶C
+ u A = -kC A
¶t ¶z

C A ( t = 0 ) = C A0, C A ( t ,z = 0 ) = C A,in (4.48)

The numerical solution of the PDE needs to be benchmarked with a known solution. For
this, we use the steady state model for the PFR:

dC A k
= - CA (4.49)
dz u

which can be solved analytically to obtain

æ kz ö
C A = C A,in exp ç - ÷ (4.50)
è u ø

The numerical solution will involve discretizing Equation 4.48 in space, followed by solv-
ing the resulting system of ODEs using an appropriate ODE solver (such as ode45 or
ode15s). The next example shows the use of central difference formula in space for the
PFR example.

Example 4.1  Transient PFR Using Central Difference in Space

Problem: Solve the species material balance for a PFR described by the PDE (4.48)
using MoL. The inlet velocity is u = 0.4 m/min, k = 0.2 min−1, length of the PFR is
0.5 m, and inlet concentration is 1 mol/L. Assume the initial concentration in the PFR
is same as 1 mol/L as well.
 Partial Differential Equations in Time   ◾    143

Solution: Equation 4.48 is discretized in n equal intervals. Since inlet conditions are
specified, we do not need to solve for the inlet node using an ODE solver. Hence, for
the sake of convenience, the inlet node is denoted as “0,” the internal nodes go from
1 to (n − 1), and the end node is denoted as nth node. The equations for the internal
nodes after discretization are

d C - Ci -1
Ci = -ui i +i - kCi , i = 2 to ( n - 1)
dt 2h (4.51)
d C - Cin
Ci = -ui i +i - kCi , i = 1
dt 2h

Since this is an IVP in spatial domain as well, boundary condition is not specified at
the end node. The domain equation itself is used at the end node, such as by using a
backward difference formula:

d C - Ci -1
Ci = -ui i - kCi , i =n (4.52)
dt h

The vector of dependent variables that is to be solved for in the ODE solver is

T
Y = ëéC1 C2  Cn ùû

Function file for ODE solver: The first step is to write the function file,
pfrMOLLinFun.m. As described in the Chapter 3, this function takes time and Y as
input arguments are returns dY/dt as the output, with variables Y and dY being n × 1
column vectors. The core of this code involves the calculation of reaction term (r) and
convection term (convec):

r = k*Y(i); is calculated for all values of i

convec=u0/(2*h)*(Y(i+1)-Y(i-1)); for i = 2 to (n–1)
convec=u0/h*(Y(i+1)-C0); for i = 1
convec=u0/h*(Y(i)-Y(i-1)); for i = n

In the above, h=L/n. The function also requires the following variables to be defined:

k, u0, C0, L, n

I have followed a consistent and modular style of coding, wherein all the parameters
related to reactor operation are defined once in the main driver script and passed on
as function arguments. Recall that the function information is provided to the solver
ode45 using the following anonymous function definition:

@(t,Y) pfrMOLLinFun(t,Y,modelParam)
144   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

where the parameters mentioned above are provided to the function using
­modelParam structure.
The complete function file pfrMOLLinFun.m is given below:

function dY=pfrMOLLinFun(t,Y,par)
% Function file for transient PFR problem
% to be solved using method of lines
%% Get the parameters
k=par.k;
C0=par.C0;
u=par.u0;
L=par.L;
n=par.n;
h=L/n;
%% Model equations
dY=zeros(n,1);
for i=1:n
r=k*Y(i);
if i==1
convec=u/(2*h) * (Y(i+1)-C0);
elseif (i==n)
convec=u/h * (Y(i)-Y(i-1));
else
convec=u/(2*h) * (Y(i+1)-Y(i-1));
end
dY(i)=-convec-r;
end

Driver script to solve the problem: As described in Chapter 1, the driver script con-
sists of three parts: defining problem parameters (the list was given above), solving
the ODE, and result output. The ODEs will be solved using ode45 in MATLAB®,
with the prescribed initial conditions. For results, the final steady state profile of CA
vs. z is plotted as figure(1) and the transients in outlet concentration plotted as
figure(2).

% Driver script for simulating transient PFR

% using Method of Lines (central difference)
%% Model Parameters
modelParam.k=0.2;
modelParam.u0=0.4; u0=modelParam.u0;
modelParam.C0=1; C0=modelParam.C0;
modelParam.L=0.5;
%% Initializing and simulating the PFR
n=100;
modelParam.n=n;
h=modelParam.L/n;
 Partial Differential Equations in Time   ◾    145

Y0=ones(n,1)*C0;
[T,CA]=ode45(@(t,Y) pfrMOLLinFun(t,Y,modelParam), ...
[0 10],Y0);

%% Plotting results
% Steady state plot
C_ss=[C0, CA(end,:)]; % Results: steady state
Z=[0:h:h*n]; % Location
CModel=C0*exp(-modelParam.k*Z/u0);
figure(1)
plot(Z,C_ss,'-',Z,CModel,'.');
xlabel('Length (m)'); ylabel('C_A (mol/L)');
% Exit concentration vs. time
figure(2);
plot(T,CA(:,end));
xlabel('time (min)'); ylabel('C_A (mol/m^3)');

The results at steady state are plotted in Figure 4.2. Symbols represent the analytical
solution for comparison, whereas the solid line represents the numerical solution.
There is clearly instability observed in the numerical solution. The numerical solution
oscillates around the true solution.

This example demonstrates the unsuitability of central difference formula in MoL solu-
tion with explicit transient ODE solver for convection-dominated systems.

4.3.3.2 MoL with Upwind Difference in Space

In Section 4.2.1, the central and upwind differencing schemes were compared. Since ode45
is a variable-step fourth-order explicit ODE solver, those actual stability results do not apply,
though the observed trend is still applicable. Analogously in MoL, upwind differencing in

0.95
CA (mol/L)

0.9

0.85

0.8

0.75
0 0.1 0.2 0.3 0.4 0.5
Length (m)

FIGURE 4.2  Numerical results with MoL employing central differences in space (solid line)
­compared with true solution at steady state (symbols).
146   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

space will provide better stability behavior when coupled with ode45. When the flow is in
the positive z-direction, upwind implies a backward difference formula. Thus

d C - Ci -1
Ci = -ui i - kCi , "i with C0 ¬ C A,in (4.53)
dt h

( )
The two-point backward difference formula is only O h1 accurate, but is easy to imple-
ment. If a greater accuracy is desired, a higher-order formula is needed for special discreti-
zation to improve accuracy. A three-point backward difference formula

d 3C - 4Ci -1 + Ci -2
Ci = -ui i - kCi , i = 2 to n with C0 ¬ C A,in (4.54)
dt 2h

( )
can be used, with an O h2 accuracy.
The most convenient option for the first internal node (i = 1) is to use a standard two-
point backward difference formula:

d C - C A,in
Ci = -ui i - kCi , i = 1 (4.55)
dt h

While this is simple to use and does not adversely affect the stability of upwind method, its
disadvantage is that it is only O ( h ) accurate. Since the leading error is governed by the least
accurate method, using a two-point formula makes the overall scheme less accurate.

NOTE ON SECOND-ORDER UPWIND

My personal experience with higher-order upwind differencing has been significantly more
positive than what the naïve view of theory would suggest. The statement made above, that
the overall accuracy of numerical method is governed by the worst-case error, is indeed cor-
rect. However, the error and stability analyses we performed were local. While Equation 4.55
( )
indeed is O h1 accurate, the boundary condition CA , in is assumed to be known exactly with-
out any error. On the other hand, all the terms on the right-hand side of Equation 4.54 may
have numerical errors.
Consequently, in my experience, the performance of MoL employing three-point upwind
formula (4.54) for internal nodes combined with the two-point formula (4.55) at the first
node has been excellent for a large fraction of practical simulation problems.

The next example presents MoL with upwind differencing in space, for the conditions
in Example 4.1. First, the standard two-point backward difference formula will be
used. A  comparison between central difference (Example 4.1) and upwind difference
(Example 4.2) will demonstrate the suitability of the latter for hyperbolic PDEs. Thereafter,
the PFR problem will be solved for a greater residence time (i.e., with lower inlet velocity)
to compare the two- and three-point upwind differences.
 Partial Differential Equations in Time   ◾    147

Example 4.2  Transient PFR with Backward Difference in Space

Problem: Solve Example 4.1 using upwind difference for spatial discretization.
Solution: The problem will be solved in two parts. First, let us compare two-point
upwind with central difference in space.
Two-point formula: The driver script remains the same as Example 4.1. In the PFR
function, the first section remains the same; only the second section (named “Model
Equations”) is modified as below:

%% Model equations
dY=zeros(n,1);
for i=1:n
r=k*Y(i);
if i==1
convec=u/h*(Y(i)-C0);
else
convec=u/h*(Y(i)-Y(i-1));
end
dY(i)=-convec-r;
end

The rest of the code remains the same. The simulations are run for a time span that
is long enough for the system to reach steady state. The concentration CA (obtained
at the last time instance) is plotted against spatial location. Figure 4.3 shows that the
numerical technique is stable and the numerical solution closely matches the true
solution at steady state.
Comparison with three-point formula: The two-point upwind method gives good
performance for the conditions above. The conversion from the PFR is less than 25%.
Conversion can be increased by increasing the residence time (increase the length or
decrease the inlet velocity). The operating condition for the PFR is changed to inlet

0.95
CA (mol/L)

0.9

0.85

0.8

0.75
0 0.1 0.2 0.3 0.4 0.5
Length (m)

FIGURE 4.3  MoL with backward differences in space (solid line) compared with true solution at
steady state (symbols). The line may not be clearly visible since the symbols overlap closely.
148   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

0.8

CA (mol/L)
0.6

0.4

0.2

0
0 0.1 0.2 0.3 0.4 0.5
Length (m)

FIGURE 4.4  Comparison of two-point (solid line) and three-point (dashed line) backward differ-
ence formula solutions at steady state.

velocity of u0 = 0.05 and the number of axial nodes is reduced to n=25. The simula-
tion time span is increased to [0, 25], which is long enough to reach steady state.
Steady state results are plotted in Figure 4.4 as a solid line. Clearly, the numerical solu-
tion differs from the analytical one by ~2%–3%.
The accuracy can be improved by using the three-point upwind method. The code
for three-point upwind method is left as an exercise. The dashed line in Figure 4.4
shows that the three-point upwind difference is more accurate, as can be expected
( )
from the fact that it is O h2 accurate. Transient evolution of the concentration at the
PFR exit is plotted in Figure 4.5 as solid (two-point upwind) and dashed (three-point
upwind) lines. The two methods show some difference as we approach steady state.
Based on comparison with steady state solution in Figure 4.4, the three-point results
are more accurate.

0.8
CA (mol/m3)

0.6

0.4

0.2

0
0 5 10 15 20 25
Time (min)

FIGURE 4.5  Comparison of transient results for two- and three-point backward difference formulae.
 Partial Differential Equations in Time   ◾    149

4.3.4 Numerical Diffusion
Another key issue in the finite difference methods is the so-called numerical diffusion. This
was discussed for the Lax-Friedrichs scheme, where the modification to improve stability
of central difference was shown to be equivalent to introducing diffusion. The reality is that
numerical diffusion is introduced by all the finite difference methods.
I will demonstrate this using the following example of a tracer injection. Let us consider
the flow of material through a pipe. In the absence of axial diffusion (i.e., for an ideal plug
flow), any packet of fluid spends its residence time τ = L/u within the pipe. Initially, pure
water flows through the pipe (initial condition is C(0) = 0). At certain time, t = 0+, a dye is
injected into the inlet at an inlet concentration of 1 mol/L. The flow of this tracer through
the pipe can be modeled as a plug flow system with no reaction:

¶C ¶C
+u = 0, C ( t ,z = 0 ) = Cin , C ( t = 0 ) = 0 (4.56)
¶t ¶z

Let the inlet velocity be 0.1 m/min and the PFR length as 0.5 m. Based on the physics of the
system, we expect that at 1 min after the start of injection, the tracer (at 1 mol/min) to cover
the first 0.1 m, whereas the remainder contains “original” dye-free fluid packets that have
not yet been pushed out of the PFR. This tracer moves as a step through the PFR as time
progresses until t = 0.5/0.1 min, after which the entire PFR contains water with dye.
The above problem can be solved using the code from Example 4.2, with k=0. Simulation
results obtained using upwind method with a very large number of nodes, n=10000, is
shown by solid lines in Figure 4.6. This is close to the true solution. The dotted lines rep-
resent n=1000, whereas dashed lines represent the original number of nodes n=100. All
these cases do not show perfectly vertical lines. Clearly, we observe that the tracer has “dif-
fused” into adjoining packets, leading to a smooth transition from 1 to 0 mol/L. The amount
of diffusion is negligible with n=10000 (solid lines), the effect is obvious with n=1000

0.8
5 min
CA (mol/L)

0.6
1 min

2 min

3 min

4 min

0.4

0.2

0
0 0.1 0.2 0.3 0.4 0.5
Length (m)

FIGURE 4.6  Simulation of tracer injected in a pipe at various times using 10,000 nodes (solid line),
100 nodes (dashed lines), and 1,000 nodes (dotted lines).
150   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

(dotted lines) and prominent with n=100 (dashed lines). The cause of this observed behav-
ior is numerical diffusion.
Consider the upwind difference in space. Although we wrote f¢i = ( fi - fi -1 ) /h, we have
neglected the higher-order terms. In fact, the approximation using Taylor’s series is

¶C A h 2 ¶ 2C A h 3 ¶ 3C A
C A,(i -1) = C A,i - h + - + (4.57)
¶z i 2 ! ¶z 2 i 3 ! ¶z 3 i

Therefore

C A,i - C A,(i -1) ¶C A h ¶ 2C A h2 ¶ 3C A

= - + - (4.58)
h ¶z i 2 ¶z 2 i 6 ¶z 3 i

Substituting in the upwind difference–based MoL from Equation 4.53

d é ¶C h ¶ 2C A h 2 ¶ 3C A ù
Ci = -ui ê A - 2
+ 3
- ú (4.59)

dt êë ¶z i 2 ¶z i 6 ¶z i úû

The leading error in the higher-order terms is

h ¶ 2C A
ui (4.60)
2 ¶z 2
xÎéëi -1,i ùû

This is indeed the numerical diffusion, with the diffusion coefficient

Dnumerical = 0.5h ui (4.61)

The numerical diffusion decreases with decreasing step-size, h, as was evident in Figure 4.6.
The reaction source term in transient PFR predominates and masks the effects of numeri-
cal diffusion. This is also true for the majority of problems of interest to chemical engineers.
Thus, first- or second-order upwind methods are sufficiently accurate with reasonable step-
size, h. However, in some problems involving tracking of a moving front, high resolution
numerical methods must be used. Such problems are not considered in this book and a
discussion of high-resolution hyperbolic PDE methods is beyond the scope of this text.

4.4 PARABOLIC PDE: DIFFUSIVE SYSTEMS

Parabolic PDEs result most often when simulating processes with diffusive component in
one direction. Common examples of such systems include transient heat conduction in a
solid body, problems involving axial convection and radial diffusion, transient reactor with
axial diffusion, etc. The discussion in the preceding section can be extended to transient
 Partial Differential Equations in Time   ◾    151

equations with diffusion in spatial dimension. Numerically, diffusion introduces second-

order differential in space, resulting in parabolic PDEs. Transient diffusion (or conduction)
equations

¶f ¶ æ ¶f ö
= D + S ( f) (4.62)
¶t ¶z èç ¶z ÷ø

or transient convection-diffusion problems

¶f ¶ ¶ æ ¶f ö
+ ( uf ) = ç D ÷ + S ( f ) (4.63)
¶t ¶z ¶z è ¶z ø

represent general model forms for parabolic PDEs.

The velocity u and the coefficient D may be constant, leading to quasilinear parabolic PDE:

¶f ¶f ¶2f
+u = D 2 + S ( f) (4.64)
¶t ¶z ¶z

Packed-bed reactor with axial mixing: The PFR model of the previous section assumed fluid
elements to move as “plugs” and axial back-mixing was ignored. A packed bed reactor with
axial mixing will be used as an example of parabolic PDE in this section:

¶C A ¶C ¶ 2C A
+ u A = De - kC A (4.65)
¶t ¶z ¶z 2

The initial condition remains the same as in the previous (PFR) case:

C A ( t = 0,z ) = C0 (4.66)

Two boundary conditions are required. The inlet boundary condition may be concentration
specified at the inlet, whereas a no-flux condition may be used at the outlet:

¶C A
C A ( t ,z = 0 ) = Cin , =0 (4.67)
¶z t ,z =L

The above two represent Dirichlet and Neumann boundary conditions, respectively.
The previous example was solved in dimensional quantities. For this example, let us use
a nondimensional formulation. Let us define variable ϕ = CA/Cin as the dimensionless con-
centration and ζ = z/L as the dimensionless length. Using the residence time as the key time
scale in the reactor, we define τ = t/(L/u). This yields

u ¶f uCin ¶f De Cin ¶ 2 f
Cin + = 2 - kCin f (4.68)
L ¶t L ¶z L ¶z 2
152   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Rearranging
¶f ¶f 1 ¶ 2 f
+ = - Da × f
¶t ¶z Pe ¶z 2
uL kL (4.69)
where Pe = , Da =
De u

are Péclet and Damköhler numbers, respectively. Péclet number is the ratio of convective to
diffusive transport rates and the Damköhler number* is the ratio of reaction to convective
transport rates. The higher the Péclet number, the greater is the contribution of the convec-
tive transport compared to axial diffusion. The reaction time scale for an nth order reaction is
r (CA )
trxn = = knC An-1 (4.70)
CA
In summary, Equation 4.69 is the parabolic PDE of interest:
¶f ¶f 1 ¶ 2 f
+ = - Da × f (4.69)
¶t ¶z Pe ¶z 2
subject to initial and boundary conditions

f ( t = 0,z ) = f0 (4.71)

¶f
éëf ùû z =0 = 1, =0 (4.72)
¶x z =1

The next subsections discuss numerical methods to solve parabolic PDEs.

A SIDENOTE ON TREATMENT IN THIS SECTION

Most books on numerical techniques provide a detailed treatment of parabolic PDEs of the
form of Equation 4.62, where the convective term is neglected. The general convective-
diffusive equation (4.64) is often treated separately, if at all. The presence of convective term
affects the nature of solution, and hence the choice of numerical scheme. However, follow-
ing the discussion in Section 4.3, we are equipped to handle the general equation (4.64).
I will therefore present a unified treatment in this section, so that the techniques discussed
herein are equally applicable to the transient diffusive PDE (4.62).

4.4.1 Finite Difference in Space and Time

The forward in time and central in space (FTCS) method can be used to discretize PDE
(4.64). Although the FTCS method was unstable for hyperbolic PDEs, the presence
of the diffusive term, Dfzz , makes the FTCS method stable for parabolic PDEs. Recall
that the Lax-Friedrichs method stabilized FTCS for hyperbolic PDEs by introducing a

*  More precisely, this is known as Damköhler number of the first kind, DaI. The Damköhler number of the second kind is the
ratio of reaction to transverse mass transport rates. Mass transfer in this example is axial mass transfer.
 Partial Differential Equations in Time   ◾    153

numerical diffusion term. The presence of a physical diffusion in parabolic PDE makes
the original FTCS method conditionally stable.
As before, let us choose Δt as the step-size in the t-direction, Δz as the step-size in the
z-direction, and n = L/Δz as the number of spatial divisions. The central difference formula
for the diffusive term is
é ¶2f ù f p,i +1 - 2f p,i + f p,i -1
ê 2ú = (4.73)
ë ¶z û p,i D 2z

The forward difference in time and central difference for convective term remain the same
as before. Substituting the finite differences in Equation 4.64 and rearranging yields the
FTCS update:
uD t DD
f p +1,i = f p,i - éëf p,i +1 - f p,i -1 ùû + 2 t éëf p,i +1 - 2f p,i + f p,i -1 ùû + Dt Sp,i (4.74)
2D z Dz

Comparing the above equation with Equation 4.37, we see that the diffusive term is additional.
DD
The diffusive term, 2 t éëf p,i +1 - 2f p,i + f p,i -1 ùû, makes the FTCS stable for parabolic PDEs.
Dz
The condition for stability of FTCS is
DDt 1 u 2 Dt
< , <1 (4.75)
D 2x 2 2D

The first condition implies Δt should be chosen such that the grid is sufficient to capture
the physical diffusive effects governed by the coefficient D. The second condition ensures
that the diffusive component at the local grid is dominant over the convective component.
Note that for a purely diffusive system, the second condition is trivially satisfied since u = 0.
Leapfrogging and Lax-Wendroff methods, which are both O Dt2 accurate, can be adapted ( )
for parabolic PDEs as well. They follow the same principles as elaborated before.

4.4.2 Crank-Nicolson Method
The implicit Crank-Nicolson method, described in Section 4.3.2, is applicable for para-
bolic PDEs as well. Crank-Nicolson method is unconditionally stable* for both hyperbolic
and parabolic PDEs. In other words, there is no limit on the step-size Δt to ensure stability.
The reader can verify that the Crank-Nicolson method for Equation 4.64 is
f p +1,i - f p,i u æ f p,i +1 - f p,i -1 f p +1,i +1 - f p +1,i -1 ö 1
+ ç + ÷ - ( Sp,i + Sp +1,i )
Dt 2è 2D x 2D x ø 2
D æ f p,i +1 - 2f p,i + f p,i -1 f p +1,i +1 - 2f p +1,i + f p +1,i -1 ö
- ç + ÷=0 (4.76)
2è D 2x D 2x ø

*  It should be noted that these stability conditions are derived with constant source term. In practice, the stability conditions
may be violated due to strongly nonlinear source terms. Also, these conditions are derived locally, implying that the effect of
( )
boundary conditions or strongly varying coefficients u or D is not covered in these derivations.
154   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The above is a nonlinear equation, which is written for each spatial location, 1 ≤ i ≤ n. The
quantities at time p + 1 should be computed simultaneously using an appropriate nonlin-
ear equation solver. Chapters 6 and 7 will discuss techniques that will equip us to solve
Equation 4.76 and the solution will be discussed in Chapter 8.

4.4.3 Method of Lines Using MATLAB® ODE Solvers

PDF (4.64) is discretized in the spatial domain using central difference formula and solved
using MoL. This works like the method discussed in Section 4.3.3, with an added benefit
that due to the axial diffusion term, the central difference is likely to be stable. I will dem-
onstrate this method using the reactor with axial mixing, modeled in Equation 4.69, with
initial conditions, (4.71) and boundary conditions, (4.72).

4.4.3.1 MoL with Central Difference in Space

As before, the solution vector is defined as
T
Y = ëéf1 f2  fn ùû (4.77)

and the step-size, h = L/n. The discretized equations for the internal nodes (i = 2 to n–1) are

d f -f f - 2fi + fi -1
fi = - i +1 i -1 + i +1 - Da i × fi (4.78)
dt 2h Pei h2

The nondimensional inlet boundary condition yields the equation for the first node (i = 1):

d f - 1 f - 2fi + 1
fi = - i +1 + i +1 - Dai × fi , i = 1 (4.79)
dt 2h Pei h2

Neumann or mixed boundary conditions can be handled in a couple of ways:

1. Use backward difference formula for the boundary node, n.

2. Use the so-called ghost-point method. This will be our method of choice.

The above domain equation for the end node (i = n) introduces a variable at a new point,
ϕn + 1. This point is not within the domain that is being solved, but can be eliminated using
the exit boundary condition. The Neumann boundary condition at exit yields

¶fn fn+1 - fn-1

= =0 (4.80)
¶z 2h

Substituting the value of ϕn + 1 into the equation above, the following ODE is obtained for i = n:

d -2fi + 2fi -1
fi = - Da i × fi , i = n (4.81)
dt Pei h2
 Partial Differential Equations in Time   ◾    155

As an example, we will modify the PFR conditions from Example 4.1. The residence
time is tres = 10 and Damköhler number is Da = 2. Considering the effective diffusivity,
De = 5 ´ 10-3 m2/min, which is at the higher end of the spectrum, for small molecules, the
value of Pe = 1. For this condition, the model at steady state is

d 2 f ¶f
- - 2f = 0 (4.82)
dx2 ¶x

Noting that the roots of the equation

(D 2
)
-D -2 f = 0

(4.83)

are (2, −1), the steady state solution for the system can be obtained as

e 2x + 2e 3-x
f= (4.84)
1 + 2e 3

The next example shows a numerical solution of the axial dispersion model using MoL for
these conditions.

Example 4.3  Reactor with Axial Dispersion

Problem: Obtain transient solutions for a reactor with axial dispersion for Da = 2, Pe = 1,
and residence time of 10 minutes.
Solution: The solution follows on similar lines as the PFR problem, except that
being a parabolic PDE, central difference formula can be comfortably used. The func-
tion file is given below:

function dY=axialDiffLinFun(t,Y,par)
% Function for transient reactor w/ axial mixing
% to be solved using method of lines
%% Get the parameters
n=par.n;
Pe=par.Pe;
Da=par.Da;
%% Model equations
h=1/n;
dY=zeros(n,1);
for i=1:n
r=Da*Y(i);
if i==1
convec=(Y(i+1)-1)/(2*h);
diffu =(Y(i+1)-2*Y(i)+1)/(Pe*h^2);
156   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

elseif (i==n)
convec=0;
diffu =(-2*Y(i)+2*Y(i-1))/(Pe*h^2);
else
convec=(Y(i+1)-Y(i-1))/(2*h);
diffu =(Y(i+1)-2*Y(i)+Y(i-1))/(Pe*h^2);
end
dY(i)=-convec+diffu-r;
end

The driver script is like the ones we have used before, and hence will be skipped for
brevity. The steady state analytical solution is computed as

CModel=(exp(2*Z)+2*exp(3-Z))/(1+2*exp(3));

and plotted as symbols for comparison. The numerical solution at various times
(τ = [0.02,   0.1,   0.2], which corresponds to 0.2, 1, and 2 min) is plotted in Figure 4.7.
The dashed line is the steady state numerical solution and the symbols are the analyti-
cal solution. Clearly, the numerical solution closely matches the analytical solution at
steady state, even with n=25 axial nodes.

As we did in the previous section, we can run the simulations with initial concentration as
ϕ = 0 and no reaction condition of Da = 0. This will simulate tracer experiment, where a dye
is injected in a reactor and its fate is tracked. Two different conditions are simulated, when
Pe = 5 (solid lines) and when Pe = 50 (dashed lines). For a system that is convection dominant,
Pe → ∞. As axial mixing increases, D increases and, consequently, Péclet number decreases.
Thus, the former case (Pe = 5) is further away from the PFR than the latter (Pe = 50).
Figure 4.8 shows the transient evolution of step tracer in a reactor with axial diffusion.
Although at steady state, both cases show uniform concentration of ϕ(ξ) = 1, the transients

1
τ = 0.02
0.9
τ = 0.1
Concentration, φ

0.8
τ = 0.2
0.7

0.6 S.S.

0.5
0 0.5 1
Distance, ξ

FIGURE 4.7  Concentration profile within a packed bed reactor with axial dispersion and first-order
reaction at various times. Symbols represent analytical solution at steady state.
 Partial Differential Equations in Time   ◾    157

1
Dash: Pe = 50
0.8

Concentration, φ
Solid:
0.6
Pe = 5

0.4

0.2

0
0 0.5 1
Distance, ξ

FIGURE 4.8  Simulation of tracer injected in a reactor with axial dispersion at various times. Solid
lines represent Pe = 5, and dashed lines represent Pe = 50.

are significantly different. For a larger Pe value, we see a diffuse tracer front traveling in the
reactor, whereas the tracer is highly diffused at the lower Pe value.

4.4.4 Methods to Improve Stability

The method of choice discussed in this chapter for parabolic PDEs is the MoL with central
difference in spatial domain. The resulting set of ODEs can be solved using MATLAB’s
ode45 solver. This provides a good trade-off between ease of implementation, stability,
and accuracy. If the problem is stiff, the implicit solver ode15s may be used instead.
Likewise, MoL using ode45 may be too slow, in which case again ode15s may be used
instead.
In some problems, the velocity may vary significantly with time and/or space. Sometimes,
the above methods do not provide stable results for such problems. Recall that the stabil-
ity condition for explicit methods require us to discretize such that the diffusive term is
dominant compared to the convective terms. If this condition is not met, a solution using
standard MoL may show unstable behavior (similar to oscillations in Figure 4.2 or instabil-
ity observed in Chapter 3). In such a case, one may resort to a mixture of central difference
formula for diffusive term and upwind difference for convective term.
If these methods fail, as is possible in some highly stiff problems, fully implicit methods
may be attempted. The Crank-Nicolson method, usually, provides a good starting point
for such cases. If all else fails, specialized solvers available at online repositories may be
used. Unfortunately, for such cases, it may be pragmatic to use alternative languages such as
FORTRAN or C++, where well-tested numerical libraries are available.

4.5 CASE STUDIES AND EXAMPLES

4.5.1 Nonisothermal Plug Flow Reactor
First, a recap of isothermal PFR with first-order reaction was considered in Example 4.2.
The model for the PFR was given by Equation 4.30. The PDE was converted into a set of
ODEs using MoL. Since this was a hyperbolic PDE, the convective term was approximated
using upwind differencing.
158   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

In this case study, we will build upon the isothermal PFR model to consider a noniso-
thermal liquid-phase PFR with complex reaction kinetics. The velocity may be assumed
constant for the liquid-phase system. The PFR material balance remains the same as before:

¶C A ¶C
+ u A = rA ( C A ) (4.30)
¶t ¶z

The reaction rate is given by

kC A
rA = -
K r + CA
(4.85)
æ E ö æ DE ö
k = k0 exp ç - ÷ , K r = K 0 exp ç - r ÷
è RT ø è RT ø

The transient energy balance for the PFR is given by

¶T ¶T ( -DH r ) r
+u = (4.86)
¶t ¶z rc p

The model for nonisothermal PFR consists of two hyperbolic PDEs, (4.30) and (4.86),
subject to Dirichlet boundary condition at the inlet (inlet concentration is specified). The
initial conditions will be assumed to be the same as at the inlet. The parameters are given
in Example 4.4 itself.
Now, we are solving for two variables, CA and T. The above two PDEs are discretized
using the upwind method. The spatial domain is discretized into n intervals and the two
variables are specified at each of the nodes. The variable to be solved for will therefore be

é C A1 ù
ê ú
ê T1 ú
êC A2 ú
ê ú
T2 ú
F = êê
 ú
ê ú
ê  ú
êC ú
ê An ú
ëê Tn úû

Note the arrangement of variables in the column vector Φ. We first list out both the vari-
ables at node-1, followed by both variables at node-2, and so on. The above structure of Φ is
a personal preference, due to convenience of this organization of the dependent variables.
Note that when Equations 4.30 and 4.86 are discretized, the concentration and temperature
depend on the values at the same ith node and the values at its neighboring nodes. Thus,
I find the above structuring more convenient to use.
 Partial Differential Equations in Time   ◾    159

MATLAB provides a useful command reshape, to reshape matrices. It is convenient to

convert the above matrix into the following form using reshape command:

éC A1 C A2  C An ù
F=ê ú (4.87)
ë T1 T2  Tn û

The MATLAB command to do this is

YBar=reshape(Y,2,n);

The individual columns of Y are reshaped into a 2 × n matrix. Reshape can also be used to
convert the above matrix back into the original form:

Y=reshape(YBar,2*n,1);

One needs to be careful in using this command. The elements in the first column are “read”
in a sequence, followed by the second column, and so on.
The transient adiabatic PFR problem is solved in the example below.

Example 4.4  Nonisothermal PFR

Problem: Consider a liquid-phase reaction takes place in a nonisothermal PFR. The
model equations are given by Equations 4.30 and 4.86. Temperature and concentra-
tion at the inlet are 450 K and 1 mol/m3, respectively.
The reaction rate is given by Equation 4.85. The activation energy is E = 60 kJ/mol
and ΔEr =  − 10 kJ/mol. The rate constants are specified at the temperature T1 = 450 K
as k1 = 2 and Kr,1 = 1. The values at any temperature T are given by

é E æ 1 1 öù é DE æ 1 1 öù
k = k1 exp ê - ç - ÷ ú , K r = K r1 exp ê - r ç T - T ÷ú
ë R è T T1 ø û ë R è 1 øû

The heat of reaction is (–ΔH) = 100 kJ/mol and fluid density and the specific heat
capacity is ρcp = 800 J/mol K.
Solve the PFR problem for L = 2 m and u0 = 0.4 m/min.
Solution: I will reuse the function file from Example 4.2 as a starting point.

Reaction rate calculation: As a first step, we will make the function more modu-
1.
lar by using a separate function to calculate the reaction rate. Since reaction rate
is dependent on only the local temperature and concentration, the function to
calculate the reaction rate is given below:

function r=rxnRate(T,C,par)
% Function computes local rate of reaction
160   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

% given temperature and concentration

Rgas=par.Rgas; % Gas constant
% Rate constants
k1=par.k1;
E=par.E;
T1=par.T1;
K1=par.K1;
DEr=par.DEr;
k =k1*exp(-E/Rgas*(1/T-1/T1));
Kr=K1*exp(-DEr/Rgas*(1/T-1/T1));
% Compute the reaction rate
r=k*C/sqrt(1+Kr*C^2);
end

The advantage of a modular function is that the overall PFR solver can be reused
for a variety of different conditions. For example, if simulating a PFR for a dif-
ferent process, the core of PFR solver does not change; only the reaction rate and
process parameters change. The former is captured in the reaction rate function,
whereas the latter are provided in the driver script.
Function for PFR balances: Next, let us write the function for PFR balance equa-
2.
tions. The function arguments will be time t and solution vector Y. First step is
to extract concentration and temperature from Y. Indeed, this can be done by
using CA=Y(1:2:end); and T=Y(2:2:end);.
However, I will show a more convenient and flexible way to do so using
reshape:

YBar=reshape(Y,2,n);
CA=YBar(1,:);
T=YBar(end,:);

Again, there is nothing special or different about using reshape. It is a per-

sonal choice based on my experience. For example, if the system contained nsp
species (instead of a single species), the second line will change to

CA=YBar(1:nsp,:);

At this stage, I should mention that using the colon-index notations is also easy,
but I find reshape method more elegant.
The discretized equation will contain two terms: the discretized convective
term and the reaction term. We will use upwind method for the former, while
the latter is computed by invoking the function rxnRate that we created ear-
lier. This is computed for each of the n nodes in a for loop. This forms the
 Partial Differential Equations in Time   ◾    161

core “%% Model Equations” section of the function file, where we will
compute both dC and dT. The vector dY will be extracted from these two using
reshape again.
The function file is given below:
function dY=pfrAdiabfun(t,Y,par)
% Function file for transient adiabatic PFR
% solved using method of lines
%% Get the parameters
n=par.n; % Number of nodes
L=par.L;
h=L/n;
u=par.u0; % Velocity remains constant
C0=par.Cin; % Inlet concentration
T0=par.Tin; % Inlet temperature
rCp=par.rCp;
DH=par.DH;
%% Variables
Y=reshape(Y,2,n);
CA=Y(1,:);
T=Y(2,:);
dC=zeros(n,1);
dT=zeros(n,1);
%% Model equations
for i=1:n
% Reaction rate
r=rxnRate(T(i),CA(i),par);
% Convection term
if i==1
convecC=u/h*(CA(i)-C0);
convecT=u/h*(T(i)-T0);
else
convecC=u/h*(CA(i)-CA(i-1));
convecT=u/h*(T(i)-T(i-1));
end

% Model equations
dC(i)=-convecC-r;
dT(i)=-convecT+(-DH)*r/rCp;
end
%% Return dY as vector
dY=reshape([dC’;dT’],2*n,1);

Recall the caution I had expressed in using reshape. Note the structure of
matrix F from Equation 4.87: The first row contains concentration and the
162   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

second row contains temperature. Since dC and dT were defined as column

vectors,* the form of matrix F can be obtained using matrix F.
This completes our description of the adiabatic PFR function file.
Driver script: As before, the driver script is in three sections: parameter defini-
3.
tion, problem solving, and postprocessing for displaying the results. The script
is given below. First, the PFR parameters are defined and stored in model-
Param structure. The solution is initialized with uniform conditions CA0 and
T0 in the PFR. Note the use of reshape to convert from Φ ↔ [CA; T]. Transient
and steady state results are plotted in the final section:
% Driver script for simulation of a PFR
% with single reaction & complex kinetics
%% Model Parameters
modelParam.k1=0.2;
modelParam.K1=1;
modelParam.T1=450;
modelParam.E=60*1000;
modelParam.DEr=-10*1000;
modelParam.DH=-100*1000;
modelParam.rCp=800;
modelParam.Rgas=8.314;
% Reactor conditions
modelParam.L=2;
modelParam.u0=0.4;
modelParam.Cin=1;
modelParam.Tin=450;
%% Simulating the PFR
n=100;
modelParam.n=n;
Y0=[ones(1,n)*modelParam.Cin;
ones(1,n)*modelParam.Tin];
Y0=reshape(Y0,2*n,1);
[tSol,Ysol]=ode15s(@(t,Y) pfrAdiabFun(t,Y,modelParam), ...
[0:0.1:10],Y0);

%% Displaying results
% Extract values for plotting
CA=Ysol(:,1:2:end);
T=Ysol(:,2:2:end);
XA=(modelParam.Cin-CA)/modelParam.Cin;
h=modelParam.L/n;
Z=[0:n]*h;

*  In fact, in this example, it may even be more convenient to define dC and dT as row vectors. However, I have found that
beginners often find it confusing when different conventions are used for different examples. Hence, it is more for the
pedagogical reason that I have stuck to the convention of defining vectors as column vectors, except when there is a good
reason to do otherwise.
 Partial Differential Equations in Time   ◾    163

% Steady state conversion vs. location

figure(1); plot(Z,XA(end,:));
xlabel('Location (m)'); ylabel('Conversion');
% Plot outlet C and T vs. time
figure(2); plot(tSol,CA(:,end));
xlabel('Time (min)'); ylabel('Outlet C_A (mol/m^3)');
figure(3); plot(tSol,T(:,end));
xlabel('Time (min)'); ylabel('Outlet T (K)');
% Plot profiles at various times
figure(4);
subplot(2,1,1); plot(Z,T([101,6,11,16,21],:));
ylabel('Temperature');
subplot(2,1,2); plot(Z,CA([101,6,11,16,21],:));
xlabel('Location (m)');
ylabel('C_A (mol/m^3)');

The results are shown in Figures 4.9 and 4.10, which will be discussed presently.

Grid independence study is an important step that must be performed to ensure that the
numerical procedure gives an acceptable solution. In examples until this point, we had the
analytical solution to compare. However, the PFR model in this example cannot be solved
analytically. As we have seen multiple times before, decreasing the step-size improves the
accuracy. Grid independence study verifies the adequacy of the chosen grid by comparing
the results with two different grid sizes. A rule of thumb that we employ is that the solution
is taken as grid-independent if halving the step-size (i.e., doubling the number of nodes)
causes no further change in the solution. Figure 4.9 shows an example of grid-independence
study. For this example, we may consider the solutions from n = 100 to be grid independent
(thick line in the figure), because doubling the number of nodes to 200 did not cause a sig-
nificant change in the axial profile of conversion at steady state.
Figure 4.10 shows the temporal evolution of concentration and temperature in the PFR.
Initially, the temperature and concentration are uniform. As reaction takes place, eventually

0.8
Conversion

0.6

0.4 n = 100
n = 200
0.2 n = 50
n = 25
0
0 0.5 1 1.5 2
Location (m)

FIGURE 4.9  Conversion vs. axial location at steady state for different spatial discretization.
164   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

600

550

Temperature
500

450
(b)
1
CA (mol/m3)

0.5

0
0 0.5 1 1.5 2
(a) Location (m)

FIGURE 4.10  Temperature (a) and axial profiles of concentration (b) at various times from start
(0.5, 1.0, 1.5, 2 min, and steady state). The arrow marks increasing time, t.

the steady state is reached. The arrow shows increasing time. As time progresses, the con-
version and temperature both increase smoothly to reach the steady state value.

4.5.2 Packed Bed Reactor with Multiple Reactions

Let us now consider an example of a packed bed reactor with multiple species and reac-
tions. Unlike the example in Section 4.4, a dimensional form of the equation will be used
in this example. To keep things simple, a constant fluid velocity is assumed. This assump-
tion is valid for liquid-phase systems and highly dilute gas-phase systems (e.g., catalyst for
exhaust emissions control). For a general gas-phase system, this assumption is not valid.
Example of a gas-phase system (with varying velocity) will be considered in a case study in
Section 9.5.3. The following reactions take place in the reactor:

A ® P + Q, 0.05C A
(4.88)
A ® P + R, 0.005C ACP

There are five species in the system: A, P, Q, R, and inerts. The model for a packed bed
reactor is given by

¶Ck ¶C ¶ 2Ck
¶t
+ u k = Deff
¶z ¶z 2
+ ån r kj j (4.89)
j
 Partial Differential Equations in Time   ◾    165

where k represents the five species and j sums over the two reactions. The value of Deff can
be computed from Taylor’s correlation as Deff = 3.57 u0d f . The boundary condition at the
inlet is the Dirichlet condition; inlet concentrations of all the species are known. The r­ eactor
inlet consists of the reactant A and inerts. A boundary condition is not implemented at the
outlet; instead, backward difference formula is used at the boundary node and the diffusive
term is neglected. The initial condition is that the reactor contains only inerts. Thus, the
initial and inlet boundary conditions are given by

C ( 0,z ) = éë0
T
0 0 0 CI 0 ùû
(4.90)
C ( t ,z = 0 ) = ëéC A,in
T
0 0 0 C I ,in ùû

We will use MoL to solve the PDE. The spatial domain is discretized in n intervals, with
step-size h = L/n. Central difference formula will be used for convective as well as diffusive
terms, which are given by

é ¶Ck ù Ck ,i +1 - Ck ,i -1 é ¶ 2Ck ù Ck ,i +1 - 2Ck ,i + Ck ,i -1

ê ¶z ú = 2h
, ê 2 ú =
h2
ë ûi ë ¶z û i

The solution vector consists of the five concentrations at each of the n locations:

éC A1 C A2  C An ù
ê ú
Y=ê     ú (4.91)
ê CI1 CI 2  CIn úû
ë

It is convenient to express Y in the above form. However, the ODE solver, ode45, requires
Y as a column vector.* The interconversion between the two can be easily done as

Y = reshape(Y, nSpecies,n);

The rate of reaction will be calculated as a 2 × 1 vector:

é k1C A ù
r=ê ú (4.92)
ëk2C ACP û

and the axial dispersion coefficient is computed as Deff = 0.013 m2 /s . The next example
demonstrates this problem.

*  MATLAB experts know that this is not strictly true. However, if you were one, you wouldn’t be reading this book. So, let us
assume this statement is true!
166   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 4.5  Isothermal Packed Bed Reactor with Multiple Reactions

Problem: Solve the isothermal packed bed reactor problem described above. The PBR
has a diameter of 25 cm and a length of 10 m, and inlet flowrate is 10 L/s. The inlet feed
contains CA = 5 and CI = 45 mol/m3.
Solution: This will be solved using MoL, as described above. The reaction rates will
be calculated using a separate function:

function r=reactionRate(C,par)
%% Calculate reaction rate
r(1,1)=par.k(1)*C(1);
r(2,1)=par.k(2)*C(1)*C(2);
end

Writing the main function file: The main function file consists of a code to compute
é dCk ù
ê dt ú . As per Equation 4.89, this will consist of three parts: convective term, conv-
ë ûi
Term; axial diffusive term, diffTerm; and reaction term, rxnTerm. The stoichio-
metric matrix for this example is defined as

é -1 -1ù
ê ú
ê1 -1ú
n=ê1 0ú
ê ú
ê0 1ú
ê0 0 úû
ë

The powerful matrix operations of MATLAB can be used to compute the reaction
term for all five species at any location simultaneously, because

é -1 -1ù
ê ú
ê1 -1ú
é k1C A ù
å n kj rj = ê 1
ê
0 úê ú
ú ëk2C ACP û
(4.93)
ê0 1 ú  
j
r
ê0 0ûú
ë

Equipped with the above information, the function for computing the overall model
can be written as follows:

function dY=packBedFun(t,Y,par)
%% Get parameters and variables
nsp=par.nSpecies;
n=par.n; h=par.h;
 Partial Differential Equations in Time   ◾    167

Y=reshape(Y,nsp,n);
dY=zeros(nsp,n);
CIn=par.CIn;
nuStoic=par.stoicCoef;
%% Model equations
for i=1:n
C=Y(:,i);
rxnTerm=nuStoic*reactionRate(C,par);
if (i==1)
diffTerm=par.DCoef*(Y(:,i+1)-2*C+CIn)/h^2;
convTerm=par.u0*(Y(:,i+1)-CIn)/(2*h);
elseif(i==n)
diffTerm=0;
convTerm=par.u0*(C-Y(:,i-1))/h;
else
diffTerm=par.DCoef*(Y(:,i+1)-2*C+Y(:,i-1))/h^2;
convTerm=par.u0*(Y(:,i+1)-Y(:,i-1))/(2*h);
end
dY(:,i)=-convTerm + diffTerm + rxnTerm;
end
dY=reshape(dY,n*nsp,1);

The use of reshape command to interconvert YÛY is underlined in the code above.
Let us investigate the term convTerm (for internal nodes). The spatial derivative is

é C A,i +1 - C A,i -1 ù
ê 2h ú
éC A ù ê ú æ éC A,i +1 ù éC A,i -1 ù ö
ê ú ê CP ,i +1 - CP ,i -1 ú çê ú ê ú÷
¶ êCP ú 1 ç êCP ,i +1 ú êCP ,i -1 ú ÷
=ê 2h ú = ç -
¶z ê  ú ê  ú 2h ç ê  ú ê  ú ÷÷
ê ú ê ê
ú
êë CI úû ê CI ,i +1 - CI ,i -1 ú ç ê CI ,i +1 úú êê CI ,i -1 úú ÷
èë û ë ûø
êë 2h ú
û

Based on the definition of Y as per Equation 4.91, the first term in the brackets is
Y(:,i+1) and the second term is Y(:,i-1). Hence, the convection term was
written as

convTerm = par.u0* ( Y (: ,i + 1) - Y (: ,i - 1) )/(2 * h ) ;

Likewise, diffTerm follows the same arguments. Both these yield a 5 × 1 column
vector. The reaction source term, ∑jνkjrj, as per Equation 4.93, is computed for all five
species in rxnTerm, which also yields a 5 × 1 column vector.*

*  This demonstrates how the power of MATLAB matrix operations is utilized fully to write highly efficient and readable
codes. Recall my insistence on defining all vectors as column vectors, unless the structure of a problem or storage of
“historical” data suggests otherwise.
168   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Driver script: The driver script is straightforward and follows the same pattern as
before. The parameters, inlet boundary values, and initial conditions are specified. The
MATLAB command repmat is used to obtain the entire initial condition ­vector Y0.
The ODE is solved using ode45 for a time span of [0 100]. The grid independence
was verified by running the code for n = 25 nodes and comparing the results with
n = 50. The closeness of the two suggests that n = 25 gives a solution with sufficient
accuracy. The code with this value of n is given below:
% Driver script for simulation of a
% packed bed reactor with multiple species
%% Model parameters
Q=0.01;
d=0.25;
Acs=pi/4*d^2;
u0=Q/Acs; modelParam.u0=u0;
L=10; modelParam.L=L;
DCoef=0.013; modelParam.DCoef=DCoef;
% Reaction conditions
modelParam.nSpecies=5;
modelParam.k=[0.05; 0.005];
modelParam.stoicCoef=[-1 -1; 1 -1; 1 0; 0 1; 0 0];
% Inlet conditions
CaIn=5.0; CiIn=45.0;
CIn=[CaIn; 0; 0; 0; CiIn];
modelParam.CIn=CIn;
%% Initialization and solution
n=25; modelParam.n=n;
h=L/n; modelParam.h=h;
C0=[0;0;0;0;CiIn];
Y0=repmat(C0,n,1);
[tSol,YSol]=ode45(@(t,Y) packBedFun(t,Y,modelParam),...
[0 100], Y0);
%% Plotting results
figure(1)
Z=0:h:L;
C_All=[CIn', YSol(end,:)];
C_All=reshape(C_All,5,n+1);
plot(Z,C_All(1:4,:));

Figure 4.11 shows the axial concentration profiles for the four species at steady state.
The profiles show expected behavior.

The code above will be used to further analyze the behavior of a packed bed reactor. Figure
4.12 shows the temporal variations in the concentrations of the four species at the exit.
The residence time in the reactor is 49 s. The concentrations stay at their initial condition
 Partial Differential Equations in Time   ◾    169

CQ

Concentrations (mol/m3)
4
CA
3 CP

1
CR
0
0 5 10
Location (m)

FIGURE 4.11  Axial concentration profiles of the four species at steady state.

4.5
CQ
Concentrations (mol/m3)

3 CP

1.5
CR

CA
0
0 50 100
Time (s)

FIGURE 4.12  Transient profiles of the four species (except the inert) at the exit. The inlet conditions
start affecting the exit only after some time, which depends on the residence time in the reactor.

for the initial 40 s. The effect of inlet conditions only start being observed at the exit after
a sufficient time has elapsed. The results seem to indicate that convection is predominant
under the operating conditions considered in this example. In the absence of the diffusive
term (and numerical diffusion), the exit concentrations would be affected only after 49 s.
However, the diffusive term makes the overall response smoother.
The importance of the diffusive term is further verified by comparing the results of
the packed bed reactor with a PFR (dashed line) in Figure 4.13. At the nominal value of
Deff = 0.013, the two curves are fairly close to each other. Since PFR represents the case with
no axial diffusion, one could conclude that the convection is dominant and diffusion plays
only a minor role in this packed bed reactor example. The dash-dot line in Figure 4.13 rep-
resents an order of magnitude greater value of Deff . Clearly, this increase in axial diffusion
results in a decrease in conversion.
170   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

5
PFR

Concentration, CA (mol/m3)
4 Deff = 0.13
Deff = 0.013
3

0
0 5 10
Location (m)

FIGURE 4.13  Axial profile of CA for packed bed reactor with Deff = 0.013 (solid line) and results
from steady state PFR simulations (dashed line) for comparison. The profile for a much higher value
of Deff = 0.13 (dash-dot line) is also shown.

4.5.3 Steady Graetz Problem: Parabolic PDE in Two Spatial Dimensions

4.5.3.1 Heat Transfer in Fluid Flowing through a Tube
Graetz problem is a standard problem in heat transfer in a fluid flowing through a tube,
where the fluid gets progressively heated due to higher boundary temperature or a constant
boundary flux. This is an example of steady state parabolic PDE. The primary mode of
transport in the axial direction is through convection while that in the radial direction is
diffusion. The steady state heat equation is given by

¶T a ¶ æ ¶T ö
u = r (4.94)
¶z r ¶r çè ¶r ÷ø

where
u is the velocity
α is the thermal diffusivity

The inlet temperature at z = 0 is specified. The symmetry boundary condition is applicable at
the center, whereas either the temperature (Dirichlet) or the heat flux (Neumann) is specified
at the wall. We will consider the problem where boundary temperature is specified:

T ( z = 0,r ) = T0
é ¶T ù (4.95)
ê ¶r ú = 0, T ( r = R ) = Tb
ë û r =0

Furthermore, parabolic velocity profile is assumed to exist in the tube:

æ ærö 2
ö
u ( r ) = umax ç 1 - ç ÷ ÷ (4.96)
ç èRø ÷
è ø
 Partial Differential Equations in Time   ◾    171

n+1
n

2
1
Parabolic Radial grid Flat profile

FIGURE 4.14  Velocity profile and radial grid used in Graetz problem.

It needs to be emphasized (for readers without heat transfer background) that for a tube,
R is a given value (radius) while r is a variable that changes from 0 at the center to R at
the wall.
We have simulated transient parabolic PDEs before in this chapter. The PDE (4.94) is
exactly of the same form, the only difference being that both independent variables are
spatial. The same tools employing MoL can be applied to this example as well. We will dis-
cretize using finite differences in radial direction. The velocity profile and computational
grid are schematically shown in Figure 4.14. The location at the axis of symmetry (r = 0)
is 1. Since the temperature at the final node is specified, we do not need to solve for the final
node. Discretizing the PDE for radian nodes 1 to n yields the following set of ODEs in axial
direction:

dT a é Tj +1 - 2Tj + Tj -1 1 Tj +1 - Tj -1 ù
= ê + ú , j = 2 to ( n - 1)
dz u j ë h2 rj 2h û
(4.97)
dT a é Tb - 2Tj + Tj -1 1 Tb - Tj -1 ù
= ê + ú, j = n
dz u j ë h2 rj 2h û

where Tb is the boundary temperature specified. The symmetry boundary condition at the
first node results in the condition T2 − T0 = 0, yielding the following ODE:

dT a é 2Tj +1 - 2Tj ù
= ú, j =1 (4.98)
dz u j êë h2 û

Note that since ∂T/∂r is zero at the boundary, the second term drops out of the above equa-
tion. The following example shows the simulation of fluid flowing in a tube with hot walls.
This is the Graetz problem with constant boundary temperature.

Example 4.6  Constant Wall Temperature Graetz

Problem with Parabolic Velocity
Problem: Solve the constant wall temperature Graetz problem of Equation 4.95, with
a fully developed parabolic velocity profile Equation 4.96 and umax = 0.5 m/s. The tube
is 2 m long and its diameter is 10 cm. Thermal diffusivity of the fluid is α = 10−4 m2/s.
172   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Solution: This is a standard parabolic PDE, where we use MoL. Discretizing in radial
direction leads to a set of ODEs given by Equations 4.97 and 4.98. The following func-
tion file, which follows the same pattern as previous examples, is used:
function dTdz=graetzFun(z,T,par)
% Function to compute dT/dz for
% heat transfer in a heated tube
r=par.r; % Radial coordinate
u=par.u; % Radial velocity profile
n=par.n; % Nbr of radial nodes
h=par.h; % Radial step-size
alpha=par.alpha;
Tb=par.Tb;
% Model equations
dTdz=zeros(n,1);
for j=1:n
if (j==1)
term1=(2*T(j+1)-2*T(j))/h^2;
term2=0;
elseif (j==n)
term1=(Tb-2*T(j)+T(j-1))/h^2;
term2=(Tb-T(j-1))/(2*h*r(j));
else
term1=(T(j+1)-2*T(j)+T(j-1))/h^2;
term2=(T(j+1)-T(j-1))/(2*h*r(j));
end
dTdz(j)=alpha/u(j)*(term1+term2);
end

Although obvious to intermediate and expert users, it bears repeating that the overall
methodology and structure of the file remains exactly as before. The following driver
script is used to solve the Graetz problem:

% Driver script for Graetz Problem:

% Heat transfer in a tube with hot wall
%% Model parameters and conditions
L=2.0; % 2 m long tube
R=0.05; % 10 cm tube dia
n=100; h=R/n;
r=[0:n]'*h; % Radial coordinate
modelPar.alpha=0.0001;
% Inlet and boundary conditions
modelPar.Tin=300;
modelPar.Tb=400;
uMax=0.5;
u=uMax*(1-(r/R).^2); % Parabolic
% u=uMax/2*ones(n+1,1); % Plug-flow
 Partial Differential Equations in Time   ◾    173

modelPar.L=L; modelPar.R=R;
modelPar.n=n; modelPar.h=h;
modelPar.r=r;
modelPar.u=u;
%% Set up and solve the PDE
T0=ones(n,1)*modelPar.Tin;
opts=odeset('relTol',1e-12,'absTol',1e-10);
[Zsol,Tsol]=ode15s(@(z,T) graetzFun(z,T,modelPar),...
[0, L], T0, opts);
%% Plot results and post-process
% Include wall temperature in Tsol
nAxial=length(Zsol);
Twall=modelPar.Tb*ones(nAxial,1);
Tsol=[Tsol,Twall];
% Temperature vs. location
figure(1);
plot(Zsol,Tsol(:,[1,26,51,76,86]));
xlabel('Axial location, z (m)');
ylabel('Temperature (K)');
% Temperature contours
figure(2)
subplot(2,1,1)
contourf(Zsol,r,Tsol');
colorbar
xlabel('Axial location, z (m)');

Figure 4.15 shows the temperature profile vs. axial distance for four different radial loca-
tions in the tube. The final temperature is higher and the temperature increases more rap-
idly as one goes closer to the hot wall.

400

380
Temperature (K)

360

340

320

300
0 0.5 1 1.5 2
Axial location, z (m)

FIGURE 4.15  Axial temperature profiles at various locations: r = 1.25, 2.50, 3.75, and 4.25 cm from
the central symmetry axis. The arrow indicates increasing radial coordinate.
174   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

0.05 400

350

0 300
0 1 2
(a)

0.05 400

350

0 300
0 1 2
(b) Axial location, z (m)

FIGURE 4.16  Contours of temperature for parabolic (a) velocity profile and plug flow (b).

4.5.3.2 Effect of Velocity Profile

The above problem was solved with parabolic velocity profile. This is an appropriate
assumption for a fully developed laminar flow, which is what one expects in practical situ-
ations. As a numerical exercise, it is worthwhile to compare the results with a flat velocity
profile (such as the one we assume under plug flow conditions). Figure 4.16 shows velocity
contours for the two cases: Darker regions indicate lower temperature and lighter regions
indicate higher temperatures. The flat velocity profile can be imposed in Example 4.6 by
uncommenting the underlined expression in the code:

u=uMax/2*ones(n+1,1); % Plug-flow

Recall that the average velocity in a tube is uavg = umax/2. Comparing the contour maps,
the warm region “diffuses” into the tube faster with plug flow than parabolic velocity profile.
This is expected since the Nusselt number (Nu) for the two cases is 5.78 (plug) and 3.66
(parabolic).

4.5.3.3 Calculation of Nusselt Number

I mentioned above that the asymptotic value of Nu for a parabolic velocity profile is 3.66.
The value of Nu is high when the thermal boundary layer is developing and settles to the
asymptotic value when the thermal boundary layer is developed. Standard heat transfer or
transport phenomena books show these correlations (Dittus-Boelter or Sieder-Tate cor-
relations are quite popular in UG chemical and mechanical engineering textbooks). Let us
numerically arrive at the Nu profile.
Recall that Nu is defined as

hD
Nu = (4.99)
k
 Partial Differential Equations in Time   ◾    175

The heat flux at the wall is given by

é ¶T ù
kê ú
ë ¶r û R

This is the rate at which energy enters the tube through a unit area of the wall. At any axial
location, if ⟨T⟩ is the average temperature, the convective term for heat transfer to the fluid
is given by

(
h Tb - T )
Since at steady state these two are equal at any axial location, we get

é ¶T ù
h ê ¶r ú
ë ûR (4.100)
Nu = D = 2R

k Tb - T ( )
Note that this definition is valid for each axial location.
The term ∂T/∂r can be obtained using three-point backward difference formula:

é ¶T ù 3Tn+1 - 4Tn + Tn-1

ê ¶r ú = 2h
(4.101)
ë ûR

The average temperature ⟨T⟩ is the so-called mixing-cup temperature:

T z =
ò T ( z,r ) × ru (r ) dr
0
R
(4.102)

ò ru (r ) dr
0

Since we have already precomputed vectors r and u, the denominator is calculated using
trapz. Likewise, we will use trapz to calculate the numerator at each axial location. The
code for calculating Nu profile is given below.

Example 4.7  Nusselt Number Profile for Example 4.6

The code for calculating Nu using Equation 4.100 is given below. This is a continua-
tion of the code from Example 4.6.

% Calculate mixing-cup T
Tavg=zeros(nAxial,1);
176   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

103
umax = 0.5 m/s
umax = 0.1 m/s
102

Nu
101

100
0 0.5 1 1.5 2
Axial location, z (m)

FIGURE 4.17  Nu profile for parabolic velocity profile for two values of umax.

denom=trapz(r,u.*r);
for i=1:nAxial
Tradial=Tsol(i,:);
numer=trapz(r,u.*r.*Tradial');
Tavg(i)=numer/denom;
end
% Calculate dT/dr at wall
dTdr=zeros(nAxial,1);
for i=1:nAxial
dTdr(i)=(3*Tb-4*Tsol(i,n)+Tsol(i,n-1))/(2*h);
end
% Calculate and plot Nusselt Nbr
Nu=2*R* dTdr ./ (modelPar.Tb-Tavg);
figure(3)
semilogy(Zsol,Nu)

Figure 4.17 shows the Nu profile for fully developed velocity in a tube. Note the
logarithmic scale on Y-axis. The value of Nu settles at its asymptotic value when
the temperature profile is fully developed. Hence, at a lower velocity of 0.1 m/s, the
asymptotic value of Nu is reached very rapidly.

The other example of Graetz problem is when the flux is specified at the boundary. This is
left as an exercise for the reader.

4.6 EPILOGUE
Numerical techniques for solving transient PDEs were the focus of this chapter. An intro-
duction to PDEs was presented in Section 4.1. Most of the distributed parameter prob-
lems of interest to chemical engineers are expressed in the form of quasilinear PDEs of the
first and second order. The historic classification of these PDEs as elliptic, hyperbolic, and
parabolic was discussed. Elliptic PDEs arise in multidimensional steady state balances of
 Partial Differential Equations in Time   ◾    177

systems where diffusion terms play an important or predominant role. Hyperbolic PDEs
describe convection-dominated systems. The solution propagates without damping along
the characteristic curves. Parabolic PDEs, on the other hand, lie somewhere between ellip-
tic and hyperbolic; like hyperbolic systems, the solution propagates along the first indepen-
dent variable (usually time), but like elliptic systems, the solution at any point in the domain
is influenced by both the boundaries.
Numerical methods based on finite difference approximation and MoL were discussed
in Section 4.3 for hyperbolic PDEs and in Section 4.4 for parabolic PDEs. Methods that
are explicit in time are attractive because they are computationally less intensive than fully
implicit methods. MoL was the predominant approach discussed in this chapter to solve the
hyperbolic and parabolic PDEs. It involves discretizing the PDEs in space to convert them
into a series of ODEs in time. ODE solution techniques from the previous chapter may then
be used for solving the resulting problem.
The physical nature of the hyperbolic and parabolic PDEs determines the choice of
numerical method to solve the problem. I showed that central difference formula for dis-
cretizing the convection term can result in an unstable behavior of the solution of PDEs.
Thus, upwind method (either first or higher order) was suggested for spatial discretization
in hyperbolic PDEs.
Section 4.3.4 also discussed the issue of numerical diffusion in hyperbolic PDEs.
The diffusion term in parabolic PDEs results in a stabilizing effect, allowing one to use
the central difference formula for discretizing in the spatial domain.
The Crank-Nicolson method was introduced as a fully implicit in-time numerical solu-
tion technique based on finite differences (Sections 4.3.2 and 4.4.2). However, this method
was not discussed further. The actual solution using Crank-Nicolson method will be dis-
cussed in Chapter 8, in Section II of this book.
In summary, MoL is the method of choice for solving hyperbolic and parabolic PDEs.
MoL allows us to use higher-order formulae for integrating in time. The nature of the two
systems dictates the use of upwind method and central difference for discretization in
hyperbolic and parabolic PDEs, respectively. The MATLAB ode45 and ode15s are the
preferred solvers for solving the discretized equations.

EXERCISES
Problem 4.1 (a) Derive the leapfrogging scheme for first-order hyperbolic PDE (4.28)
using a central difference in time and central difference in space.
(b) Derive forward-in-time second-order upwind method for first-order
hyperbolic PDE (4.28) with u > 0. Use forward difference approximation
for ϕt and a three-point backward difference formula for ϕx.
(c) How does the upwind method derived in (b) above change for u < 0?
(d) Derive the fully implicit formula for hyperbolic PDE using first-order
approximation in time and central difference in space. Extend it to para-
bolic PDEs as well.
178   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Problem 4.2 Solve the PFR with first-order reaction (see Example 4.1) using various
explicit forward difference in time and upwind in space discretization from
Section 4.3.1.
Problem 4.3 Complete the problem in Example 4.2 by writing the code for MoL with
three-point upwind method. Verify results shown in Figures 4.4 and 4.5.
Problem 4.4 Convert the general parabolic PDE (4.64) into a set of ODEs using MoL.
Use central difference formula for the diffusive term and upwind method
for the convective term.
Problem 4.5 The adiabatic PFR problem in Section 4.5.1 was solved ignoring the axial
­diffusion. If the axial diffusion was relevant, this will result in parabolic PDE.
(a) If D is the diffusivity and λ is the thermal conductivity, then write down
the mass and energy balance equations for a reactor with axial diffusion.
(b) Solve the above problem using MoL. The Péclet number for heat and
mass transfer are PeH = uL/α = 1 and Pe M = uL / D = 2.5, respectively.
Note that α = λ/ρcp is the thermal diffusivity. No-flux boundary condi-
¶C ¶T
tions may be chosen at the exit, that is, = 0 and = 0.
¶z z = L ¶z z = L
Problem 4.6 Solve the Graetz problem with flux specified at the boundary. The model
equation and boundary conditions are given by

¶T a ¶ æ ¶T ö
u = r (4.94)
¶z r ¶r çè ¶r ÷ø

T ( z = 0,r ) = T0
é ¶T ù é ¶T ù (4.103)
ê ¶r ú = 0, ê ¶r ú = \beta
ë û r =0 ë ûr =R

æ æ r ö2 ö
u ( r ) = umax ç 1 - ç ÷ ÷ (4.96)
ç èRø ÷
è ø

Problem 4.7 Compute the Nu profiles for the above problem and compare with the
­constant wall temperature case.
 CHAPTER 5

Section Wrap-Up
Simulation and Analysis

Several examples were covered as case studies in this part of the book. Chapter 2 laid the
linear systems basics, which we will use in this chapter to bring together the contents in this
part. The next two chapters focused on process simulation examples, where the model was
intended to capture how the solutions evolve in time.
Chapter 3 covered examples that can be cast into an ordinary differential equation–initial
value problem (ODE-IVP) of the type

dy
= f ( t ,y ) (5.1)
dt

y (t0 ) = y 0 (5.2)

These included transient simulations, where y ∈ R n is a solution vector that varied in time,
as well as cases where the solution variable y varied along a single spatial direction. The fol-
lowing case studies were discussed:

• A steady state plug flow reactor (PFR)

• Batch and continuous stirred reactors for exothermic reactions and biological reactions
• A two-tank heater, which presented an example of a hybrid* system

*  A hybrid system is governed by continuous dynamics and binary (or integer) switching variables. In the two-tank heater
case study, the flow between two tanks was turned on or off based on the height of the liquid in the two tanks. In systems
engineering parlance, such systems are known as autonomous hybrid systems. In contrast, the other type of hybrid systems
involves ones where an inlet may be switched on or off (binary decision).

179
180   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Chapter 4 extended our analysis to systems that vary in more than one dimensions (space
and time, or two spatial dimensions). Such systems* are governed by partial differential
equations (PDEs). The chapter focused on hyperbolic and parabolic PDEs. Such systems
arise due to material, energy, or momentum balance equations and are represented as

¶f ¶ ¶ æ ¶f ö
+ ( uf ) = ç G ÷ + S ( f ) (5.3)
¶t ¶z ¶z è ¶z ø

The first term on the right-hand side is the diffusive term. The PDE is said to be parabolic if
this term is included in the model, whereas it is hyperbolic if it can be ignored. The method
of lines approach used finite difference approximation to discretize the z-­dimension and
convert the PDE (5.3) into a set of ordinary differential equations (ODEs) of the form
Equation 5.1. With such a conversion

é f1 ù
ê ú
f2
yê ú (5.4)
êú
ê ú
êëfn úû

where ϕi represents the variable ϕ at the ith spatial node. A good balance of case studies was
provided in Chapter 4 to cover the most important systems:

• Transient PFR (an example of first-order hyperbolic PDEs)

• Transient packed bed reactor (an example of parabolic PDEs)
• Steady state heat transfer in a heated tube (parabolic PDE in two spatial dimensions)

This chapter builds upon the understanding gained in the previous two chapters for simu-
lation and linear analysis of process systems. The examples are meant to highlight a rather
broad spectrum of problems. Often, textbooks or courses deal with examples that can be
bucketed into “ODE-IVP” or “parabolic PDE” or “hyperbolic-PDE” molds. However, in
simulating practical systems, such distinctions are not so clearly defined. The case studies
in this chapter are intended to break these definitions. The intention here is to show that
concepts in the previous chapters are very much applicable, it is just a matter of breaking
these molds from our minds.

*  Process variables in such systems vary with both time and space. Hence, systems governed by PDEs are referred to as
distributed parameter systems. On the other hand, systems defined by ODEs have their properties evolve in one direction
(time for transient systems, or one spatial dimension for examples such as PFR), and are therefore termed as lumped
parameter systems. This distinction is not particularly useful for simulating the processes, but is sometimes useful in
analysis and control.
 Section Wrap-Up   ◾    181

The core concepts that I will build on in this chapter include eigenvalues, eigenvectors,
and decomposition (Chapter 2); explicit and stiff ODE solving using ode45 and ode15s
(Chapter  3); and finite difference discretization using central or upwind differencing
(Chapter 4).*

5.1 BINARY DISTILLATION COLUMN: STAGED ODE MODEL

Distillation is an important unit operation in chemical engineering. A continuous dis-
tillation column is used for the separation of two or more miscible close-boiling fluids.
Figure  5.1 shows schematic of a distillation column. Distillation is an example of staged
equilibrium operation. Mole fraction of a component is a key process variable, which var-
ies along the height of the column. The condenser at the top of the column forms the first
stage, whereas the reboiler at the bottom of the column forms the Nth stage. The feed is
introduced at the feed tray, which is somewhere between the bottom and top stages. In
a standard binary distillation column, the light component is obtained at the top and the
heavier component at the bottom.

5.1.1 Model Description
The mole fraction of the lighter component will be the process state variable.
Figure 5.1 also shows representation of a single equilibrium stage in the column. The liq-
uid and vapor are in equilibrium, and they flow from one stage to the next, and the process
is thus modeled as a sequence of equilibrium stages. The figure also shows a single ith stage
in the column. The mole fractions of the lighter component in the liquid and gas phase on
this stage are represented as xi and yi, respectively. These are assumed to be in equilibrium.
The molar flowrate of liquid and vapor streams exiting the stage are Li and Vi, respectively.

D, xD

F, z

Vi, yi
yi

xi
B, xB
Li, xi
(a) (b)

FIGURE 5.1  Schematic of (a) a distillation column and (b) a single equilibrium stage in the column.

*  In each chapter, we spent some time discussing theory, and then solving problems that used these concepts to provide
efficient solutions. I would like to emphasize that the definitions such as stiff vs. nonstiff or hyperbolic vs. parabolic are
not critical. What matters more is an understanding about how these categories affect our choice of numerical techniques.
182   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The distillate is drawn from the condenser at the top of the column. The distillate flow-
rate is D and the mole fraction is xD. The bottoms is drawn from the reboiler at a flowrate of
B and mole fraction xB. The feed enters the feed tray as a saturated liquid, with a flowrate F
and mole fraction z.
The liquid holdup on each stage is assumed constant. Thus, the overall material balance
requires the following condition to be satisfied:

F = D + B

A couple more assumptions are made to simplify the model. The first one is that of constant
relative volatility, which is defined as

y/(1 - y )
a= (5.5)
x/(1 - x )

Larger the value of α, easier it is to separate the two components. Constant relative volatility
is a reasonable assumption for mixtures that are close to ideal. Thus, the liquid- and vapor-
phase compositions are related to each other as

ax i
yi = (5.6)
1 + ( a - 1) xi

The second assumption is that of a constant molar flowrate. In other words, Li and Vi are con-
stant in the stripping (below the feed stage) and rectification (above the feed stage) sections.
The molar balance on the light component (see schematic in Figure 5.1) on each tray
yields

dxi
Mi = Vi +1 yi +1 + Li -1 xi -1 - Vi yi - Li xi (5.7)
dt

The model for the feed tray (see Equation 5.12) will include feed term as well.
One of the assumptions was the molar flowrate remains constant. Thus, the vapor-phase
flowrate remains constant at V within the entire column. Likewise, within the rectification
section (i > ifeed), the liquid molar flowrate is constant at L. However, feed gets added as liq-
uid on the feed tray; so, in the stripping section (i ≤ ifeed), Li = L + F.
The liquid stream that enters the reboiler is split into two streams, bottoms and a boil-up
stream. Thus

L + F = V + B

Likewise, the vapor that enters condenser is split into distillate and reflux stream:

V = L + D
 Section Wrap-Up   ◾    183

Thus, in the rectification section

Li = L, Vi = V (5.8)

and in the stripping section

Li = Ls , Vi = V , where Ls = L + F (5.9)

5.1.2 Model Equations and Simulation

Final model equations for all stages can now be summarized as

dx1
Condenser: MC = Vy2 - Dx1 - Lx1 (5.10)
dt

dxi
Rectification stage: M = V ( yi +1 - yi ) + L ( xi -1 - xi ) (5.11)
dt

dxi
Feed stage: M = V ( yi +1 - yi ) + Lxi -1 + Fz f - Ls xi (5.12)
dt

dxi
Stripping stages: M = V ( yi +1 - yi ) + Ls ( xi -1 - xi ) (5.13)
dt

dx N
Reboiler: M R = Ls x N -1 - Vy N - Bx N (5.14)
dt

The following example simulates the binary distillation column for an easy separation
­process with α = 4. The distillation column has five stages, one each in the rectification and
stripping sections.

Example 5.1  Binary Distillation with Five Stages

Problem: Starting with an initial mole fraction of 0.5, simulate a binary distillation
column with five stages for the conditions given in the following table:

Feed: F = 25 mol/s Distillate: D = 12.5 mol/s Tray holdup: M = 200 mol

xf = 0.5 Vapor: V = 30 mol/s Holdup: MC = MR = 2 kmol

Solution: We will simulate the system in the so-called “D-V mode.” Here, the distil-
late and vapor flowrates are specified. Since there are only two degrees of freedom,
the other flowrates are computed from these two. Other modes are the L-V mode, or
where reflux ratio (RR = L/D) is specified along with one bottoms parameter.
184   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The readers who have followed the previous chapters will realize that the binary distil-
lation function file is written in the same manner as before:

function dx = binaryDistFun(t,x, par)

% Five-stage binary distillation column
%% Distillation Parameters
alpha=par.alpha;
M=[ par.Mc;
par.M*ones(3,1);
par.Mr]; % All liquid holdup

V=par.V; L=par.L;
D=par.D; B=par.B;
F=par.F; xf=par.xf;
Ls = L+F;

%% Binary distillation model

y = (alpha*x) ./ (1 + (alpha-1)*x);

dx(1,1) = -L*x(1) - D*x(1) + V*y(2);

dx(2,1) = L*(x(1)-x(2)) + V*(y(3)-y(2));
dx(3,1) = L*x(2) + F*xf - Ls*x(3) + V*(y(4)-y(3));
dx(4,1) = Ls*(x(3)-x(4)) + V*(y(5)-y(4));
dx(5,1) = Ls*x(4) - B*x(5) - V*y(5);
dx = dx ./ M;

The driver code for the distillation column is given below. Again, the driver script is
self-explanatory. The above code as well as the driver script are hard-coded for five
stages. Expanding it to a larger number of stages is left as an exercise. Since α = 4, this
is a rather easy separation.

% Transient binary distillation simulation

%% Inlet and design conditions
modelPar.xf=0.5;
modelPar.M=200;
modelPar.Mc=2000;
modelPar.Mr=2000;

F=25;
D=12.5; % D-V mode: D is given
V=30.0; % D-V mode: V is given
L=V-D;
B=F-D;
modelPar.F=F;
modelPar.B=B; modelPar.D=D;
modelPar.V=V; modelPar.L=L;
modelPar.alpha=4;
 Section Wrap-Up   ◾    185

0.8

Composition, xi
0.6

0.4

0.2

0
0 200 400 600 800
Time (s)

FIGURE 5.2  Transient results for the data given in the table.

%% Initial condition and time

tSpan = [0, 2000]; % Time span
x0 = 0.5*ones(5,1); % Initial conditions
[tSol,xSol]=ode45(@(t,x) binaryDistFun(t,x,modelPar),...
tSpan, x0);

%% Plotting results
figure(1)
plot(tSol,xSol);
figure(2)
plot(xSol(end,:)); hold on;

R=L/D;
disp(['Reflux ratio: ',num2str(R), ...
'=> xd: ',num2str(xSol(end,1))]);

The transient simulation results are shown in Figure 5.2. Starting at the initial condi-
tions, the compositions settle at their steady state values in about 10 min. At simulation
conditions, the distillate at 12.5 mol/s contains 89.2% by moles of lighter component.
The reflux ratio is 1.4.

5.1.3 Effect of Parameters: Reflux Ratio and Relative Volatility

Textbooks on mass transfer and separations focus on reflux ratio (RR = L/D) as a key vari-
able for designing a distillation column. Keeping D constant at 12.5 mol/s, increasing the
reflux ratio increases the liquid reflux flowrate L as well as the reboiler vapor flowrate V.
The steady state results for three different values of V are shown in Figure 5.3. The value
of reflux ratio is indicated in the figure for comparison. The three conditions correspond
to V = 30.0, 37.5, and 112.5 mol/s, respectively. Increasing the reflux ratio clearly shows an
increase in the purity of the distillate and bottom. This comes at the cost of a higher amount
of energy input. Vaporizing a higher amount of fluid in the reboiler increases reboiler duty,
and therefore, energy is required. Additionally, for the same external flowrate, the internal
186   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

1
RR = 1.4
0.8 RR = 2
RR = 8

Composition, xi
0.6

0.4

0.2

0
1 2 3 4 5
Tray location

FIGURE 5.3  Steady state profile of compositions at various trays for three different conditions.

1
α=4
0.8 α=3
α=2
Composition, xi

0.6

0.4

0.2

0
1 2 3 4 5
Tray location

FIGURE 5.4  Effect of relative volatility on separation efficiency of binary distillation.

flowrates (L, V, and Ls) are significantly higher to achieve the same separation. This will
require a larger distillation column.
Alternatively, a distillation column with a larger number of trays may be used to achieve
a higher amount of separation. This is left as an exercise.
Relative volatility is an indicator of how easy or difficult separation through distillation
will be. Two close-boiling liquids will have relative volatility closer to 1 and are difficult to
separate. On the other hand, mixtures with large α are easier to separate. Figure 5.4 shows
the performance of a distillation column for three different values of relative volatility. As
relative volatility decreases, the purity of the two components also decreases. This indicates
that separation of liquids with small values of α would require a larger number of trays or
higher reflux or both.

5.2 STABILITY ANALYSIS FOR LINEAR SYSTEMS

Analysis of nonlinear systems is a vast and important field. A nonlinear system displays a
very rich repertoire of interesting dynamics. We will defer nonlinear analysis and bifurca-
tion to Chapter 9 in Section II of this book. The first step toward the analysis of nonlinear
 Section Wrap-Up   ◾    187

systems in multiple dimensions is linear stability analysis. In this section, the need for a
linear stability analysis will be first motivated using the chemostat example. Qualitatively
different types of dynamical behavior of linear systems will be reviewed in subsequent sub-
sections in this section.
As I shall argue in this section that analysis of linear systems itself is an important field.
The analysis in this section will build upon linear algebra concepts discussed in Chapter 2,
specifically eigenvalues and eigenvectors and vector subspace. It will be useful to review
those concepts to get a better understanding of linear system analysis.
Even to an undergraduate student, this topic is not entirely new. We have been intro-
duced to the topic of stability analysis in the Process Dynamics and Control course. One
may recall the discussion that a stable system has all its poles in the left-half plane. The same
requirement for closed-loop systems gave rise to the Routh-Hurwitz criterion for stability.
These criteria were introduced for analysis in the Laplace domain; similar criteria will be
generalized and discussed in the time domain, applied to a (multidimensional) system* of
ODEs y′ = Ay.

5.2.1 Motivation: Linear Stability Analysis of a Chemostat

A detailed nonlinear and bifurcation analysis of a chemostat will be discussed in
Section  9.2. Here, we will motivate linear stability analysis using the chemostat example
from Section 3.5.4. Recall that one of the steady states for the chemostat was

Sss = 0.091, X SS = 3.68, PSS = 3.19 (5.15)

Since S and X do not depend on P, we will ignore P from further discussion. Recall from
Chapter 3 that starting at an arbitrary initial condition, the system attained steady state
and reached the above values. This indicates that the above steady state is a stable steady
state.
The stability of a system can be analyzed in the vicinity of the steady state by linearizing
the nonlinear model at that steady state. A function f(y) can be linearized around steady
state ySS using multivariate Taylor’s series expansion:

f ( y ) » f ( y SS ) + Ñf ( y SS ) ( y - y SS ) (5.16)

where J = ∇f(ySS) is the Jacobian. Only the first-order term is retained for linearization. By
definition, at the steady state solution, f(ySS) = 0. Thus, the linearized model is given by

d
y » Jy (5.17)
dt

*  The discussion in control texts is for a controlled system y′ = Ay + Bu. Here, we are only analyzing the “autonomous” part of
the system, without the input manipulation. The stability concepts, though, are general.
188   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

where y = y - y SS represents deviation from the steady state value. In the case of the chemo-
stat, the Jacobian is calculated as

é ¶f1 ¶f1 ù
ê ¶X ú
J = ê ¶S ú (5.18)
ê ¶f 2 ¶f 2 ú
ëê ¶S ¶X úû

Since the model equations for the system are written as

é mSX ù
é f1 ù ê D ( S f - S ) - K + S ú
ê ú=ê ú (5.19)
ë f 2 û ê DX - mSX Yxs ú
êë K +S úû

the partial derivatives can be calculated analytically to yield the Jacobian:

é mXK mS ù
ê -D - - ú
(K + S)
2
K +S
ê
J =ê ú (5.20)
mXK mS ú
ê Y
2 xs
-D + Yxs ú
êë ( K + S ) K +S ú
û

The Jacobian value at this steady state is

é -4.06 -0.1333ù
J =ê ú
ë 2.97 0 û

The eigenvalues and eigenvectors of the system are computed using the eig command.
The eigenvalues are λ1 =  − 3.96 and λ2 =  − 0.1, and the corresponding eigenvectors are

é -0.8 ù é 0.0337 ù
v1 = ê ú , v2 = ê ú
ë 0. 6 û ë -0.9994 û

Eigenvalue decomposition was discussed in Chapter 2. Any matrix with distinct eigenval-
ues can be written in the form J = VΛV−1, where V is a matrix whose n columns are com-
posed of n eigenvectors of the matrix. Coordinate transformation was also discussed in
 Section Wrap-Up   ◾    189

Chapter 2. Change of coordinates to the above eigenvectors can be represented as matrix

multiplication:

y = [ v 1 v 2 ] y (5.21)

so that y = [v1 v2 ] y , where y is the same vector in the transformed coordinate system.
Therefore

V y ¢ = JV y
(5.22)
y ¢ = V -1
JV  y
L

Since Λ is a diagonal vector, we can write the two ODEs as

d
y = li yi Þ yi = e lit (5.23)
dt i

The above is stable iff the real part of the eigenvalues, re(λi) < 0. In vector form

y = e Lt Þ y = Ve LtV -1

Stability condition for y' = Jy: Thus, the condition for stability of a linear ODE is that the
real part of all eigenvalues of the matrix J should be less than zero. When the eigenvalues
of the Jacobian are plotted on a complex plane, all the eigenvalues should lie in the left-half
plane for the system to be linearly stable.

Example 5.2  Stability of Linear System

mu=0.5; K=0.25;
Yxs=0.75;
Sf=5; D=0.1;
% First steady state
S=0.0909; X=3.6818;
a1=mu*S/(K+S);
b1=mu*X*K/(K+S)^2;
% Linearization and analysis
J=[-D-b1, -a1;
b1*Yxs, -D+a1*Yxs];
[V, Lambda]=eig(J);
% Verify Stability
x0=[1;1];
f=@(t,y) J*y;
[tSol,xSol]=ode45(f,[0 100],x0);
190   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

One can check that the linear system is indeed stable, as evidenced by xSol reaching
the origin at the end time. The values of Jacobian and its eigenvalues and eigenvectors are

é -4.06 -0.1333ù
J =ê ú, li = {-3.96, - 0.1} (5.24)
ë 2.97 0 û

é -0.8 ù é 0.0337 ù
v1 = ê ú , v2 = ê ú (5.25)
ë 0. 6 û ë -0.9994 û

5.2.1.1 Phase Portrait at the Steady State

A phase plane is a plane with the two state variables plotted as two axes. Each curve on the
plot represents a trajectory that the system takes starting at various locations in the plane.
A collection of such curves that defines the dynamic response of the system constitutes
the phase portrait. Figure 5.5 shows the phase portrait for the linear bioreactor example.
Circles denote the various initial conditions in the 2D space. Starting at any point, the sys-
tem responds rapidly along the first eigenvector v1, whereas the response along the second
eigenvector v2 is more sluggish. This gives rise to the phase portrait as seen in Figure 5.5.
Eigenvalues and eigenvectors can be used to qualitatively analyze the dynamic response of
a system, which will be discussed in this section.

5.2.1.2 Trivial Steady State and Analysis

The above steady state is not the only steady state of the system. If the bioreactor does not
initially contain any biomass, no reaction can take place since the reactor input also does
not contain any microorganisms. Thus, with X(0) = 0, the exit concentrations are X = 0 and
S = Sf. This can also be derived from the chemostat model:

mSX
S¢ = D ( S f - S ) - (5.26)
K + S

x2

x1

FIGURE 5.5  Phase-plane plot for linear bioreactor from Example 5.2. The two dashed lines repre-
sent the two eigenvectors.
 Section Wrap-Up   ◾    191

mSX
X ¢ = -DX + Yxs (5.27)
K +S

At steady state, S′ = X′ = 0; the second equation

æ mS ö
0 = X ç -D + Yxs ÷ (5.28)
è K + S ø

has two solutions. The first one was mentioned in (5.15) above, whereas X = 0 (and hence
S = Sf ) is the second solution. This second solution may be called trivial solution.
Starting from a condition X = 0, we always reach the trivial solution. However, if the sim-
ulations are started with a very small positive value (say X = 10−3), the system still reaches
the steady state denoted in (5.15). This behavior can be further understood by calculating
the Jacobian at the trivial steady state. Specifically

é -0.1 -0.476 ù
J =ê ú
ë 0 0.257 û

the two eigenvalues are λ1 =  − 0.1 and λ2 = 0.257, and the corresponding eigenvectors are

é1 ù é -0.8 ù
v1 = ê ú , v2 = ê ú
ë0 û ë 0. 6 û

With a change of coordinate axes to the eigenvectors, the first eigenvalue represents a stable
response. The first eigenvector is the Stable Subspace: Starting at any arbitrary point along
v1, the system asymptotically approaches the steady state. Since the first eigenvector is the
S-axis, an initial condition [S0 0]T , where S0 is any arbitrary value, will result in a stable
response. This is exactly what we observed with a nonlinear system in Chapter 3, where
X(0) = 0 led to the trivial solution. The system linearized at the trivial steady state can be
analyzed in a manner similar to Example 5.2, with steady state values, S=5 and X=0.
In summary, the eigenvalues of the Jacobian matrix determine the local stability of a
system. For an n × n Jacobian matrix, if all n eigenvalues have negative real parts, then the
system is stable in the vicinity of that steady state. If only m eigenvalues have negative real
parts (with m < n), the m-dimensional subspace spanned by the corresponding eigenvectors
is the stable subspace, whereas the remaining (n–m)-dimensional subspace is the unstable
subspace of the system. The stability of a linear system is further analyzed in this section.

5.2.2 Eigenvalues, Stability, and Dynamics

Any nonlinear system can be analyzed in the vicinity of a steady state by linearizing
it and computing its eigenvalues to predict is dynamic behavior near the steady state.
Additionally, linear system analysis provides an extremely powerful tool to analyze a
192   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

general n-dimensional  system. The preceding discussion not only motivates the need to
better understand linear dynamics but also provides a template to do so.
The case of real and distinct eigenvalues was discussed in the preceding section. Consider
the ODE

y ¢ = Ay (5.29)

Coordinate transformation of the form

y ¢ = V -1
 AV y (5.22)
L

converted the original ODE into a set of decoupled ODEs. Based on this diagonalization,
we argued that eigenvalues in the left-half plane (i.e., eigenvalues with negative real parts)
are stable. This result is not limited to distinct eigenvalues but is applicable for all linear
dynamical systems. The proof of the above result is skipped since this is beyond the focus
of this book.
Nonetheless, let us take the discussion further using 2D examples in the rest of this sec-
tion. We will first take the case of real and distinct eigenvalues, and then extend it to other
general cases.

5.2.2.1 Dynamics When Eigenvalues Are Real and Distinct

Solution for linear differential equations is often a part of first-year undergraduate calculus
course. Let us relate the results obtained for matrix system in Equations 5.22 and 5.23 to the
more familiar form. For a 2 × 2 matrix, A, the solution derived in Equation 5.22 was

é c e l1t ù
y = ê 1 ú (5.30)
l t
êëc2e 2 úû

The solution, y, is obtained by changing the coordinate system back to the original coor-
dinates. From Equation 5.21

é c1e l1t ù
y = éë v 1 ù
v2 û ê l t ú
êëc2e 2 úû (5.31)

y = c1 v 1e l1t + c2 v 2e l2t

which is a familiar result from an introductory calculus course. The constants of integration
are obtained by substituting the initial condition:

é c1 ù
y 0 = c1 v 1 + c2 v 2 = éë v 1 v 2 ùû ê ú (5.32)
ëc2 û
 Section Wrap-Up   ◾    193

The implication of the above result is interesting. If the initial condition y0 lies on the first
eigenvector, y0 = c1v1 and c2 = 0.
The expression (5.32) also clarifies the geometric interpretation of results discussed in
previous subsection, which is summarized below:

1. If both λ1 and λ2 are negative, the system is stable, starting at any point in the state
space.
2. If both λ1 and λ2 are positive, the system is unstable at any point in the state space.
3. If λ1 is negative and λ2 is positive, then the system is a saddle node, with the first eigen-
vector as stable subspace and the second eigenvector as unstable subspace. In other
words, if the initial condition is y0 = αv1, then the system is stable. This is because as
per (5.32), the solution is y(t) = αv1e l1t ; since λ1 < 0, the system is stable.
The dynamics for this case is interesting. If y0 is not in the stable subspace, the final
solution is represented as

y ( t ) = c1 v 1e l1t + c2 v 1e l1t

The dynamics along v1 are convergent and stabilize after sufficient time, whereas
dynamics in the direction of v2 are divergent.
4. The final case is when λ1 is negative and λ2 = 0. The system is stable along the first
eigenvector, whereas it remains unchanged along v2.
As a first example, consider

é -4 1ù
y¢ = ê úy (5.33)
-3û
ë2
A

The two eigenvalues are λ = {−5, −2}, and the two eigenvectors are

é1ù é1 ù
v1 = ê ú , v 2 = ê ú
ë -1û ë2 û

Figure 5.6 shows the transient response of the ODE for two different initial conditions.
The first is starting from the first eigenvector. Specifically, y0 = v1. The system will evolve
along this eigenvector, with its response governed by the first eigenvalue; that is

é e -5t ù
y ( t ) = ê -5t ú
êë -e úû
194   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

–1
1

0.5

0
Time

FIGURE 5.6  Transient response and phase portrait for linear ODE with A=[-4, 1; 2, -3].
The two eigenvectors are v1=[1; -1] and v2=[1; 2].

In contrast, when y0 = 0.5v2, the system response will be given by

é0.5e -2t ù
y ( t ) = ê -2t ú
êë e úû

These two are shown on the left panels of Figure 5.6. Clearly, the system responds faster if
the initial condition is along the eigenvector v1, whereas the response is slower if the initial
condition is along the eigenvector v2. Thus, the more negative eigenvector is the fast mode
of the system and the less negative eigenvector is the slow mode of the system.
The right-hand panel of Figure 5.6 shows a phase-planeplot (also known as phase por-
trait). This is a 2D plot of state variable y1 vs. y2. It shows how the system responds starting
at various points in the state space. Specifically, with various initial conditions, ode45 is
used to find the variation of y with time; the locus of points y1 vs. y2 on the phase plane
gives the overall phase portrait of the system. The phase portrait charts out the dynamic
response of the system in the relevant regions in the two main dimensions. The dashed
lines on the phase portrait represents the system starting along either of the two eigenvec-
tors. Since v1 = [1  − 1]T is the fast eigenmode, the system response along v1 is faster than
the response along v2. The trajectories therefore approach v2 and then move along it to
reach the origin.
Figures 5.7 and 5.8 show the phase portraits of the linear system when the eigenvalues are
real and distinct. The eigenvalues are mentioned in the figure captions, and the eigenvec-
tors are indicated as dashed thick lines. When the two eigenvalues are negative and close
to each other (Figure 5.7a), the trajectories move uniformly in the state space. When the
two eigenvalues are an order of magnitude different (as in panels b and c), the trajectories
move ­rapidly along the fast eigenvector to reach the slow eigenvector; after this, the trajecto-
ries move along the slow eigenvectors. When the eigenvalue is increased to 0, the trajectories
move only along the first eigenvector and remain unchanged along the second eigenvector.
 Section Wrap-Up   ◾    195

(a) (b)

(c) (d)

FIGURE 5.7  Phase portrait for various 2D linear systems with two distinct real eigenvalues: (a) a
stable node with (λ1 =  − 5, λ2 =  − 4), (b) a stable node with (λ1 =  − 5, λ2 =  − 0.5), (c) a stable node with
(λ1 =  − 0.5, λ2 =  − 5), and (d) a case when one eigenvalue is 0. The two eigenvectors are v1=[1; -1]
and v2=[1; 2].

(a) (b)

FIGURE 5.8  Phase portrait for various unstable 2D linear systems with two distinct real eigenval-
ues: (a) an unstable saddle node (λ1 =  − 5, λ2 = 2) and (b) an unstable node (λ1 = 5, λ2 = 2). The two
eigenvectors are v1=[1; -1] and v2=[1; 2].

When one of the eigenvalues becomes positive (see Figure 5.8a), the system behaves as a
saddle node. The first eigenvector is the stable subspace, whereas the second eigenvector is
unstable. The overall system is unstable. If the initial condition is along the stable eigenvec-
tor, the system asymptotically goes to origin. Starting from other points in the state space,
the system reaches the unstable eigenvector and moves along that eigenvector to instability.
When the other eigenvalue is positive as well (Figure 5.8b), the system becomes unstable in
the entire 2D space. The linear systems of ODEs for which the results in Figures 5.7 and 5.8
196   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

are generated are given below. The subscripts represent the phase portrait responses (a)
through (f):

é -4.667 0.333 ù é -3.5 1.5ù

A(a ) = ê ú A(b ) = ê ú
ë 0.667 -4.333û ë 3 -2 û
é -2 -1.5ù é -3.333 1.667 ù
A(c ) = ê ú A(d ) = ê ú
ë3 -3.5û ë 3.333 -1.667 û
é -2.667 2.333 ù é4 -1ù
A(e ) = ê ú A( f ) = ê ú
ë 4.667 -0.333û ë -2 3û

One can easily verify using the eig command that the above matrices represent the ODE
systems y′ = A(⋅)y for Figures 5.7 and 5.8.
The phase portrait when eigenvalues are complex is shown in Figure 5.9. Complex eigen-
values always occur in complex conjugate pairs. Since

e(
a +ib )t
(
= e at cos ( bt ) + i sin ( bt ) )
the real part of the eigenvalues determine stability and the imaginary part results in oscilla-
tory behavior. Thus, if the real part of the eigenvalues re(λi) is negative, the system exhibits

(a) (b)

(c)

FIGURE 5.9  Various examples when eigenvalues are a complex conjugate pair: (a) a stable spiral
when re(λi) < 0, (b) a center when λi are imaginary, and (c) an unstable spiral when re(λi) > 0.
 Section Wrap-Up   ◾    197

stable spiral in phase portrait, if re(λi) is positive, the system exhibits unstable spiral, and if
the eigenvalues are purely imaginary, the phase portrait consists of concentric closed cyclic
trajectories. This is known as center. This behavior is discussed in the next example.

5.2.2.2 An Example
A classical example is a mass-spring system. The motion of a mass suspended from an ideal
spring that is displaced from its natural position is given by

mx ¢¢ + kx = 0 (5.34)

Consider displacement (x) and velocity (v) as the two state variables:

d éx ù é 0 1ù é x ù
ê ú=ê úê ú (5.35)
dt ë v û ë -k / m 0û ë v û

The eigenvalues of the above matrix are li = ±i k / m . Thus, the mass-spring system is qual-
itatively represented by the phase portrait in Figure 5.9b. The mass at rest in its equilibrium
position, x = 0, continues to remain at rest at that position. If the mass is displaced from its
equilibrium position, the spring makes the mass return to its original position. However,
in the absence of damping, the mass will keep oscillating around its equilibrium position.
If the original displacement of mass was greater, the mass will keep oscillating with a larger
amplitude. The phase portrait would therefore be one of the various closed cycles, which
depends on the original displacement of the mass from its equilibrium position.

5.2.2.3 Summary
Figure 5.10 summarizes the qualitative responses of the system for various eigenvalues
denoted in the central figure on a complex plane. Eigenvalues on a real axis result in stable
Im(λ)

Re(λ)

FIGURE 5.10  Eigenvalues and qualitative response of the systems.

198   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

(left-half plane) or unstable (right-half plane) responses without oscillations. Eigenvalues

on the imaginary axis, on the other hand, result in oscillatory responses, with the ampli-
tude of oscillations remaining constant. Finally, complex eigenvalues (with nonzero real
and imaginary components) result in oscillatory responses that stabilize or grow, based on
the real part.

5.2.3 Transient Growth in Stable Linear Systems

The discussion on the dynamics of a linear system of ODEs

y ¢ = Ay

has so far focused on the effect of eigenvalues on the system dynamic behavior. The eigen-
values determine the asymptotic or long-time behavior of the system. Eigenvalues with
negative real parts indicate stable response. When the two eigenvalues are close to each
other, the system does not “favor” any direction (see Figure 5.7a). However, when the
ratio of eigenvalues increases, the system response shows “faster” and “slower” modes (see
Figure 5.7b and c). The larger the magnitude of negative eigenvalue, the faster is the sys-
tem response along the corresponding eigenvector. This contrasting behavior along fast and
slow modes becomes especially significant as the ratio of the eigenvalues increases.
While the previous discussion focused on eigenvalues, the importance of eigenvectors
will be highlighted in this subsection.

5.2.3.1 Defining Normal and Nonnormal Matrices

Before proceeding further, let us define what is meant by a normal matrix. A matrix A is
said to be normal if it commutes with its (conjugate) transpose. For a real-valued matrix A,
the condition for normality is

AAT = AT A (5.36)

An important property that follows from this definition is that the eigenvectors of a nor-
mal matrix are orthogonal to each other. Conversely, a nonnormal matrix is one where
the eigenvectors are not orthogonal. Geometric interpretation is that a highly nonnormal
matrix will have its eigenvectors further away from being orthogonal (or at a closer angle
to each other).
There are several ways to quantify nonnormality. The one definition that is aligned to
the discussion in this section is adapted from the one presented by Ruhe.* When a matrix
is normal, the eigenvalues and singular values are equal. Thus, if |λi| and σi represent an
ordered set of eigenvalues (based on modulus) and singular values, respectively, then

max si - li (5.37)
i

*  Ruhe, A., On the closeness of eigenvalues and singular values for almost normal matrices, Linear Algebra Applications,
11 (1975), 87–94.
 Section Wrap-Up   ◾    199

is one measure of nonnormality. Another measure is based on condition number. The condi-
tion number of a normal matrix is equal to the ratio of its largest and smallest (by modulus)
eigenvalues. Thus, the relative values of condition number and the ratio of eigenvalues, that is

s1 l max
m= , m= (5.38)
sn l min

quantifies the nonnormality of a matrix. A normal matrix has m / m = 1; an increase in this

ratio indicates greater departure from normality.

5.2.3.2 Analysis of Nonnormal Systems

Now that the normal and nonnormal systems have been defined, let us shift the focus on
using the simple 2 × 2 example to demonstrate the salient features of a system that displays
nonnormal dynamical behavior. Such an analysis has been used to study weather patterns,
instabilities in combustion systems, etc., where both the long-term system stability as well
as short-term transients are equally important. Short-term surges in the energy of the sys-
tem may result in severe weather conditions or high-energy failure of devices.
Transient response of the original system

é -4 1ù
y¢ = ê úy (5.33)
-3û
ë2
A

was shown in Figure 5.6. The matrix is nonnormal; however, the two eigenvectors are close
to being orthogonal. Hence, the condition number

>> cond(A)
ans =
2.6180

is close to the ratio of its eigenvalues, 2.5. Thus, the system is only slightly nonnormal. Thus,
starting at an initial condition, the magnitude of dependent state variables y1 , y2 falls mono-
tonically to origin.
Now consider another matrix

é4 -9 ù
A1 = ê ú
ë6 -11û

which has the same eigenvalues (λ = {−5,   − 2} as the original matrix, A. The eigenvectors
of A1 are given as

é1ù é1.5ù
w1 = ê ú , w 2 = ê ú
ë1û ë 1 û
200   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The eigenvectors of matrix A1 make a small angle (w1 and w2 are 11.3° apart). The condition
number of this matrix

>> cond(A1)
ans =
25.3606

is an order of magnitude greater than the ratio of its eigenvalues. The condition number
is a metric that indicates how sensitive a system is to a change in the input parameters.
The asymptotic (long-term) response of the system is stable, and no eigenvector is signifi-
cantly faster or slower than the other. However, the closeness of the eigenvectors affects the
short-term transients of the system.
The transient response of the system for various initial conditions is shown in Figure 5.11.
The two panels on the left show the response of the system vs. time starting at four different
initial conditions:

é 0. 8 ù é 0. 8 ù é 0. 2 ù é 0. 2 ù
y (0) = ê ú , y (0) = ê ú , y (0) = ê ú , y (0) = ê ú
ë 0. 6 û ë -0.6 û ë0.98 û ë -0.98 û

2
3

2 1
E(t)

y1

1 0

0 –1
0 2.5 5 0 2.5 5
(a) Time (b) Time

1.5

–1.5 1.5

–1.5

(c)

FIGURE 5.11  Demonstration of transient growth in a nonnormal system: (a) energy E(t) vs. time,
(b) transient response of y1(t) vs. time, and (c) phase portrait. The four thick lines in the phase
­portrait correspond to the four lines in the two left transient panels.
 Section Wrap-Up   ◾    201

Figure 5.11a shows the change in energy of the system with time. For the purpose of this
example, energy E(t) is defined as

yT y y12 ( t ) + y22 ( t )
E (t ) = = (5.39)
y T0 y 0 y12 ( 0 ) + y22 ( 0 )

The first initial condition, y0 = [0.8  0.6]T, starts between the two eigenvectors (see phase
portrait in Figure 5.11c, where the dashed lines represent eigenvectors). The value of E(t) as
well as y1(t) and y2(t) decrease monotonically. This behavior seems qualitatively similar to
that observed in nearly normal systems.
The transient response starting at the second initial condition is shown as dash-dot lines
in all the three panels. A fairly large surge in energy is observed, with the maximum value
of E(t) exceeding 3. Likewise, the maximum value of y1(t) attained is 1.575. Some initial
conditions show large transient growth, whereas some other initial conditions do not. This
is an important feature of transient response of nonnormal systems: For certain initial con-
ditions, a large surge in short-term transients of the system is observed before the system
settles down asymptotically to its equilibrium point (origin).
The phase portrait of the nonnormal system (Figure 5.11c) is exactly as expected. The
initial response of the system is along the fast eigenvector, w1, and eventually approaches
and moves parallel to the slower eigenvector, w2 = [1.5  1]T. Since the two eigenvectors
form an acute angle, any trajectory starting from outside this region gets stretched along
w1, before returning to the origin along w2.
The transient growth will be even higher if either the two eigenvectors are brought closer
to each other or if the ratio of eigenvalues is increased. For example, with

é 8. 5 -13.5ù
A2 = ê ú
ë9 -14 û

the transient growth in E(t) is significantly higher. Note that the eigenvectors of A2 are the
same (w1, w2) as those of A1, whereas the eigenvalues are λ = {−5,   − 0.5}. Since the ratio of
eigenvalues is much greater than in the previous case, a larger transient growth is observed.
Note that the condition number for this matrix is μ = 212. Phase-plane analysis and tran-
sient growth for this system is left as an exercise.
Although the rules for phase-plane analysis remain the same for highly nonnormal sys-
tems, the consequence of skewed eigenvectors manifests as a large transient growth.

5.3 COMBINED PARABOLIC PDE WITH ODE-IVP: POLYMER CURING

This is an example that is relevant to the curing of thermosetting polymers or natural rub-
ber. The process, in the familiar case of rubber, is known as vulcanization. In either case,
the polymer or rubber sap is mixed with cross-linking agents (e.g., sulfur, in case of rub-
ber), promoters, and additives. The mixture is put in a mold and heated to a predeter-
mined temperature. Reactions take place at these elevated temperatures, which result in a
202   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

cross-linking of the polymeric chains. The mixture solidifies and gets its properties based
on the degree of cross-linking that happens during the process. Indeed, the actual process
involves tens or hundreds of reactions and is complicated. Moreover, geometries required
of these materials (such as tyre) are also highly complex. What we will do in this case study
is to define a simplified problem that is motivated by this important process. We will retain
just a couple of reactions and simulate a 1D slab geometry as a representative system.
Consider a 2 cm long slab, which is originally at room temperature. The two ends of the
slab are heated using a constant temperature source, which results in a rise in slab tempera-
ture due to conduction. At elevated temperature, the following reactions take place:
k1 k2
P ® C ® D

where
P is the original polymer
C is the cross-linked polymer
D is dead-ended polymer

A specific range of C and D are needed for the product to have desired properties.
The simplified geometry is a 1D slab with its ends kept at 180°C. Since the material is a
semisolid material in a mold, the temperature effects are modeled by a 1D transient heat
equation:

¶T ¶ 2T
= a 2 + S (T ,C ) (5.40)
¶t ¶z

where S (T,C ) is the source term due to reactions. We will neglect reaction heat effects. The
two reactions take place at each location in the slab. Since there is no transport of material
within the solid slab, the equations governing the concentration are

¶
CP = -r1
¶t
(5.41)
æ E ö
r1 = k10 exp ç - 1 ÷ CP
è RT ø

¶
CC = r1 - r2
¶t
(5.42)
æ E ö
r2 = k20 exp ç - 2 ÷ CC
è RT ø

¶
CD = r2 (5.43)
¶t

The initial concentration of P in the mixture is 0.5 mol/L; there is no C or D initially.

The ­system is initially at room temperature (25°C), when the heating is started. Dirichlet
 Section Wrap-Up   ◾    203

boundary conditions are imposed at the two ends of the slab since the temperature is speci-
fied. The next example shows the methodology.

Example 5.3  Heat Transfer and Reactions of Thermosetting Polymer

Problem: Solve the example of thermosetting polymer slab, which is cured by exposing
it to elevated temperature. The slab is 2 cm wide and thermal diffusivity is 5 × 10−8 m2/s.
The rate constants are given by

E1 E2
k1 = 5 ´ 108 min -1 , = 9500 K, k2 = 1011 min -1 , = 13, 500
R R

Compute the temperature profile and how the cross-link and dead-end concentra-
tions vary within the slab with time. The slab is heated for 75 min with the two ends
held at 180°C and allowed to cool under ambient conditions.
Solution: We will discretize the parabolic PDE (5.40):

dTi (Ti +1 - 2Ti + Ti -1 ) + S T ,C

=a ( i i) (5.44)
dt h2

Equations 5.41 through 5.43 are written for each node:

d
C X ,i = R X ,i (5.45)
dt

where X ≡ P , C , D represents the three species. Since the boundary temperatures are
known, we will write the above equations for only the (n − 1) internal nodes. We define
the solution variable as

T
F = éëT1 CP1 CC1 C D1  Tn-1 CP ,n-1 CC ,n-1 CD ,n-1 ùû (5.46)

and write the function file that computes dΦ as below:

function dPhi=curingFun(t,Phi,par)
% Model for simplified polymer curing example
% Combination of parabolic PDE for energy
% and ODE for material balances
%% Model parameters
alpha=par.alpha;
Tb1=par.Tb1;
Tb2=par.Tb2;
n=par.n;
h=par.h;
diffPar=alpha/h^2;
204   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

%% Model variables
Phi=reshape(Phi,4,n-1);
T=Phi(1,:);
C=Phi(2:end,:);

%% Model equations
dT=zeros(1,n-1);
dC=zeros(3,n-1);
for i=1:n-1
r=rxnRate(T(i),C(:,i),par);

% Energy balance
if (i==1)
diffCoef=T(i+1)-2*T(i)+Tb1;
elseif (i==n-1)
diffCoef=Tb2-2*T(i)+T(i-1);
else
diffCoef=T(i+1)-2*T(i)+T(i-1);
end
dT(i)=diffPar*diffCoef;
% Material balance
dC(:,i)=par.nuStoich * r;
end
dPhi=reshape([dT;dC],(n-1)*4,1);
end

Calculation of the reaction rate involves two reactions. The reaction term for each
species is given by

RX = ån r
X, j j (5.47)
j

where νX , j is the stoichiometric coefficient for species X in jth reaction. The matrix ν
is a 3 × 2 matrix, whereas the reaction rate vector is a 2 × 1 vector. The stoichiometric
matrix is

é -1 0ù
ê ú
nX, j =ê1 -1ú (5.48)
ê0 1 úû
ë

The reaction rate is computed in the function given below:

function r=rxnRate(T,C,par)
k0=par.k0;
E=par.E;
k=k0 .* exp(-E/T);
 Section Wrap-Up   ◾    205

% First reaction
r(1,1)=k(1)*C(1); % k1*C_P
% Second reaction
r(2,1)=k(2)*C(2); % k2*C_C
end

Note that the main challenge in this problem was converting the given set of PDE and
ODEs into a standard form after discretization. Once this was achieved as Equations
5.40 through 5.43, the rest followed the same procedure as we have done before. On
the same lines, the driver script also follows the same structure as earlier problems.
Since the solution vector is in the form of Equation 5.46, the initial conditions need to
be handled appropriately.
We will split the driver solution into two parts. The first part is slab heating, and
the second part is cooling down. The ODE solver, ode45, is used for a time span of
[0:75]. We use colon notation in time span because the solution is desired at every
1 min interval. When the solution is obtained, the last row of the solution vector con-
tains the values at time 75 min.
Thereafter, to simulate cooling in atmosphere, the solver is called again with a time
span of [75:90] and with the initial condition on the second call being the value at
the final time of the first call. The driver script is given below:

% Simulation of "simplified" polymer curing

% Combination of parabolic PDE for energy
% and ODE for material balances
%% Model parameters
L=0.02;
n=50;
h=L/n;
slabParam.L=L;
slabParam.n=n; slabParam.h=h;
% Energy balance parameters
Tb1=180+273;
Tb2=180+273;
slabParam.Tb1=Tb1;
slabParam.Tb2=Tb2;
slabParam.alpha=5e-8*60;
% Reaction parameters
slabParam.k0= [5e8, 1e11];
slabParam.E = [9500, 13500];
slabParam.nuStoich=[-1, 0;
1, -1;
0, 1];
%% Initial conditions and simulation
T0=25+273;
C0=[0.5;0;0];
Y0=repmat([T0;C0],n-1,1);
206   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

% Part-1: Heating up
tSpan=0:75;
[tSol,YSol]=ode15s(@(t,y) curingFun(t,y,slabParam),...
tSpan,Y0);
Y0=YSol(end,:); % Solution at t=75

% Part-2: Cool-down
tSpan=75:120;
slabParam.Tb1=25+273;
slabParam.Tb2=25+273;
[tSol2,YSol2]=ode15s(@(t,y) curingFun(t,y,slabParam),...
tSpan,Y0);
tSol=[tSol;tSol2(2:end)];
YSol=[YSol;YSol2(2:end,:)];

%% Plotting results
figure(1)
Z=[0:n]*h;
T1=YSol([6,11,21,41,81],1:4:end);
T1=[Tb1*ones(5,1), T1, Tb2*ones(5,1)];
plot(Z,T1);

MidT=YSol(:,101);
MidC=YSol(:,102:104);
figure(2);
subplot(2,1,1); plot(tSol,MidT);
subplot(2,1,2); plot(tSol,MidC(:,2)./midC(:,1));

Figure 5.12 shows the temperature profile along the length of the slab at various times
(5, 10, 20, 40, and 80 min). The last line occurs 5 min after the start of the cool-down

450 40 min
80 min
Temperature (K)

400 20 min

350 10 min

5 min
300
0 0.005 0.01 0.015 0.02
Location (m)

FIGURE 5.12  Evolution of spatial temperature profile in the 1D slab at various times. Solid lines
represent heating phase and dashed line 5 min into the cooling phase.
 Section Wrap-Up   ◾    207

0.5

0.4

Concentration (mol/L)
CC
0.3

0.2 CD
CP
0.1

0
0 40 80 120
Time (min)

FIGURE 5.13  Concentration of the three species at the center of the slab during the 2 h process.

450
Temperature (K)

400

350

300
(a)

20

15
CC/CD

10

0
0 40 80 120
(b) Time (min)

FIGURE 5.14  Variation of (a) temperature and (b) ratio of crosslink and dead-end concentrations
(CC/CD) at the center of the slab as a function of time.

period and is shown as dashed line. Due to low thermal diffusivity, significant tem-
perature gradients are present during the process.
Figures 5.13 and 5.14 show temporal variations in several key variables at the center
of the slab. Figure 5.13 indicates that the cross-link concentration, CC goes through
maxima. Moreover, although significant temperature gradients exist in the slab, the
reactions stop nearly 6 min into the cooling period, although the center temperature
208   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

is still quite high (Figure 5.14 top panel). This is attributed to the fact that the reac-
tion rate falls significantly due to large activation energy. Finally, the bottom panel
of Figure 5.14 shows that at the end of the process, the two desirable conditions of
curing are met: complete conversion of the original polymer (CP ≈ 0) and a good
crosslink:dead-end ratio.

A real polymer curing process is more complex, with tens or hundreds of reactions.
Moreover, heat effects due to reaction may also be important. The aim of this case study
was to introduce students to a different type of problem, where parabolic PDE and ODE-
IVP are solved simultaneously in process simulation. The intent of this exercise is to dem-
onstrate that a complex problem is easily solvable using tools in this book, once we break it
down to a standard form.

5.4 TIME-VARYING INLET CONDITIONS AND PROCESS DISTURBANCES

The examples considered so far in this book considered constant values of inlet. For exam-
ple, we simulated examples where the inlet flowrate or temperature was constant or there
was a single step change. In this section, I will present examples where the inlet conditions
or process parameters change with time. We will take the example of a biological reactor
with Monod kinetics, which was discussed in detail in Section 3.5.4.
The model and parameters for simulating a continuous stirred bioreactor summarized
from Chapter 3 (along with parameters) are given below:

dS
= D ( S f - S ) - rg
dt
dX
= -DX + rg Yxs (5.49)
dt
dP
= -DP + rg Yps
dt

æ éS ù ö
where rg = ç m max ë û ÷ éë X ùû (5.50)
ç K S + ëéS ùû ÷ø
è

The rate constants are given as μmax = 0.5, KS = 0.25, Yxs = 0.75, and Yps = 0.65.

5.4.1 Chemostat with Time-Varying Inlet Flowrate

Incorporating a time-varying inlet flowrate is straightforward. However, it can sometimes
be confusing if the flowrate varies in a complex manner. We will tackle this problem in a
couple of steps. First, we consider the flowrate to vary in a sinusoid manner around the
nominal value. Next, we will consider the case where the flowrate is varied as a series of
steps and ramps. The nominal value of dilution rate D = Q/V = 0.3 h−1; the dilution rate will
vary ±20% around this value.
 Section Wrap-Up   ◾    209

Example 5.4  Chemostat with Sinusoidal Input

Problem: Solve the chemostat problem with sinusoid input, where the dilution rate
varies by ±20% round the nominal value of 0.2 h−1.
Solution: The driver script remains the same as before. The frequency of the sinu-
soid is defined in a monodParam structure.
The function file used in the calculation of dY/dt (for a constant dilution rate) was
­discussed in Section 3.5.4. The fourth line in that function was

D=monodParam.D;

It is easy to see that simulating sinusoid input simply means replacing that line with a
sine function that calculates

D = D0 éë1 + 0.2 sin ( 2pft ) ùû (5.51)

where f is the frequency of the sinusoid. Indeed, simulating a sinusoidal input is as

simple as replacing the original assignment for D with the expression (5.51).
However, to set ourselves up for the next example, we will define a separate func-
tion, varyingInlet, to do this calculation. It is easy to see that this function is

function D=varyingInlet(t,y,par)
D0=par.D;
f=par.freq;
D=D0*(1+0.2*sin(2*pi*f*t));
end

This function will be used within a monodFun.m function:

function dy=monodFun(t,y,monodParam)
%% System parameters
mu=monodParam.mu;
K=monodParam.K;
Yxs=monodParam.Yxs;
Yps=monodParam.Yps;
Sf=monodParam.Sf;
D=varyingInlet(t,y,monodParam);

%% Variables to solve for

S=y(1);
X=y(2);
P=y(3);
%% Calculating the model
rg=mu*S/(K+S)*X;
dy=zeros(3,1);
210   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

3.5

[S] or [X ] (mol/L)
2.5

1.5

0.5
0 10 20 30 40 50
Time (h)

FIGURE 5.15  Simulation of a chemostat with ±20% sinusoid input for a frequency of 0.5 Hz
(solid line) and 0.2 Hz (dashed line). The results with constant (nonsinusoidal) input are shown as
dash-dot line.

dy(1)=D*(Sf-S) - rg;
dy(2)=-D*X + Yxs*rg;
dy(3)=-D*P + Yps*rg;

The underlined line is where we inserted the calculation of dilution rate, D. Figure 5.15
shows the transient behavior of chemostat with sinusoidal input, with the dash-dot
line representing the case with constant D for comparison. The solid line indicates a
0.5 h−1 input sinusoid, whereas the dashed line indicates a slightly lower frequency
of 0.2 h−1. The output oscillates in both the cases. The output oscillates with a greater
amplitude when the frequency of sinusoid is lower.

The above example demonstrates how a sinusoidal input can be used in simulations. The
sinusoid can be replaced by a square wave using the following command instead:

D=D0*(1+0.2*square(2*pi*f*t));

Note again how straightforward it is to include periodic input signals in simulations.

The comparison between sinusoidal and square-wave inputs with a frequency of 0.2 h−1 is
shown in Figure 5.16.
In my experience teaching MATLAB®, students have often found it easy to incorporate
a periodic input trajectory, as shown in Example 5.4. However, using a more complex input
trajectory was more challenging. The next example will show how easy it is to incorporate
complex input trajectories as well. Let us modify the above problem as follows for peda-
gogical reasons: We wish to decrease the dilution rate to 0.1 h−1 for improving the product
yield. However, due to the fragile nature of the bioorganisms, we are unable to do so rapidly.
Hence, we will hold the dilution rate at 0.3 h–1 for one hour, then ramp down to 0.25 h–1 in
the next hour, hold it at 0.25 h–1 for another hour, ramp down to 0.2 h–1 in the next hour,
and so on until we reach 0.1 h–1.
 Section Wrap-Up   ◾    211

3.5

[S] or [X] (mol/L)

2.5

1.5

0.5
0 10 20 30 40 50
Time (h)

FIGURE 5.16  Simulation of chemostat using sinusoid and square waves at the same frequency of 0.2 Hz.

Example 5.5  Chemostat with Gradual Ramping Down of Input

Problem: Repeat the chemostat problem with the dilution rate ramped down gradually
from 0.3 to 0.1 h−1 in four ramp-down sequences.
Solution: In this example, we have retained the same driver script and chemostat
function as before. The only change will be in the function varyingInlet:

function D=varyingInlet(t,y,par)
% Dilution ramped down in a series of four
% ramp-down-and-hold sequence
if (t<1)
D=0.3;
elseif(t<2)
D=0.3-0.05*(t-1);
elseif(t<3)
D=0.25;
elseif(t<4)
D=0.25-0.05*(t-3);
elseif(t<5)
D=0.2;
elseif(t<6)
D=0.2-0.05*(t-5);
elseif(t<7)
D=0.15;
elseif(t<8)
D=0.15-0.05*(t-7);
else
D=0.1;
end

The chemostat is simulated, and the results are shown in Figure 5.17, with the top
panel showing the output concentration and bottom panel showing input dilution rate.
212   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

[S],[X],[P] (mol/L)
2

0.3
Dilution (h–1)

0.2

0.1
0 5 10 15
Time (h)

FIGURE 5.17  Chemostat with dilution rate ramped down in a sequence of ramp-down-and-hold.
Starting at 0.3 h−1, the dilution rate is held for an hour followed by ramp down at the rate of 0.05 for
the next hour.

5.4.2 Zero-Order Hold Reconstruction in Digital Control

Modern advanced computer control systems are digital controllers, in contrast to conven-
tional analog controllers. In a digital controller, the process variables are measured from
the system (and control actions injected) at discrete intervals of time. The chemostat is a
­continuous-time system, which is governed by a set of ODEs of the type

dy
= f ( t ,y ) (5.1)
dt

The time interval at which measurements are available in a discrete-time system is known
as sampling interval. We will represent sampling interval as Δts. Let us say that the che-
mostat was monitored at the rate of Δts = 0.2 h, then information is available at times t = 0,
0.2, 0.4, …. In discrete time, this is represented at measurement intervals k, which is an
integer. We represent these values as y(k). In other words, the values at times mentioned
above are represented as y(0), y(1), y(2), … and the equivalent discrete-time model is
given by

(
y ( k + 1) = f D y ( k ) ) (5.52)
 Section Wrap-Up   ◾    213

Analog

D/A Process A/D

Digital

FIGURE 5.18  Block diagram of the chemostat process with digital-to-analog reconstruction at the
input and analog-to-digital sampling of the output.

Let us say that the dilution rate was a manipulated variable, then the discrete-time model
with manipulated control input is given by

(
y ( k + 1) = f D y ( k ) ,v ( k ) ) (5.53)

The process of converting a discrete-time signal v(k) to a continuous-time input D ≡ v is

known as reconstruction, whereas the process of obtaining fΔ(⋅) of Equation 5.53 from f(⋅)
of Equation 5.1 is known as model discretization.
I will use an example to describe both reconstruction (using zero-order hold) and
­discretization. Figure 5.18 shows block diagram for this procedure.
For the sake of this example, let us consider that the controller uses some algorithm to
determine the following input sequence (which is repeated three times).
Zero-Order Hold (ZOH) is a method for reconstructing a continuous-time input from a
discrete-time signal, wherein the value of the input is held constant for the duration of the
time interval. In other words, for the data given in the Table 5.1, the dilution rate is kept at
D = 0.3 for 0–0.2 h, then at D = 0.28 for 0.2–0.4 h, then at D = 0.26 for 0.4–0.6 h, and so on.
The mathematical representation of ZOH is

v = vk , for k Dt s < t £ ( k + 1) Dt s (5.54)

At time kΔts, the value of state variables is y(k). Based on the ZOH reconstruction, the value
of v is kept constant in the interval. We can solve the ODE-IVP starting at t = kΔts and y = y(k).
This will yield us behavior of the system at future time instances. The system is sampled at
t = (k + 1)Δts, until which time, the input is held constant. Therefore, the discrete-time model
is nothing but the ODE-IVP solution at time (k + 1)Δts, starting with y = y(k) at t = kΔts.

TABLE 5.1  Discrete-Time Signal for a Chemostat

k 0 0.25 0.5 0.75 1 1.0 1.25 1.5 1.75 2 2.25 2.5 2.75 3.0
v(k) .3 .28 .26 .27 .3 .28 .24 .21 .20 .20 .18 .19 .17 .18
214   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 5.6  Chemostat with Discrete-Time Inputs

Problem: Solve the chemostat problem with discrete-time inputs given in Table 5.1.
Solution: In this example, the chemostat function, monodFun remains the same
as the one from Section 3.5.4. The driver script is adequately modified for the dis-
crete-time system to (i) incorporate ZOH to get input signal for the chemostat from
the discrete-time signal from Table 5.1, (ii) solve ODE for a single time-step Δts, and
(iii) sample the output at the end of the time-step. The driver script is given below:
% Simulates a discrete-time Chemostat with
% zero-order-hold inlet flowrate
%% Reactor parameters
monodParam.mu=0.5;
monodParam.K=0.25;
monodParam.Sf=5;
monodParam.Yxs=0.75;
monodParam.Yps=0.65;
%% Initial conditions and flowrate
S0=1.5;
X0=2.5;
P0=2.0;
monodParam.D=0.3;
monodParam.ts=0.25; % Sampling time
% Define all input values
VALL=[0.3; 0.28; 0.26; 0.27; 0.3; 0.28; 0.24;...
0.21; 0.20; 0.20; 0.18; 0.19; 0.17; 0.18];
VALL=repmat(VALL,3,1);
% Obtain time instances
n=length(VALL);
time=[0:n]*monodParam.ts;
%% Solving for discrete-time system
YALL=zeros(3,n); % For results
YALL(:,1)=[S0;X0;P0]; % Initial value

for k=1:n % Cycle over all time-steps

yk=YALL(:,k);
vk=VALL(k);
% (i) ZOH with D constant at vk
monodParam.D=vk;
tSpan=[time(k), time(k+1)];
% (ii) Solve for single time-step
[tSol,YSol]=ode45(@(t,y) monodFun(t,y,monodParam),...
tSpan, yk, opts);
% Sampling to extract value at final time
yk_plus_1=YSol(end,:);
YALL(:,k+1)=yk_plus_1';
end
 Section Wrap-Up   ◾    215

[S],[X],[P] (mol/L)
2

0.3

0.25
Dilution (h–1)

0.2

0.15
0 2 4 6 8 10
Time (h)

FIGURE 5.19  Simulation of chemostat with ZOH. Top plot: sampled output variables; bottom plot:
manipulated input dilution rate.

%% Plotting the results

subplot(2,1,1);
plot(time,YALL);
ylabel('[S],[X],[P] (mol/L)');
subplot(2,1,2);
stairs(time(1:end-1),VALL);
ylabel('Dilution (hr^{-1})'); xlabel('Time (hr)');

Figure 5.19 shows the results of discrete-time simulation of the chemostat. The top
panel shows the state variables, with symbols representing the actual measured values.
Since this is a sampled-data system, there is no information between consecutive time-
steps. The bottom panel represents the input. Here, a stairs plot is used for ZOH.

5.5 SIMULATING SYSTEM WITH BOUNDARY CONSTRAINTS

An adiabatic PFR was simulated in Section 4.5.1. Due to the exothermic heat of reaction,
temperature at steady state increased from 450 K at the entrance to 575 K at the exit of the
PFR. Since all the process parameters were known, it was possible to simulate this sys-
tem and obtain the temperature and concentration distribution in the reactor. One of the
more important sets of parameters in a PFR is the reaction kinetics (or broadly, the reac-
tion mechanism). The process of identifying the kinetic mechanism and estimating the
rate parameters is a crucial aspect of chemical engineering. Much of kinetic information
is obtained from reactors where temperature and other conditions are carefully controlled.
216   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

However, in some cases, (for example, highly exothermic system) the temperature may vary
within the system.
Analysis of reactors with strong temperature effects can indeed be done by solving mass
and energy balances for the PFR simultaneously. However, at times, detailed analysis or
parameter estimation in the presence of local temperature trends calls for an approach to
decouple temperature and mass balance effects. In other cases, the boundary temperature
may act as a constraint to the overall system.*

5.5.1 PFR with Temperature Profile Specified

In this case study, we consider the systems similar to the adiabatic PFR example from
Section 4.5.1. Let us say that we conducted experiments on this reactor under controlled
conditions, with temperature being measured at several axial locations along the reactor.
The concentration profile in the reactor with a given temperature profile is to be simulated
in this example. The steady state material balance in a PFR is given by

dC A kC A
u =- (5.55)
dz K r + CA

æ E ö æ DE ö
k = k0 exp ç - ÷ , K r = K 0 exp ç - r ÷ (5.56)
è RT ø è RT ø

The activation energy is E = 60 kJ/mol and ΔEr =  − 10 kJ/mol. The rate constants are speci-
fied at the temperature T1 = 450 K as k1 = 2 and Kr , 1 = 1. The inlet temperature was 450 K,
concentration 1 mol/m3, and flowrate 0.4 m/min. The temperature profile was measured in
the experiments at six different locations:

z (cm) 0.25 0.5 1.0 1.25 1.5 2.0

T (K) 454 460 480 520 595 605

Example 5.7  PFR with Specified Temperature Profile

Problem: Simulate the PFR to obtain a concentration profile along the length of the
PFR for which the measured temperatures are specified above.
Solution: The temperatures specified in the problem are those measured in the PFR.
We are not given other conditions (e.g., heat loss or heat gain if the PFR is in a fur-
nace). Hence, we will solve the material balance Equation 5.55 with the given temper-
ature profile superimposed. The PFR solution will require the temperature specified
at various points within the reactor (and not just the six points above). Thus, we will
need to use interpolation to obtain values within these spatial intervals.

*  A simplified version of this was seen in the Graetz problem in Section 4.5.3, where the temperature at the external bound-
ary (walls) was specified. An analogous problem of relevance in this case study is when the boundary temperature profile
is specified. There are several examples of practical relevance where one needs to implement a boundary value profile as a
constraint. This case study provides a way to solve problems of similar nature.
 Section Wrap-Up   ◾    217

Interpolation is discussed in Appendix D. We will use the MATLAB spline

c­ ommand to interpolate within the data given above. This will be done in two parts:
first, to fit the spline piecewise polynomial to data above and then to use this fit to
obtain T at any location. The former is done as

pfrTProfile=spline(zMeas,TMeas);

The above command generates an interpolating polynomial structure, ­pfrTProfile.

The value of T at any z, T(z), can be obtained using the ppval command:

T=ppval(pfrTProfile,z);

We will use this within the PFR simulations. The driver script is given below:
% Driver script for simulation of a PFR
% with specified temperature profile
%% Model Parameters
modelParam.k1=0.2;
modelParam.K1=1;
modelParam.T1=450;
modelParam.E=60*1000;
modelParam.DEr=-10*1000;
modelParam.Rgas=8.314;
% Reactor conditions
modelParam.u0=0.4;
L=2;
Cin=1;

% Measured profile
zMeas=[0, 0.25, 0.5, 1.0, 1.25, 1.5, 2.0];
TMeas=[450, 454, 460, 480, 520, 595, 605];
% Spline interpolating polynomial
modelParam.pfrTProfile=spline(zMeas,TMeas);

%% Simulating and Plotting

[Z,CA]=ode15s(@(z,C) pfrModelFun(z,C,modelParam), ...
[0, L], Cin);
figure(1); plot(Z,CA);
xlabel('Length (m)'); ylabel('C_A (mol/m^3)');

The key difference from the earlier PFR example is that the temperature is speci-
fied. However, since the temperature is not available as an explicit function, we fit a
spline interpolating polynomial to data. The PFR function, given below, uses this
spline polynomial to simulate the reactor with specified boundary temperature:

function dC=pfrModelFun(z,Ca,modelParam)
% To compute dC/dz for a PFR with a single reaction
% and reactor temperature specified
218   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

%% Model Parameters
u=modelParam.u0;
pfrTProfile=modelParam.pfrTProfile;
% Interpolate to obtain T(z)
T=ppval(pfrTProfile,z);
% Calculate reaction rate
r=rxnRate(T,Ca,modelParam);
% Model equation
dC=-1/u*r;
end

The following is a function for calculating reaction rate. This is same as the function
used in transient PFR example from Chapter 4:

%% Get reaction rate

function r=rxnRate(T,C,par)
% Function to compute reaction rate
Rgas=par.Rgas; % Gas constant
% Rate constants
k1=par.k1;
E=par.E;
T1=par.T1;
K1=par.K1;
DEr=par.DEr;
k =k1*exp(-E/Rgas*(1/T-1/T1));
Kr=K1*exp(-DEr/Rgas*(1/T-1/T1));

r=k*C/sqrt(1+Kr*C^2);
end

Figure 5.20 shows the concentration profile in the PFR. Since the temperature is rather
low in the initial section of the PFR, only a modest amount of reaction takes place,

0.8
CA (mol/m3)

0.6

0.4

0.2

0
0 0.5 1 1.5 2
Length (m)

FIGURE 5.20  Concentration vs. length of the PFR, simulated with a given temperature profile.
 Section Wrap-Up   ◾    219

and the conversion is about 43% at z = 1 m from the inlet. As we move further down-
stream, the temperature increases, which results in a rapid increase in conversion of A
and complete conversion is observed in less than z = 1.5 m of the reactor.

5.6 WRAP-UP
This chapter built upon the case studies from previous chapters in Section I of the book.
The previous chapters simulated cases where the system was represented by a set of ODEs
(Chapter 3) or PDEs (Chapter 4) with specified initial and boundary conditions.
The first section of this chapter focused on simulating a staged operation. Like a distrib-
uted parameter system (DPS), the modeled variables of interest vary in time and location.
However, unlike a traditional DPS, the model is not governed by PDEs; instead, the model
consists of multiple interconnected stages, with the process variables’ values specified only
at these discrete stages.
The second section of this chapter focused on using linear algebra tools for analysis and
understanding of transient systems. Specifically, we observed how rich dynamic behavior
emerges for even a simple example of linear ODE in two dimensions. We limited ourselves
to 2D since it is easy to visualize behavior in 2D pictorially. The concepts of linear system
analysis are more general, and extendible to multiple dimensions as well. A thorough non-
linear analysis will have to wait until we cover additional topics in Section II of this book.
The first two case studies in Chapter 9 will extend this linear analysis and cover nonlinear
analysis and bifurcation. An interesting concept of nonnormal system analysis is also intro-
duced in this section, as an extension of linear stability analysis. While most books on linear
systems focus on long-term asymptotic response, this section brought out the importance
of short-term transient growth.
Thereafter, we took a few examples to extend our analysis of transient systems. We con-
sidered a system where the energy balance leads to a parabolic PDE and material balance to
an ODE-IVP. The overall system of equations was solved simultaneously. A combination of
ODE and PDE occurs in practical examples but is usually not covered in numerical simula-
tion textbooks.
Finally, the next two case studies demonstrated simulations of systems where (i) a pro-
cess input or parameter varies with time and (ii) a boundary profile constraint is imposed
on a system.
This completes our discussion of transient systems in Section I of this book. The next
part will cover (nonlinear and linear) algebraic equations, ODE-BVPs (boundary value
problems), elliptic PDEs, and differential algebraic equations (DAEs, which are a combina-
tion of ODEs and algebraic equations).

EXERCISES
Problem 5.1 Repeat the simulations for a binary distillation column from Example 5.1 for
three stages each in rectification and stripping sections. Compare the results
with a five-stage column for the same operating conditions.
220   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Problem 5.2 Repeat the previous problem for a tougher distillation, with α = 1.75. How
many trays are required to get 95% purity (if it is possible) in the distillate?
Let D = 12.5 mol/s and V = 37.5 mol/s.
Problem 5.3 A mass-spring-damper system consists of a mass suspended by a spring and
a damper that damps the oscillations. The model is given by

mx ¢¢ + cx ¢ + kx = 0

Show that the overall system can be written as

x ¢¢ + ( 2zw) x ¢ + w2 x = 0

What is/are the conditions on ζ for the system to have oscillatory response?
Problem 5.4 Use the methodology of Section 5.2.3 for analysis of transient growth and
phase portrait of the system, y′ = A2y, where

é 8. 5 -13.5ù
A2 = ê ú
ë9 -14 û

Problem 5.5 Consider a linear system given by

é -1 - cot ( q ) ù
y¢ = ê úy
êë 0 -2 ûú

The eigenvalues of this matrix are λ = {−1, −2}. Show that the eigenvectors of
T
this matrix are v 1 = ëé1 0 ùû , v 2 = éëcos ( q ) sin ( q ) ùû .
T

Verify transient growth in the system for different values of

p p p p
q= , , , . Using MATLAB simulations, show that the maximum
2 6 20 100 p
transient growth is the highest when q = .
100
Problem 5.6 Simulations for thermosetting polymer reaction in a 1D slab were discussed
in Section 5.3. We ignored the heat of reaction. If the heat of reaction is
included in the simulations, the source term in Equation 5.40 becomes

S (T ,C ) = ( -DH1 ) r1 + ( -DH 2 ) r2 (5.57)

where (−ΔH1) = 75 kJ/mol and (−ΔH1) = 100 kJ/mol are exothermic heats of

the two reactions. Repeat Example 5.3 by including the heat of reaction in the
energy balance.
 Section Wrap-Up   ◾    221

Problem 5.7 In this problem, we will simulate a condition similar to Example 5.5 but with
variations in the substrate concentration. Consider that the chemostat is
used for effluent treatment. The substrate concentration is measured every
half hour and is found to be as follows:

t 0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Sf 5.72 3.67 5.23 4.96 4.15 4.58 4.97 5.59 5.18
t(cont.) 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0
Sf(cont.) 4.13 5.32 5.16 4.77 5.16 4.70 4.74 5.54

Use spline to fit a smooth spline function to the above values, and hence
use the spline interpolation to simulate the effect of the above variations in Sf
on the performance of a chemostat. Choose D = 0.1 and start with an initial
condition of Y0 = [0.1; 3.6; 3.2];.
Problem 5.8 In Example 5.5, the dilution rate was ramped down in a series of steps. The
problem was simulated with a continuously varying input. Instead, a dis-
crete-time controller with a sampling time of 0.25 h is used. The trajectory
with ZOH that is implemented is shown in the figure below:
0.3
v(k)

0.2

0.1
0 5 10
Time (h)

Repeat Example 5.5 with a discrete-time input signal reconstructed with

zero-order hold. Hint: The first few terms of the discrete signal are

t 0 0.25 0.50 0.75 1.00 1.25 1.50 1.75

v 0.3 0.30 0.30 0.30 0.30 0.2875 0.275 0.2625
 II
Linear and Nonlinear Equations and Bifurcation

223
 CHAPTER 6

Nonlinear Algebraic
Equations

6.1 GENERAL SETUP
Section I of this book focused on methods to solve ordinary differential equations (ODEs).
This first chapter of Section II will deal with solving a set of algebraic equations of the type

g ( x ) = 0 (6.1)

where
x ∈ R n is an n × 1 solution vector
g(⋅) is a vector-valued function

I will retain the convention followed in Section I: All vectors (unless otherwise specified)
will be column vectors. Thus, x is a n × 1 column vector and g(⋅) is an n × 1 function vector.
Prior to generalizing the discussion to an n-variable problem, interpretation of equation
solving for a single variable is first discussed. Solving algebraic equation is essentially find-
ing the value(s) of variable x that satisfy Equation 6.1. The notation x⋆ will be used to denote
the solution. Thus, g(x) represents how the value of the function varies with x, whereas g(x⋆)
represents the value at a specific point x = x⋆. Since x⋆ is the solution, the function value at
this point is, by definition, 0.
The geometric interpretation of solving a single nonlinear algebraic equation in one vari-
able is shown in Figure 6.1. The function g(x) varies with varying x and intersects the X-axis
at two points, x1 and x2 . The points are known as the roots of the function, since they satisfy
Equation 6.1.

225
226   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

g(x)
x*1 x*2

FIGURE 6.1  Schematic for a curve g(x), which intersects the X-axis at two points, x1 and x2 .

6.1.1 A Motivating Example: Equation of State

The ideal gas law gives the relationship between volume occupied by a gas and its pressure
and temperature:

Pv = RT

where
P is the pressure in Pa
v is the molar volume in mol/m3
R is the ideal gas constant
T is the temperature in K

The ideal gas law does not accurately capture the behavior of real gases. Equations of
state (EOS) provide a better prediction of the volumetric properties of fluids. One such
popular EOS is Redlich-Kwong (RK) EOS:

RT a/ T
P= - (6.2)
v - b v (v + b)

The problem of finding the molar volume of a gas at a particular temperature and pres-
sure using the ideal gas EOS is straightforward since it provides volume as an expression,
v = RT/P. On the other hand, RK EOS is a cubic equation.
Both the EOS can be put in the standard form of Equation 6.1 as

- RT
Pv
  =0
 (6.3)
g ideal ( v )

v -b a
g ( v ) º P ( v - b ) - RT + =0 (6.4)
v (v + b) T
 Nonlinear Algebraic Equations   ◾    227

1000

500

g(v)
0
g΄(v) v*

–500

v(1) or v(L) v(U)

–1000
0.5 1 1.5 2 2.5
v ×10–4

FIGURE 6.2  Plot of g(v) vs. v for Redlich-Kwong EOS using Equation 6.4 for the chosen values of
RK parameters at 100 bar and 340 K. The dashed arrow represents working of bisection rule while
the solid arrow represents working of Newton-Raphson method.

The latter equation is obtained by multiplying the RK EOS by (v − b) and rearranging.
The value, v⋆, that satisfies the above equation is the molar volume of gas at the correspond-
ing temperature and pressure.
In this chapter, the RK EOS will be used to compute the molar volume of a fluid at 340 K
temperature and 100 bar pressure and hence demonstrate solution of nonlinear equations.
The values of the two parameters in the RK EOS that I will use in this example (in SI units)
are a = 6.46 and b = 2.97 × 10−5. Figure 6.2 shows plot of g(v) vs. v for a range of values of v
using Equation 6.4. The curve intersects the X-axis at v⋆ = 1.646 × 10−4. This is the solution
of the nonlinear equation and hence represented as v⋆.
The corresponding molar volume using ideal gas assumption is videal 
= 2.827 ´ 10-4.
Solving the equation (6.3) signifies finding videal

, the point at which the function gideal(v)
(which is a straight line) intersects the X-axis.
Numerical methods for solving a single nonlinear equation in one unknown are dis-
cussed in the next section using the above example. Thereafter, the methods are extended
to a general n-variable case. Subsequently, MATLAB® functions fzero and fsolve used
to solve algebraic equations are discussed, followed by a few exemplary case studies.

6.2 EQUATIONS IN SINGLE VARIABLE

Solution to nonlinear algebraic equations requires iterative numerical techniques to be used.
The chosen numerical technique starts with an initial guess of the solution, and the cho-
sen technique is used to move in the direction of the solution. This is shown in Figure 6.2
for bisection and Newton-Raphson method, which will be discussed presently. Two initial
guesses are used in bisection method (denoted as x(L) and x(U)), and a single initial guess is
used in Newton-Raphson (denoted as x(1)). The aim of both the methods is to “move” in the
direction of the true solution x⋆. Note that typically this solution is not known a priori, and
the intent of the numerical technique is to be able to find this solution efficiently (i.e., with
low computational time).
228   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The following notations are used in this chapter. Various guesses are represented as
x(i), where i is the iteration index. Approximation error between subsequent iterations is
e(i) = x(i) − x(i − 1) and the true approximation error is et( ) = x  - x ( ) . The corresponding rela-
i i

tive errors will be represented as ε(i) and et( ). The notation Δ will be used to represent differ-
i

ence, which will be explained based on the context in this chapter. The term g(i) will be used
as a shorthand notation for g(x(i)). By definition of the solution, g⋆ = g(x(⋆)) = 0.

6.2.1 Bisection Method
Bisection method is an example of bracketing method, where two initial guesses are chosen.
These are represented as x(L) and x(U). They are chosen such that they lie on either side of the
desired solution. Thus, the function values for admissible initial guesses satisfy the relation

( )( )
g x( ) g x( ) < 0
L U

(6.5)

The two guesses, x(L) and x(U), shown in Figure 6.2, lie on either side of the true solution, x⋆.
The value of g(L) is negative and that of g(U) is positive, thus satisfying the condition (6.5). The
new guess using bisection method is generated by simply bisecting the line segment joining
x(L) and x(U). Thus

x( ) + x( )
L U
x( ) =
i +1
(6.6)
2

is the new iteration value. The condition (6.5) is verified for the new iteration value x(i + 1),
and either x(L) or x(U) is retained so that the current guesses still bracket the true solution.
Thus, if x(i + 1) lies on the same side as x(L), then x(i + 1) replaces x(L) for the next iteration while
x(U) remains unchanged; else, x(L) remains unchanged and x(i + 1) replaces x(U). Numerically

( i +1
)( )
if g x ( ) g x ( ) > 0, x ( ) = x ( ) , else x ( ) = x ( )
L L i +1 U i +1

(6.7)

Thereafter, the algorithm continues. At each iteration, Equation 6.6 is used to compute the
next guess, whereas the condition in Equation 6.7 is used to determine whether this iterant
replaces x(L) or x(U), based on the sign of g(i + 1). This method is continued iteratively until the
error e(i + 1) falls below a predetermined tolerance threshold:

e ( ) º x ( ) - x ( ) < etol
i +1 i +1 L
(6.8)

If the initial length of the line segment is e(0) = x(U) − x(L), then after the first iteration

e( )
0
e( ) =
1

2
 Nonlinear Algebraic Equations   ◾    229

Each subsequent iteration also halves the line segment. Thus, the bisection method has a
linear rate of convergence. The box below discusses convergence order of an iterative numer-
ical method.

DEFINITION: ORDER OF CONVERGENCE

An iterative numerical method generates new guess values of solution, x(1) ,  …  , x(i) , …. If the
consecutive errors between subsequent iterations satisfy

( )
m
e( ) = k e( )
i +1 i

then m is known as order of convergence of the numerical method.

If m = 1, the method is said to have a linear rate of convergence.
If m = 2, the method is said to have a quadratic rate of convergence.
For bisection method, κ = 0.5 and m = 1.

Continuing for n iterations

(0)
e
e( ) = n
n
(6.9)
2

If the error e(n) falls below the desired error tolerance threshold, etol in n iterations, then the
value etol satisfies Equation 6.9. Thus, irrespective of the form of function, g(x), the number
of iterations required to meet the desired error threshold can be computed a priori as

e( )
0
n = log 2 (6.10)
etol

The following example demonstrates the bisection method for finding the molar volume of
a fluid represented by RK EOS.

Example 6.1  Redlich-Kwong Equation of State Using Bisection Method

Problem: Use the bisection rule to compute molar volume at 100 bar and 340 K
for a fluid that obeys RK EOS (Equation 6.4), with parameters a = 6.46 and
b = 2.97 × 10−5.
Solution: Since this is the first example in Section II, I will use a single MATLAB
script to solve the problem using the bisection method. Thereafter, I will modify the
code to write in the recommended, modular coding.
At the risk of sounding repetitive, this example is not an approach I recommend.
230   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The core of the code involves computing the function g(v) as per Equation 6.4
for =340 , P = 100 × 105 , and the current guess value v(i). A new guess will be computed
using Equation 6.6, x(i) will replace either x(L) or x(U) using condition (6.7), and the
stopping condition will be verified using Equation 6.8.

% Molar volume using Redlich-Kwong EOS

a=6.46;
b=2.97e-5;
R=8.314;
% Operating conditions
P=1e7; % Pressure (Pa)
T=340; % Temperature (K)

%% Initial guesses and verification

vL=0.8e-4;
vU=2.2e-4;
gL=P*(vL-b) - R*T + (vL-b)/(vL*(vL+b))*a/sqrt(T);
gU=P*(vU-b) - R*T + (vU-b)/(vU*(vU+b))*a/sqrt(T);
if (gL*gU>0)
error('Inconsistent initial guesses');
end
X=vU; % Storing iterated values
G=gU;

%% Bisection method iterations

maxIter=50;
eTol=1e-8;
for i=1:maxIter
v=(vL+vU)/2;
g=P*(v-b) - R*T + (v-b)/(v*(v+b))*a/sqrt(T);

% Verify and change bracket limits

if (g*gL>0)
gL=g; vL=v;
else
gU=g; vU=v;
end

% Store results and compute error

G(i+1)=g;
X(i+1)=v;
err=vU-vL;
if (err<eTol)
break
end
end
 Nonlinear Algebraic Equations   ◾    231

%% Display result
disp(['Molar volume, v = ', num2str(v)]);

The result using RK EOS is 1.65 × 10−4 m3/mol:

Molar volume, v = 0.0001646

The bisection method required i=14 iterations to converge.

The two initial guesses were such that

e ( ) = v ( ) - v ( ) = 1.4 ´ 10-4
0 U L

The desired error tolerance was etol = 10−8. Thus, according to Equation 6.10

( )
n = log 2 1.4 ´104 = 13.8

(6.11)

Thus, the error falls below the tolerance threshold in 14 iterations, as seen in Example 6.1.
The bisection method is easy to use, and the number of iterations required for its con-
vergence is known a priori. It is also robust because the two guesses always bracket the
solution, and the new guess being midpoint of the current guesses can always be obtained
(irrespective of the nature of g(x)). There are, however, certain cases where the bisection
method fails. These are shown in Figure 6.3a: Although a root exists, there are no feasible
starting points for the bisection method. Figure 6.3b shows that feasible starting points fall
in a narrow range and are therefore difficult to obtain. Figure 6.3c shows where the feasible
starting points bracket a singularity and not a solution.

(a) (b) (c)

FIGURE 6.3  Three examples of functions where the bisection method “fails.”
232   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

I will end this section with a modular code for solving Example 6.1. Hereafter, similar
modular coding will be practiced.

Example 6.2  A Modular MATLAB® Code for Bisection Method

Problem: Redo Example 6.1 using a modular code.
Solution: The first part of writing the code is to separate out g(v) as a separate func-
tion, as shown below:

function gVal = RK(v,par)

% Returns g(v) at a particular T and P
% All values are in SI units
% Parameters
R=par.R;
a=par.a; b=par.b;
% Operating conditions
T=par.T;
P=par.P;
% Function value
gVal=P*(v-b) - R*T + (v-b)/(v*(v+b))*a/sqrt(T);
end

Once the above function is written, it may be directly used for computing g(v) within
the main script. The main script is given below. The script has undergone only modest
changes to make it modular: (i) g(v) is computed through the above RK function and
(ii) parameters are passed on to the function as a structure. Both these will make the
code less prone to errors. The driver script is

% Molar volume using Redlich-Kwong EOS

% Model parameters for the EOS
param.a=6.46;
param.b=2.97e-5;
param.R=8.314;
% Operating conditions
param.P=1e7; % Pressure (Pa)
param.T=340; % Temperature (K)

%% Initial guesses and verification

vL=0.8e-4;
vU=2.2e-4;
gL=RK(vL,param);
gU=RK(vU,param);
if (gL*gU>0)
error('Inconsistent initial guesses');
end
X=vU; % Storing iterated values
G=gU;
 Nonlinear Algebraic Equations   ◾    233

%% Bisection method iterations

maxIter=50;
eTol=1e-8;
for i=1:maxIter
v=(vL+vU)/2;
g=RK(v,param);

% Verify and change bracket limits

if (g*gL>0)
gL=g; vL=v;
else
gU=g; vU=v;
end

% Store results and compute error

G(i+1)=g;
X(i+1)=v;
err=vU-vL;
if (err<eTol)
break
end
end
disp(['Molar volume, v = ', num2str(v)]);

6.2.2 Secant and Related Methods

While the bisection method is easy to use and robust, it is often slow to converge.
Hence, alternatives with faster convergence rates have been proposed. One such
alternative is the secant method, where a straight line joins the two current guesses.
If x(i − 1) and x(i) are the two guesses, then the straight line joining the points (x(i), g(i))
and (x(i − 1), g(i − 1)) is

x - x( ) x( ) - x( )
i i i -1
= (6.12)
y - g( ) g( ) - g( )
i i i -1

The point at which the line intersects the X-axis is given by y = 0. Substituting and rearrang-
ing, the following equation can be used to update the secant solution:

x ( ) - x ( ) (i )
i i -1
x ( ) = x ( ) - (i )
i +1 i
×g (6.13)
g - g( )
i -1

The secant method starts with two initial guesses, g(0) and g(1) , and uses the above expres-
sion to generate the next guess. The code for the secant method is given in the next example.
234   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 6.3  Secant Method for Redlich-Kwong EOS

Problem: Solve Example 6.1 using the secant method.
Solution: The same function file, RK.m, will be used to generate g(v). The driver script
for the secant method is given below. Notice that the problem definition and preamble
sections remain same as before. Only the core numerical part of the code changes.
As before, arrays X and G will be used to store the values of v(i) and g(v(i)), respec-
tively. Since MATLAB array indices start from 1, the two initial values are represented
as X(1) and X(2). Therefore, the for loop starts from index i=2, instead of i=1 as
before. The code for using the secant method is given below:

% Molar volume using Redlich-Kwong EOS

% Model parameters for the EOS
param.a=6.46;
param.b=2.97e-5;
param.R=8.314;
% Operating conditions
param.P=1e7; % Pressure (Pa)
param.T=340; % Temperature (K)

%% Initial guesses and verification

vL=0.8e-4;
vU=2.2e-4;
gL=RK(vL,param);
gU=RK(vU,param);
X=[vL, vU]; % Storing iterated values
G=[gL, gU];

%% Secant method iterations

maxIter=50;
eTol=1e-8;
for i=2:maxIter+1
v=X(i) - (X(i)-X(i-1))/(G(i)-G(i-1))*G(i);
g=RK(v,param);

% Store results and compute error

G(i+1)=g;
X(i+1)=v;
err=abs(X(i+1)-X(i));
if (err<eTol)
break
end
end
disp(['Molar volume, v = ', num2str(v)]);

The result from the secant method is same as before. The secant method takes only
five iterations (at value of i=6) to converge.
 Nonlinear Algebraic Equations   ◾    235

The locations of key differences between bisection and secant codes are underlined
above. The main difference, of course, is how the next iteration value, x(i + 1) , is calcu-
lated. This is the first line in the for loop, where Equation 6.13 is used to compute the
next iteration value and is stored in variable v. The value g(v) is calculated as before;
however, the sign of g(v) need not be compared with the sign of g(v(L)).

The rate of convergence of the secant method is said to be super linear, since it converges
faster than linear convergence. Specifically, it can be shown that for the secant method
g -1
æ f ¢¢ ( x ) ö
(e( ) ) , 5 +1
g
(i +1) i
e =ç g= = 1.618 (6.14)
ç 2 f ¢ ( x ) ÷÷ 2
è ø
The exponent, γ, in the above equation is called the golden ratio.

6.2.2.1 Regula-Falsi: Method of False Position

The intermediate values obtained using the secant method in Example 6.3 were

1.5299e-4 1.6259e-4 1.6470e-4 1.6460e-4 1.6460e-4

The first two values, v(2) and v(3) , in the list above both lie on the left of the solution 1.646 × 10−4.
This shows that the secant method is not a bracketing method since g(2) × g(3) > 0. Method
of false position, on the other hand, is a bracketing method. A new guess is generated in a
similar way as Equation 6.13, though it uses x(L) and x(U) instead:

x( ) - x( ) (L)
U L
x ( ) = x ( ) - (U )
i +1 L
×g (6.15)
g - g( )
L

and then using condition (6.7) to determine whether x(L) or x(U) gets replaced. Thus, calculation
of the new approximation is similar to secant method, though it is a bracketing method where
the approximations retained are the ones that have opposite signs like the bisection method.

6.2.2.2 Brent’s Method
Equation 6.12 used in the derivation of the secant method involves fitting a straight line to
two points, (x(i), g(i)) and (x(i − 1), g(i − 1)). A more accurate method can be derived by fitting
a quadratic curve to three points, followed by the location where the curve intersects the
X-axis. Using Lagrange interpolating polynomial (see Appendix D)

x=x (i -2 ) ( y - g ( ) )( y - g ( ) )
i -1

+x ( )
i
( y - g ( ) )( y - g ( ) )
i -1
i -2 i

( g ( ) - g ( ) )( g ( ) - g ( ) )
i -2 i -1 i -2
( g ( ) - g ( ) )( g ( ) - g ( ) )
i i -1 i -2 i -1 i

() (
y - g ( ) )( y - g ( ) )
i -2 i -1
i
+x (6.16)

( g ( ) - g ( ) )( g ( ) - g ( ) )
i i -2 i i -1

236   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The above quadratic curve intersects the X-axis when y = 0. Thus, the next approximation is

x( ) g ( ) g ( ) x( ) g ( ) g ( )
i -2 i -1 i i -1 i -2 i
x( ) =
i +1
+
(g( i -2 )
- g( )
i -1
)( g ( i -2 )
- g( )
i
) (g( i -1)
- g( )
i -2
)( g ( i -1)
- g( )
i
)
x( ) g ( ) g ( )
i i -2 i -1
+ (6.17)
( g ( ) - g ( ) )( g ( ) - g ( ) )
i i -2 i i -1

The above expression can be used directly, or may be simplified algebraically. If the function
g(x) is smooth in the region [x(L), x(U)], this quadratic method converges rapidly.
Brent’s method is more popularly known as inverse quadratic interpolation, because a
quadratic function of Equation 6.16 is employed for the next guess. It is called inverse qua-
dratic because here x is interpolated as a function of g(i)’s.
I end this section by mentioning that the four methods discussed herein, bisection,
regula falsi, secant, and inverse quadratic interpolation, are methods that work with multi-
ple initial guesses. Here, they are arranged in ascending order of their order of convergence.
I will refer to these methods again when discussing MATLAB algorithm in Section 6.4.1.
The next two methods discussed presently use a single initial guess.

6.2.3 Fixed Point Iteration

Fixed point iteration, also known as method of successive substitution, expresses the origi-
nal nonlinear equation in the form

x = G ( x ) (6.18)

The above equation is used as an expression to generate subsequent approximate solutions

to the nonlinear algebraic equation. In other words, starting with x(0), new guesses are gen-
erated using

x( ) = G x( )
i +1 i
( ) (6.19)

One simple way to get (x) related to the original problem (6.1) is to write

G ( x ) = x + ag ( x )

though more often, it is better to rearrange the nonlinear equation appropriately. For exam-
ple, the RK EOS (6.2) may be rewritten as

RT v -b a
v =b+ - (6.20)
P v (v + b ) P T
 Nonlinear Algebraic Equations   ◾    237

The code of fixed point iteration using the equation above is skipped. Starting with the ini-
tial guess of v = 2.2 × 10−4, it took 14 iterations for this method to converge. The linear rate
of convergence is one disadvantage of fixed point iteration. A greater disadvantage is that it
is not a robust method, since there are stringent requirements on G(x) for stability of fixed
point iteration.
These results can be derived by expanding the function G(x) around the current guess
x(i) using Taylor’s series:

( x - x( ) )
2
i

G ( x ) = G ( x ) + ( x - x )G ( x ) +
() () ¢ ()
G¢¢ ( x ( ) ) + 
i i i i
(6.21)
2

( x - x( ) )
2
i

G ( x ) = x( )
+ ( x - x )G ( x ) +
() ¢ ()
G¢¢ ( x ( ) ) + 
i +1 i i i

The above is obtained by using the expression (6.20) in the first term of Equation 6.21.
The solution x⋆ satisfies the condition x⋆ = G(x⋆). Substituting in the above

(x ) G¢¢ x ( ) + 
2
- x( )
 i

( )

i
(
G x  = x ( ) + x  - x ( ) G¢ x ( )
i +1 i
) ( ) +
2
( ) i
(6.22)
x

Applying the mean value theorem

( )
x  - x ( ) = x  - x ( ) G¢ ( x ) , x Î é x ( ) , x  ù
i +1 i
ë
i
û
(6.23)

Using the definition of true error

et( ) = G¢ ( x ) × et( )
i +1 i
(6.24)

Thus, fixed point iteration has a linear rate of convergence, and the error converges if
|G′(ξ)| ≤ 1. If the value of G′(ξ) is negative, the error will switch sign at every iteration.
If G′(ξ) is positive and less than 1, then the error will decrease monotonically.
The error analysis can be performed for Redlich-Kwong problem analyzing G′(v⋆):

( v - b ) - 2b2
2
a
G¢ ( v ) = (6.25)
v2 (v + b )
2
P T

The computed value of G′(v⋆) = 0.56. Thus, it is estimated to take 15 iterations to converge,

starting from v(0) = 2.2 × 10−4.
238   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

One must exercise caution while using the condition for stability of fixed point iteration.
If the derivative G′(ξ) changes significantly in the vicinity of the solution, the estimates
based on Equation 6.24 can be highly incorrect. Secondly, the stability for convergence of
fixed point iteration in Equation 6.24 is a rather stringent condition. Although fixed point
iteration has an advantage of simplicity, it finds limited real-world applications because the
method is stable for only a restricted set of applications.

6.2.4 Newton-Raphson in Single Variable

Newton-Raphson or related methods are arguably the most widely used methods for
solving nonlinear equations. Before proceeding to multivariable Newton-Raphson
(next section), the single-variable version is discussed here. As seen in Figure 6.2, the
slope of tangent to the curve at a point (x(i), g(x(i))) is g′(x(i)). Thus, the equation for the
tangent is

y - y( ) = g ¢ x( )
i
( ) ( x - x ( ) )
i i
(6.26)

The point where the above line intersects the X-axis is obtained by substituting y = 0.
Newton-Raphson method uses this as the next iteration value for solving the nonlinear
equation

x (i +1)
=x (i )
-
( )
g x( )
i

(6.27)
g ¢( x( ) )
i

Note that I used the fact that the point y(i) on the curve is actually g(x(i)). I will now use the
Newton-Raphson method to solve the RK EOS problem.

Example 6.4  Newton Raphson

Problem: Use the Newton-Raphson method to obtain molar volume for the system in
Example 6.1.
Solution: The function developed in Example 6.1 will be used to obtain g(v). The
derivative g′(v) is

a æ v ( v + b ) - ( v - b ) ( 2v + b ) ö
g ¢(v ) = P + ç ÷
( )
2
T ç v 2
v + b ÷
è ø (6.28)
a æç 2vb - v 2 + b2 ö
g ¢(v ) = P + ÷
T ç v2 (v + b)
2
÷
è ø
 Nonlinear Algebraic Equations   ◾    239

The function, RKdg.m, is written to obtain g′(v) as below:

function dg = RKdg(v,par)
% Returns g'(v) at a particular T and P
% Parameters and operating conditions
a=par.a; b=par.b; R=par.R;
T=par.T; P=par.P;
% Function value
dg=P + a/sqrt(T)*(2*v*b-v^2+b^2)/v^2/(v+b)^2;
end

The main driver script for Newton-Raphson is similar to those of bisection and secant
methods. The only change is that RKdg is used to calculate g′(v) and v(i + 1) is calculated
from Equation 6.27. For the sake of brevity, only the Newton-Raphson loop is given
below:

%% Newton-Raphson iterations
X=v; % For storing v values
G=g; % For storing g(v)
for i=1:maxIter
dg=RKdg(v,param);
v=v-g/dg;
g=RK(v,param);
% Store values & check convergence
X(i+1)=v;
G(i+1)=g;
err=abs(X(i+1)-X(i));
if (err<eTol)
break
end
end

The following are the values of v(i) generated, starting from v(0) = 2.2 × 10−4:

1.7169e-4 1.6478e-4 1.6460e-4 1.6460e-4

In contrast to the bisection, secant, and fixed point iterations, Newton-Raphson con-
verged in four iterations.

A formal error analysis of Newton-Raphson method, as seen before, involves using Taylor’s
series expansion of g(x) around x(i):

( x - x( ) )
2
i

( ) ( ) ( )
g ( x ) = g x( ) + x - x( ) g ¢ x( )
i i i
+
2
( )
g ¢¢ x ( ) + 
i

(6.29)
240   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

If x = x⋆, the solution of Equation 6.1, then

( x *- x ( ) )
2
i

( ) ( ) ( ) 2 g ¢¢ ( x ( ) ) + 
0 = g x ( ) + x *- x ( ) g ¢ x ( )
i i i
+
i

( x *- x ( ) )
2
i

( x *- x ) g ( x ) = g ( x ) + 2 g ¢¢ ( x ( ) ) + 
() ¢ ()
i i () i i
(6.30)

g ( x ( ) ) ( x * - x ( ) ) g ¢¢ ( x ( ) )
2
i i i

( x *- x ) = g ¢ x ( ) + 2 g ¢ x ( ) + 
()
i

( ) i
( )
i

The above equation can be rearranged to give the Newton-Raphson method. The infinite
series can be truncated to the first-order term (i.e., the first term on the right-hand side) and
the remainder is the error. Thus

( ) ùú + éê- ( x *- x( ) ) g ¢ ( x ( ) ) + ùú
2
é g x( )
i i i
ê (i )
x = x -

(6.31)

ê
êë ( ) úúû êêë 2 g ¢ ( x ( ) ) úúû
g ¢ x( )
i i

The term in the first bracket is the new iterated value x(i + 1), whereas the term in the second
bracket is the error, e(i + 1):

x (i +1)
=x (i )
-
( )g x( )
i

(6.27)
g ¢( x( ) )
i

( e( ) )
2
i
g ¢¢ ( x )
e( )
i +1
=- (6.32)
2 g ¢(x)

Note that the mean value theorem is used to convert the higher order terms of the infinite
series, where ξ ∈ [x(i), x(i + 1)]. It is clear from the above expression that the Newton-Raphson
method has a quadratic rate of convergence. Hence, in the vicinity of the solution, x⋆, Newton-
Raphson converges faster than the other methods discussed in this section. Consequently,
it emerged as one of the most popular methods for solving nonlinear algebraic equations.

6.2.5 Comparison of Numerical Methods

The five numerical methods considered here—bisection, secant, regula falsi, fixed point
iteration, and Newton-Raphson—were analyzed for their error behavior. The error propa-
gation equation is

( )
m
e( ) = k e( )
i +1 i
(6.33)

 Nonlinear Algebraic Equations   ◾    241

10–4

10–8

e (i + 1)
10–12

10–16
10–10 10–8 10–6 10–4
e(i)

FIGURE 6.4  Plot of errors e(i + 1) vs. e(i) for fixed point iteration (diamonds), secant (squares), and
Newton-Raphson (circles). The Newton-Raphson method has significantly lower errors and shows
a faster drop in error.

If the error in the (i + 1)th iteration is plotted on X-axis against error in the (i)th iteration
on a log-log plot, it will result in a straight line with a slope, m, equal to the order of con-
vergence of the numerical method. Figure 6.4 shows this log-log plot for three methods.
Bisection and regula falsi are skipped for ease of discussion. As is clear from the figure, all
the three are straight lines, with slopes of 1, 1.6, and 2, respectively. The slope can either be
computed from the figure or qualitatively confirmed. For example, e(i) and e(i + 1) decrease by
almost four orders of magnitude for the bisection method. For Newton-Raphson, on the
other hand, e(i + 1) decreases by 12 orders of magnitude when e(i) has decreased by six orders
of magnitude (indicating a quadratic rate of convergence).

6.3 NEWTON-RAPHSON: EXTENSIONS AND MULTIVARIATE

The Newton-Raphson and related methods are investigated in more detail in this section,
considering a general n-dimensional system of equations:

g ( x ) = 0, x ÎR n , g : R n ® R n (6.1)

6.3.1 Multivariate Newton-Raphson
Derivation of a general Newton-Raphson method uses multivariate Taylor’s series expan-
sion. If the n elements of the n-dimensional function g(x) are g1(x) ,  …  , gn(x), then

( ) i
( )( x - x( ) ) +
0 = g 1 x ( ) + Ñg 1 x ( )
i i

 (6.34)

0 = gn x( ) + Ñg ( x ) ( x - x ) +
(i )
n
(i ) (i )
242   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

where the gradient ∇gk(x(i)) is a 1 × n row vector:

( ) é ¶g ¶g k
Ñg k x ( ) = ê k
i

¶
ë 1x ¶x 2
¶g ù
 kú
¶xn û
(6.35)

These equations can be combined into the following matrix form:

( ) ( ) ( x - x ( ) ) + 
0 = g x( ) + J x( )
i i i
(6.36)

In the above, J(x(i)) is called the Jacobian, which is an n × n matrix. Unlike the single vari-
able case, the order of matrix multiplication is important. The Jacobian premultiplies the
difference (x − x(i)). It is easy to see that the above can be rearranged to obtain multivariate
Newton-Raphson formula as below:

x ( ) = x ( ) - J -1g x ( )
i +1 i i
( ) (6.37)

é ¶g 1 ¶g 1 ¶g 1 ù
ê ¶x 
¶x2 ¶xn ú
ê 1 ú
ê ¶g ¶g 2 ¶g 2 ú
ê 2  ú (6.38)
J = ê ¶x1 ¶x2 ¶xn ú
ê ú
ê     ú
ê ú
ê ¶g n ¶g n

¶g n ú
êë ¶x1 ¶x2 ¶xn úû x = x (i )

In the rest of this chapter, I will drop the boldface. The examples considered hereafter will
be multivariate. It bears repeating that all the vectors, unless stated otherwise, will be col-
umn vectors; subscripted number indicates corresponding element of the vector, and the
iteration index is indicated by superscript in bracket.
The multivariate Newton-Raphson technique will be demonstrated using the chemostat
example from Chapter 3. The model for the growth of microorganisms, substrate consump-
tion, and product formation in a continuous stirred reactor is given by

0 = D ( S f - S ) - rg
0 = -DX + rg Yxs
0 = -DP + rg Yps (6.39)
SX
rg = m max
Ks + S

The model parameters and solution conditions may be used from the case study in Chapter 3.
The solution is given in the next example.
 Nonlinear Algebraic Equations   ◾    243

Example 6.5  Steady State in a Chemostat (Using “Vanilla” Newton-Raphson)

Problem: Determine the steady state concentrations of substrate (S), biomass (X), and
product (P) for the chemostat of Equation 6.39 using Newton-Raphson method.
Solution: Two functions, funMonod and jacMonod, are written as below to com-
pute g(x) and J(x), respectively. The former returns a 3 × 1 column vector, whereas
the latter returns a 3 × 3 Jacobian matrix for current values of input parameter x. The
Jacobian matrix is given by

é ¶rg ¶rg ù
ê -D - ¶S -
¶X
0 ú
ê ú
¶rg ¶rg
J = ê Yxs -D + Yxs 0 ú
ê ¶S ¶X ú
ê ¶r ¶rg ú
ê Yxs g Yps -D ú
êë ¶S ¶X úû

¶rg mXK ¶rg mS

where = , =
¶S ( K + S )2
¶X K + S

The function funMonod.m is similar to the one in Chapter 3:

function gVal=funMonod(C,monodParam)
mu=monodParam.mu; K=monodParam.K;
Yxs=monodParam.Yxs; Yps=monodParam.Yps;
D=monodParam.D; Sf=monodParam.Sf;
%% Variables to solve for
S=C(1); X=C(2); P=C(3);
%% Model equations
rg= mu*S/(K+S)*X;
gVal(1,1)=D*(Sf-S) - rg;
gVal(2,1)=-D*X + Yxs*rg;
gVal(3,1)=-D*P + Yps*rg;
end

The only difference in the above function being that it is a function of only C, and
not of time t, since a steady state solution is sought. The function jacMonod.m for
calculation of numerical Jacobian is

function J=jacMonod(C,monodParam)
mu=monodParam.mu; K=monodParam.K;
Yxs=monodParam.Yxs; Yps=monodParam.Yps;
D=monodParam.D; Sf=monodParam.Sf;
%% Variables to solve for
S=C(1); X=C(2); P=C(3);
244   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

%% Jacobian calculation
r_s=mu*X*K/(K+S)^2; % drg/dS
r_x=mu*S/(K+S); % drg/dX
J = [-D-r_s, -r_x, 0;
r_s*Yxs, -D+r_x*Yxs, 0;
r_s*Yps, r_x*Yps, -D];
end

The function g(C) and Jacobian J(C) can then be used in Newton-Raphson solver. The
driver script, monodRun.m, is given below:

% Chemostat using Vanilla Newton-Raphson

% Reactor parameters
monodParam.mu=0.5;
monodParam.K=0.25;
monodParam.Sf=5;
monodParam.D=0.1;
monodParam.Yxs=0.75;
monodParam.Yps=0.65;
% Initial guess for Newton-Raphson
C0=[0.25; 4.0; 4.0];
g=monodFun(C0,monodParam);
X=C0; G=g; % Storing results

% Newton Raphson Iterations

maxIter=25;
eTol=1e-8;
for i=1:maxIter
J=monodJac(X(:,i),monodParam);
X(:,i+1)=X(:,i)-inv(J)*g;
err=abs(X(:,i+1)-X(:,i));
if(max(err)<eTol)
return
end
g=monodFun(X(:,i+1),monodParam);
G(:,i+1)=g;
end

The value of the three state variables at steady state using the above code is

C = 0.0909 3.6818 3.1909

On the other hand, if the initial guess were changed to C0=[4; 1; 1], then

C = 5.0000 0.0000 0.0000

Note that the above signifies multiple coexisting steady states. This will be discussed
in further detail in Case Studies (Section 6.5).
 Nonlinear Algebraic Equations   ◾    245

The above example demonstrates steady state multiplicity. When there are no microor-
ganisms in the chemostat, no conversion of substrates into products occurs, and the out-
let stream contains unconverted substrate (at concentration of sf ), without any biomass or
product. On the other hand, for a range of values of dilution rate, D, there exists a steady
(
state C = éë0.091 3.68 3.19 ùû
T
) with a significant conversion of the substrate to the
product.
Numerically, Newton-Raphson suffers from a couple of problems. First, the intermediate
solutions may violate bounds on variables. For example, with C0=[4; 1; 1], the vari-
ous iterated values in the above Newton-Raphson example were

X =
4.0000 5.0281 5.0000 5.0000 5.0000
1.0000 -0.0211 -0.0000 -0.0000 -0.0000
1.0000 -0.0183 -0.0000 -0.0000 -0.0000

Note that the values of X and P at the first iteration are negative. This does not affect conver-
gence in Example 6.5. However, if the function g(C) included square root or logarithm of
C(2) or C(3), then Newton-Raphson would give complex values or fail. Another problem is
that while Newton-Raphson converges rapidly in the vicinity of the solution, x⋆, its global
convergence behavior is poor. That means starting from arbitrary initial guess, as would
be the case when the solution x⋆ is unknown, it often does not converge. It also fails if the
guess values or iterated values are close to local maxima or minima (where g′(x) is zero or
Jacobian is noninvertible). While this may not be a major issue for small problems (single to
a few variables), it can be a significant problem for Newton-Raphson in multiple variables.
Finally, the Jacobian may not be explicitly known. Some of these issues are discussed in the
rest of this section.

6.3.2 Modified Secant Method

I will tackle the “simplest” issue first: when the Jacobian is not explicitly available. In such
a scenario, one option is to compute numerical Jacobian (see Appendix B for numerical
integration):

(i )
J k ,l =
gk ({x} + h ) - g ({x} ) ,
(i )
l k
(i )
l
h = xl( ) ´10-8
i
(6.40)
h

(i )
Here, the notation {x}l represents that only the lth element of the vector x is changed,
and all other elements of x(i) are kept at their original values. We have used the forward
difference formula for numerical integration. While the central difference formula is more
(i )
( )
accurate, it involves an additional function calculation, g {x}l - h . The following example
shows the use of Newton-Raphson with numerical Jacobian.
246   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 6.6  Newton-Raphson with Numerical Jacobian

Problem: Solve Example 6.5 using Newton-Raphson with numerical Jacobian.
Solution: The driver script, monodRun.m, and the function, monodFun.m,
remain similar to the previous solution. The only difference being the first line of
the Newton-Raphson loop is replaced by numerical Jacobian calculation. Numerical
Jacobian is calculated in the following code:

function J=monodJacNum(x,g,par)
% This function takes the current value x(i) and g(i)
% and returns the numerical Jacobian
for l=1:3 % Cycle over all x(l)
xbracket=x;
h=abs(xbracket(l))*1e-8;
xbracket(l)=x(l)+h;
g1=monodFun(xbracket,par);
J(:,l)=(g1-g)/h;
end

The driver can now be executed with the numerical Jacobian replacing the previous
case of analytical Jacobian. The code takes exactly the same number of iterations and
converges to the same solution:

C = 0.0909 3.6818 3.1909

Since numerical Jacobian requires additional function calculation, multivariate secant

method is another option. The reader can verify that this method can be executed as

( )
-1
x ( ) = x ( ) - é B( ) ù g x ( )
i +1 i i i

ë û

(i )
Bk ,l =
( ) ( )
g k xl( ) - g k xl( )
i i -1

(6.41)

( x( ) - x( ) )
l
i
l
i -1

Broyden’s Method is a better method to calculate B(i) instead:

(- éëg )
T
(i )
- g ( ) ù - B( ) éd ( ) ù éd ( ) ù
i -1 i -1 i i
û ë û ë û
B( ) = B( )
i i -1
T
(6.42)
é d (i ) ù é d (i ) ù
ë û ë û

where d ( ) = x ( ) - x ( )
i +1 i +1 i
(6.43)

Broyden’s method is mentioned for the sake of completeness and will not be investi-
gated further.
 Nonlinear Algebraic Equations   ◾    247

6.3.3 Line Search and Other Methods

The issue of poor global convergence is a major problem for Newton-Raphson method.
A large portion of work in the literature is dedicated to this issue. Before discussing these
methods, let us define the following:

( ) ( )
-1
s( ) = é J x ( ) ù g x ( )
i i i
(6.44)
ëê úû

Note that in “vanilla” Newton-Raphson method

x ( ) = x ( ) - s( )
i +1 i i
(6.45)

Consider a scalar-valued function:

1
G ( x ) = gT g (6.46)
2

Since the above function is a quadratic function of real-valued vector, its minimum
value is 0. It is easy to see that the roots of g(x) form the minima of G(x). It can be shown
that the vector −s above provides the direction of steepest decrease in the value of G(x), and
thus the direction of steepest approach of g(x) to a root. Instability in Newton-Raphson
arises because the complete step may be too aggressive. In order to improve robustness, a
partial step may be taken:

x ( ) = x ( ) - ws( )
i +1 i i
(6.47)

There are various ways to obtain the line search parameter, ω. Several algorithms exist that
try to obtain ω in an “optimal” way. The key idea is to “search along the direction” −s such
that the most optimal reduction in the value of G(x(i + 1)(ω)) is obtained. Note that as per
Equation 6.47, the next iteration value x(i + 1) is written in terms of the parameter ω. This
is mentioned for the sake of completeness; the discussion of these methods is beyond the
scope of this text.
For the purpose of this section, I will discuss some heuristic ways to improve the per-
formance of Newton-Raphson. One simple way is to start with the full Newton-Raphson
step, that is, ω = 1. If the x(i) is in bounds and g(x(i)) has decreased, retain the step. Else, ω is
halved. This can be progressively done until a reasonable step is obtained. This back-tracing
process is repeated at each iteration.
Another option, which may work for certain specific problems (though it is not a gen-
eral purpose algorithm) is to choose an appropriate ω that works for the problem under
consideration. We often need to solve not a single problem but a family of problems involv-
ing the solution of nonlinear equations. For example, we may execute the simulation of
Example 6.5 for various different values of dilution rates (D), feed substrate concentration
(Sf ), or rate constants (μmax, Ks). One can set up a nominal case, and try the simulation
248   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

with  ω = 1. If that does not yield a solution, choose ω = 0.5 and keep it constant for all
maxIter iterations. If that does not converge, repeat for ω = 0.25, etc. It should be noted
that using lower values of ω would necessitate a larger number of iterations; so maxIter
should be a reasonably large number (~100 × n, where n is the number of equations to
be solved). I have usually used ω > 0.1, and very rarely have I had to use ω = 2−4 or 2−5, for
reasonably tough problems.
The next example demonstrates one simple way to use the line-search parameter ω to
avoid negative values of concentrations. As we will see in Chapter 7, this idea of under-
relaxation is used in other iterative numerical techniques as well. It is widely used in com-
putational fluid dynamics (CFD) and finite element software to ensure stable performance
of the solver.

Example 6.7  Newton-Raphson with Under-Relaxation

Problem: Repeat Example 6.5 with an appropriate value of ω to avoid negative values
of concentration.
Solution: Consider the solution of Example 6.5, where the first iteration values
starting from [4   1   1]T were

5.0281
-0.0211
-0.0183

Note that the step taken in value of S was 1.0281, while the maximum allowable step is
1 (since S cannot exceed Sf ). Based on this, we will redo Example 6.5 with ω = 0.9. The
following results are obtained:

4.0000 4.9253 4.9926 4.9993 4.9999 etc.

1.0000 0.0810 0.0080 0.0008 0.0001 etc.
1.0000 0.0835 0.0083 0.0008 0.0001 etc.

As can be seen above, negative values are avoided in the iterations. Moreover, it takes
nine iterations for Newton-Raphson to converge.

PERSONAL NOTE:
I personally find the dichotomy between line search and under-relaxation quite interesting.
I use the two terms replaceably, since the core idea is the same: to use the parameter ω to
slow down or speed up an iterative numerical technique. The term “line search” is often used
with the Newton-Raphson method (or optimization methods) when the aim is to find the
value ω so that the one approaches the solution (or minima) in the “best” manner. The term
“under-relaxation” is commonly used in Gauss-Siedel (Chapter 7) or in CFD, where the aim
is to slow down the steps in order to ensure robust and stable algorithm.
 Nonlinear Algebraic Equations   ◾    249

If the above heuristic ideas do not solve the problem, more advanced techniques based
on trust region or other methods (such as those used by MATLAB solvers) need to be
used. Besides, there exist other methods, rather than the one shown in Example 6.7, that
are designed for nonlinear equations in the presence of constraints. Either of these are not
within the scope of this book.

6.4 MATLAB® SOLVERS
MATLAB solvers for nonlinear algebraic equations are provided in the Optimization
Toolbox and are not available in the base MATLAB package. If optimization toolbox is not
available, one may need to write one’s own solution code based on algorithms discussed in
the previous sections. This section discusses two MATLAB methods, fzero and fsolve,
to solve single-variable and multivariable nonlinear equation problems, respectively.

6.4.1 Single Variable Solver: fzero

MATLAB function fzero is used to obtain a root of a single equation in one unknown.
It  uses a combination of Brent’s inverse quadratic interpolation (Section 6.2.2) and the
bisection method (Section 6.2.1). It typically requires two initial guesses that bracket the
solution, but also works with a single initial guess as well. The following reproduces infor-
mation help fzero, relevant to solving a nonlinear equation:

X = fzero(FUN,X0)
Find a zero of the function FUN near X0, if X0 is scalar.
X = fzero(FUN,X0), where X0 is a vector of length 2,
Assumes X0 is a finite interval where the sign of
FUN(X0(1)) differs from the sign of FUN(X0(2)).

Calling fzero with an initial interval (using X0 as a vector of length 2) guarantees fzero
will return a solution if it exists. The fzero algorithm first attempts an inverse quadratic
step; if that results in x(i + 1) that lies between x(L) and x(U), then the solution is accepted. If the
value x(i + 1) lies outside the interval, a bisection step is used instead. The solution v⋆ remains
bracketed all the time. I recommend using fzero supplying an initial interval (rather than
a scalar initial value), as seen in the next example.

Example 6.8  Using fzero for Redlich-Kwong EOS

Problem: Solve Example 6.1 using fzero.
Solution: The function file, RK.m, created to obtain g(v), can be used with fzero.
As before, the problem definition and preamble sections remain unchanged. For the
sake of completeness, the full code is given below:

% Molar volume using Redlich-Kwong EOS

% Model parameters for the EOS
param.a=6.46;
param.b=2.97e-5;
param.R=8.314;
250   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

% Operating conditions
param.P=1e7; % Pressure (Pa)
param.T=340; % Temperature (K)

%% Solution using fzero

vL=0.8e-4;
vU=2.2e-4;
vSol=fzero(@(v) RK(v,param),[vL,vU]);
disp(['Molar volume, v = ', num2str(vSol)]);

Note that the underlined line was the only line that was added to solve the problem
using fzero. The result using the above code is the same as those in the previous
examples:

Molar volume, v = 0.0001646

The above call to fzero uses default optimization parameters. User-specified options
can be supplied to fzero using

X = fzero(FUN,X0,OPTS)

where OPTS is a structure that can be created using the OPTIMSET command. Setting
options will be covered in the next section, while discussing fsolve.
If more information regarding the solution is required, the following output arguments
can be used with fzero:

[v,gVal,flag,info]=fzero(@(v) RK(v,param),[vL,vU]);

When used in the above example, the value returned for flag = 1, indicating that the
solution was found successfully by fzero. The following information is obtained from the
structure info: that fzero required seven iterations and it used a combination of bisec-
tion and Brent’s inverse quadratic interpolation methods.

6.4.2 Multiple Variable Solver: fsolve

In Example 6.8, let us replace the underlined command with the following:

>> vSol=fsolve(@(v) RK(v,param),vU)

With the above expression, I am using another nonlinear equations solver, fsolve, avail-
able in MATLAB (optimization toolbox). fsolve solves the above problem and returns
the value

vSol =
1.6460e-04

This solution is same as the ones obtained using other techniques in this chapter.
 Nonlinear Algebraic Equations   ◾    251

The syntax for using fsolve is similar. Let us go over the similarities and differences in
the usage of fzero and fsolve: (i) Like fzero, it requires users to supply function and
an initial guess, and (ii) unlike fzero (and similar to Newton-Raphson), fsolve accepts
only a single initial guess and not an interval. The second point is quite important because
fsolve is a multivariate solver for nonlinear equations of the type

g ( x ) = 0, x Î R n , g : R n ® R n (6.1)

The corresponding syntax for fsolve is

X = fsolve(FUN,X0)

where the size of vector X0 is n × 1, where n is the number of equations to be solved. Thus,
as per the above equation, the size of X0 and the size of function values returned by FUN
should be the same.
Coming back to the Redlich-Kwong example, the solution of the nonlinear equation is

v  = 1.646 ´ 10-4

fsolve uses the following default tolerance values: tolX=1e-6 and tolFun=1e-6.
With this option, the solution is considered to be converged if

x ( ) - x ( ) < tolX
i +1 i
(6.48)

( ) ( )
g x ( ) - g x ( ) < tolFun
i +1 i

(6.49)

Since the value of molar volume is expected to be of the order of 10−4 for this problem,
tighter tolerance values—at least four orders of magnitude lower—are recommended. The
tolerance values can be specified using the optimset command and then passing the
options structure to fsolve:

opts=optimset('tolX',1e-10,'tolFun',1e-10);
vSol=fsolve(@(v) RK(v,param),vU,opts);

With this change, the solution is now obtained with a more stringent set of error tolerance
values. I bring to your attention that in this particular example, higher tolerance values
resulted in almost the same solution. However, this is not always the case, and the tolerance
values should be carefully chosen based on the order of magnitude of the expected solution
x⋆ and the order of magnitude of the function g(x(0)).
Since fsolve is a multivariate solver, I will now use it for the chemostat example below.
252   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 6.9  Chemostat Solution Using fsolve

Problem: Use fsolve to obtain steady state values of chemostat from Example 6.5.
Solution: The function, funMonod, was written in Example 6.5 to compute g(x).
We will use this function with fsolve as shown in the code below:

% Driver script: monodRun_fsolve.m

% To demonstrate use of fsolve for Chemostat problem
%% Reactor parameters
monodParam.mu=0.5;
monodParam.K=0.25;
monodParam.Sf=5;
monodParam.D=0.1;
monodParam.Yxs=0.75;
monodParam.Yps=0.65;

%% Solving and displaying result

C0=[0.25; 4.0; 4.0];
X=fsolve(@(c) monodFun(c,monodParam),C0);
disp(X);

The result obtained using fsolve is the same as before:

0.0909
3.6818
3.1909

Let us now analyze the above problem a bit further. First, the solutions are concentrations
of substrate, biomass, and product. All of these are expected to be of the order ~ O (1). The
initial guess was C0=[0.25; 4.0; 4.0]. The function, monodFun, evaluated at this
initial condition gives

>> monodFun(C0,monodParam)
ans =
-0.5250
0.3500
0.2500

The typical values of the function g(x) computed by monodFun are of the order O ( 0.1).
Therefore, the default tolerance values of tolX=1e-6 and tolFun=1e-6 are suffi-
cient and need not be changed for this example. Although the readers know this, it still
is worth repeating that the initial guess and solution vectors C0 and X (respectively) are
3 × 1 vectors; the function monodFun returns g(x) as a column vector of the exact same
dimension.
 Nonlinear Algebraic Equations   ◾    253

6.5 CASE STUDIES AND EXAMPLES

6.5.1 Recap: Equation of State
The first example we considered was a demonstration of solving a single nonlinear equation
in one unknown in finding the molar volume for a system described by RK EOS:

RT a/ T
P= - (6.2)
v - b v (v + b)

The above equation was put in the standard form of nonlinear equations in one unknown as

v -b a
P ( v - b ) - RT + =0 (6.4)
v (v + b) T
  
g (v )

The above nonlinear equation was solved for given values of T and P to obtain the corre-
sponding molar volume, v.
Another popular EOS is Peng-Robinson EOS:

RT a
P= - (6.50)
V - b V (V + b ) + b (V - b )

An interested reader may use the above PR EOS and obtain the molar volume for given T
and P. You may choose the parameter values of a = 0.364 and b = 3 × 10−5.

6.5.2 Two-Phase Vapor-Liquid Equilibrium

Calculation of vapor-liquid equilibrium involves calculating dew point and bubble point
for a given system. Antoine’s equation will be used for calculating the saturation conditions:

b

( )
ln Pksat = a -
T + c
(6.51)

where
Pksat is the saturation pressure in kPa
T is the temperature in °C

Given a temperature, the above equation can be used to calculate the saturation vapor pres-
sure, or vice versa.
Now consider a mixture of two components. If the mixture obeys Raoult’s law, then the
vapor pressure of the component in the gas phase is simply the saturation pressure from
Equation 6.51 multiplied by its liquid-phase mole fraction:

pk = x k Pksat (6.52)
254   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

This can be used for vapor-liquid equilibrium (VLE) calculations. At the boiling point of
a pure fluid, the saturation pressure equals the total pressure.* In case of a mixture, we
equivalently calculate bubble point and dew point temperatures for the mixture at a given
pressure (or pressure at a given temperature) for various liquid- and gas-phase composi-
tions, respectively.

6.5.2.1 Bubble Temperature Calculation

In order to find bubble point for a two-component mixture, the following iterative proce-
dure is used. If T is the current guess of the bubble point, the saturation pressures of the two
components are given by Antoine’s equation (6.51). From Raoult’s law, the net pressure is
given by

P = x1P1sat (T ) + (1 - x1 ) P2sat (T ) (6.53)

The value of temperature that solves the above equation is the bubble point. Note that the
function g(T) is a single function in one variable, given by

P1sat (T ) P2sat (T )
1 - x1 + (1 - x1 ) =0 (6.54)
 P  P
gB (T )

Additionally, to obtain the initial guesses, we will use the property that the bubble point of
ideal mixture lies between the boiling points of the two individual species.

6.5.2.2 Dew Temperature Calculation

Given the vapor-phase composition and pressure, the partial pressure, ykP, for each compo-
nent is known. From Raoult’s law

y k P = x k Pksat (T ) (6.55)

where T is the guess value of dew temperature. Rearranging,

x1 =
yP 1 (1 - y1 ) P
, 1 - x1 = sat (6.56)
P (T )
1
sat
P1 (T )

Adding the two, we get a single function in one variable:

P P
1 - y1 sat + (1 - y1 ) sat =0 (6.57)
P1 (T ) P2 (T )

gD (T )

*  For example, at its boiling point of 100°C, the saturation pressure of water is 1 atm.
 Nonlinear Algebraic Equations   ◾    255

6.5.2.3 Generating the T–x–y Diagram

The above two can be used to generate a T–x–y diagram for a binary mixture of acetoni-
trile and nitromethane. Antoine’s coefficient for the two species is a =14.2724, b = 2945.47,
and c = 224.0 and a = 14.2043, b = 2972.64, and c = 209.0, respectively. The T–x–y diagram
involves generating the bubble and dew point curves and plotting them on the same plot.
This is demonstrated in the following example.

Example 6.10  T–x–y Diagram for VLE Calculations

Problem: Generate the T–x–y diagram for acetonitrile–nitromethane system for
Antoine’s vapor pressure parameters given above. Assume Raoult’s law holds.
Solution: We will use fzero to solve the two equations: Equation 6.54 to get the
bubble point and Equation 6.57 to get the dew point. These are two different cal-
culations, which will require separate function files (bublFun.m and dewFun.m,
respectively). These functions are given below:

function gB=bublFun(T,par)
% Bubble point residual function (6.54) for fzero
pSat=antoine(T,par); % Get pSat for both species
x=par.x;
P=par.P;
gB=1-x*pSat(1)/P-(1-x)*pSat(2)/P;
end

function gD=dewFun(T,par)
% Dew point residual function (6.57) for fzero
pSat=antoine(T,par); % Get pSat for both species
y=par.y;
P=par.P;
gD=1-y*P/pSat(1)-(1-y)*P/pSat(2);
end

Both these functions require antoine.m, which takes in the temperature and cal-
culates the saturation pressure of all the species using Equation 6.51. This function is
given below:

function pSat=antoine(T,par)
a=par.a;
b=par.b;
c=par.c;
pSat=exp(a - b./(T+c));
end

Note that the underlined command is vectorized with respect to the species. Given
Antoine’s coefficients for n species, it will return the saturation pressures Pksat for all the
species as a vector at the temperature T.
256   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Both the bubble point and dew point calculations are performed in the same driver
script VLEdriver.m. The calculations are performed in a loop, for a range of values
of x1 ∈ [0, 1] for bubble point and y1 ∈ [0, 1] for dew point:

% To obtain the T-x-y curve

% for acetonitrile-nitromethane mixture
% Antoine constants
par.a = [14.2724, 14.2043];
par.b = [2945.47, 2972.64];
par.c = [224.0, 209.0];
% Operating points
par.P=101.3; % 1 atm in kPa
n=20;
h=1/n;
for i=1:n+1
par.x=(i-1)*h;
par.y=(i-1)*h;
Tbubl(i)=fzero(@(T) bublFun(T,par), [50 150]);
Tdew(i) =fzero(@(T) dewFun(T,par), [50 150]);
end
% Plot the results
plot(0:h:1,[Tbubl; Tdew]);

Figure 6.5 shows the T–x–y curve for this system. The last point, corresponding to
x1 = 1, is the boiling point of acetonitrile, and the first point, corresponding to x1 = 0,
is the boiling point of nitromethane. The lower line is the bubble point curve, whereas
the upper line is the dew point curve.

This method can be easily extended to any system in m-components. Standard thermody-
namics texts use the example of ternary mixture of acetonitrile, nitromethane, and acetone

105

100

95
T (°C)

90

85

80
0 0.5 1
(x or y)acetonitrile

FIGURE 6.5  T–x–y diagram for acetonitrile-nitromethane mixture, with mole fraction of acetoni-
trile as the abscissa.
 Nonlinear Algebraic Equations   ◾    257

as a standard three-component example. Antoine’s coefficients of acetone are a = 14.5463,

b = 2940.46, and c = 237.22. This is left as an exercise.

6.5.3 Steady State Multiplicity in CSTR

An example of a nonisothermal continuous stirred tank reactor (CSTR) was discussed in
Chapter 3. This same example will be further discussed in Chapter 9 in context of stability
analysis and bifurcation in a formal way. Prior to that, obtaining steady state solutions for a
range of operating parameters will be considered in this section. The system being modeled
is shown in Figure 6.6. The model equations for the CSTR at steady state are given below
(also see Chapter 3):

é æ E ö ù
0 = F ( C A0 - C A ) - êk0 exp ç - ÷ CA ú V
ë è RT ø û
é æ E ö ù
0 = F rc p (T0 - T ) + ( -DH ) êk0 exp ç - ÷ C A ú V - UA (T - Tj ) (6.58)
ë è RT ø û
0 = Fj r j c j (Tj 0 - Tj ) + UA (T - Tj )

The parameters for this system are given in Table 6.1 (reproduced from Chapter 3). In
Chapter 3, an ODE solver (ode45) was used to obtain the transient simulation results
for the CSTR. After 50 s of operating time, the CSTR exit conditions were obtained
as CA = 461.0, T = 647.6, Tj = 472.6. Thereafter, the inlet temperature was reduced to
298 K, and the exit conditions obtained at the end of 200 s were CA = 3991, T = 298.8,
and Tj = 298.4.
Note the qualitative difference between the solutions obtained with T0 = 350  K and
T0 = 298  K. In the former case, there is significant conversion of the reactant and a

CA0, T0

Tj0

CA, T
Tj

FIGURE 6.6  A schematic of jacketed CSTR modeled in this case study

258   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

TABLE 6.1  Model Parameters and Operating Conditions for Jacketed CSTR
CSTR Inlet Cooling Jacket Other Parameters

F = 25 L/s Fj = 5 L/s CA0 = 4 mol/L

V = 250 L Vj = 40 L k0 = 800 s−1
ρ = 1000 kg/m3 ρj = 800 kg/m3 E/R = 4500 K
cp = 2500 J/kg · K cp = 5000 J/kg · K (−ΔH) = 250 kJ/mol
T0 = 350 K Tj0 = 25°C UA = 20 kW/K

corresponding increase in temperature. In the latter case, conversion is negligible, and

the reactor exit temperature is very close to the inlet temperature itself. Thus, we observe
a qualitative change in the nature of solution when an operating parameter, inlet tem-
perature T0 in this case, is varied. While the temporal evolution of modeled variables is
interesting, it is also important to study various steady state solutions. Before we move on
to study how the operating parameter affects steady state solution, I will discuss the use
of nonlinear equation solver to obtain steady state values of the modeled variables in the
next example.

Example 6.11  Steady State Solution of Nonisothermal CSTR

Problem: Obtain steady state solution for a CSTR described by Equation REF using
fsolve.
Solution: The transient solution of CSTR was already discussed in Chapter 3.
The development of the CSTR driver code and solver function follow similar lines
as the examples before. The function file, cstrFun.m, to compute g(x) is given
below.
Part-1: A first attempt at cstrFunTry.m:

function gVal=cstrFunTry(x,par)
%% Inlet and current conditions
C0=par.C0; T0=par.T0; Tj0=par.Tj0;
Ca=x(1); T=x(2); Tj=x(3);

%% Key Variables
rxnRate=par.k0*exp(-par.E/T)*Ca;
hXfer=par.UA*(T-Tj);
FRhoCp=par.F*par.rho*par.cp;
FjRhoC_j=par.Fj*par.rhoj*par.cj;

%% Model Equations
gVal=zeros(3,1);
gVal(1)=par.F*(C0-Ca)-rxnRate*par.V;
gVal(2)=FRhoCp*(T0-T)+par.DH*rxnRate*par.V-hXfer;
gVal(3)=FjRhoC_j*(Tj0-Tj)+hXfer;
 Nonlinear Algebraic Equations   ◾    259

Before discussing the CSTR driver script, let us check the values of g(x(0)). Based on
the solution obtained in the case study from Chapter 3, the value of initial guess is
chosen as:

x0=[500; 600; 470];

The value of g(x(0)) can be verified using

>> cstrFunTry(x0,modelPar)
ans =
1.0e+06 *
0.0000
-4.3979
-0.8400

The function file needs to be modified based on these observations, as discussed below.

The value of g1(x) is several orders of magnitude lower than the other two functions. As a
result, the three equations are modified as follows:
0 = F ( C A0 - C A ) - rAV

0 = (T0 - T ) +
( -DH ) rAV - UA (T - Tj ) (6.59)
F rc p
UA (T - Tj )
0 = (Tj 0 - Tj ) +
Fj r j c j
CSTR function file is now modified. The modified file is shown below.

Example 6.11  (Continued) Steady State Solution of Nonisothermal CSTR

The CSTR function is now written as

function gVal=cstrFun(x,par)
%% Inlet and current conditions
C0=par.C0; T0=par.T0; Tj0=par.Tj0;
Ca=x(1); T=x(2); Tj=x(3);

%% Key Variables
rxnRate=par.k0*exp(-par.E/T)*Ca;
hXfer=par.UA*(T-Tj);
FRhoCp=par.F*par.rho*par.cp;
FjRhoC_j=par.Fj*par.rhoj*par.cj;

%% Model Equations
gVal=zeros(3,1);
gVal(1)=par.F*(C0-Ca)-rxnRate*par.V;
260   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

gVal(2)=(T0-T) + (par.DH*rxnRate*par.V-hXfer)/FRhoCp;
gVal(3)=(Tj0-Tj)+hXfer/FjRhoC_j;

Let us now check the values of g(x):

>> cstrFun(x0,modelPar)

ans =
32.1916
-70.3663
-42.0000

Since the three elements of g(x) are of the same order of magnitude as the other,
this function will be used in solving the CSTR model equations. The driver script,
cstrDriver.m, is given below:

% Steady state solutions for jacketed CSTR

% with exothermic first-order reaction
%% Define model parameters (SI units)
modelPar.F=25/1000; % CSTR parameters
modelPar.V=0.25;
modelPar.rho=1000;
modelPar.cp=2500;

modelPar.Fj=5/1000; % Cooling jacket

modelPar.Vj=40/1000;
modelPar.rhoj=800;
modelPar.cj=5000;

modelPar.k0=800; % Rate constants

modelPar.E=4500;
modelPar.DH=250000;
modelPar.UA=20000;

%% Define inlet conditions

modelPar.C0=4000;
modelPar.T0=350;
modelPar.Tj0=298;
%% Solving using fsolve
x0=[500; 600; 470];
[X,gVal]=fsolve(@(x) cstrFun(x,modelPar), x0);

When the above script is executed, fsolve converges and value of X returned is:

X = [458.6 mol/m3; 648.1 K; 473.1 K]

( )
The value of gval at the above conditions is of the order ~ O 10-10 , indicating that
the solution is converged.
 Nonlinear Algebraic Equations   ◾    261

Furthermore, there isn’t just one solution at this value of T0 = 350 K. There are, in fact, three
solutions, as demonstrated in the example below.

Example 6.11  (Continued) Steady State Solution

of Nonisothermal CSTR (Multiple Steady States)
Problem: Find all the three solutions at T0 = 350 K.
Solution: The other solution corresponds to the case of nearly no conversion of A.
Thus, choose x(0) = [C0; T0; Tj0]:

>> x0=[4000; 350; 298];

>> [X,gVal]=fsolve(@(x) cstrFun(x,modelPar), x0);

This leads to the other solution, x = [3918.8 mol/m3;   349.8 K;   323.9 K].

In fact, there exists a third solution as well, for which intermediate values are c­ hosen
as initial guess*:

>> x0 = [2000; 500; 400];

>> [X,gVal]=fsolve(@(x) cstrFun(x,modelPar), x0);

This leads to the third and final solution, x = [2450.2 mol/m3; 476.4 K; 387.2 K].

(
In all the three cases, the value of gVal returned by fsolve was O 10-8 , indicating that the )
function g(x⋆) is converged successfully.

6.5.4 Recap: Chemostat
The chemostat example was covered in Section 6.4.2 (Example 6.9). It involved solving
three equations in three unknowns simultaneously:

0 = D ( S f - S ) - rg
0 = -DX + rg Yxs
0 = -DP + rg Yps (6.39)
SX
rg = m max
Ks + S

The code for solving this problem is given in Example 6.9.

Just like Section 6.5.3, multiple steady states can be shown for a chemostat as well. This is
left as an exercise for the readers.

*  At this stage, this is being presented as trial and error. The case study in Chapter 9 will provide specific details on how to
obtain a reasonable initial guess close to the solution.
262   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

6.5.5 Integral Equations: Conversion from a PFR

Most of the problems in chemical engineering involve algebraic equations or differential equa-
tions. Another class of equations is known as integral equations. Ivar Fredholm extensively
studied integral equations. The following is Fredholm integral equations of the first kind:

ò
f ( x ) = K ( x ,s ) j ( s ) ds
a
(6.60)

Note that f(x) is a function of x only, and not of s. A related equation is Volterra integral
equation of the first kind:

ò
f ( x ) = K ( x ,s ) j ( s ) ds
a
(6.61)

The main difference is that one of the limits of integration is also the variable x. The main
crux of integral equations is that the left-hand side f(x) is known. The function K(x, s) is
called kernel function and is also known.
Consider the design equation of a plug flow reactor (PFR) (see Chapter 3) with an inlet
concentration of reactant as 1 mol/m3:

Cout
V dC

Q
=-
ò r (C )
1
(6.62)

In Chapter 3, we integrated the above to find the volume of the PFR that achieves 75% con-
version. In other words, Q and Cout were known, whereas V was unknown. This was there-
fore a straightforward numerical integration problem. We used an ODE solver in Chapter 3
when we asked the question, “find the conversion from a reactor of volume 0.125 m3.” Let
us now see an alternative way to pose the problem as nonlinear integral equation and solve
the problem using techniques from this chapter.
If the volume is given, the right-hand side is known, whereas the upper limit of integra-
tion (Cout) is the unknown to be found. Thus, x ≡ Cout in Equation 6.61. Rearranging the
above equation

Cout
V dC
Q
+
ò r (C )
=0 (6.63)
 1 
g ( Cout )

The aim of the nonlinear equation solver is to compute the Cout that is achieved in a PFR
with residence time, V/Q = 1.25 s. We will do this for two cases: first-order reaction and a
 Nonlinear Algebraic Equations   ◾    263

complex kinetic model from Chapter 3. In either case, the nonlinear equation (6.63) to be
solved may be written as

V
g ( Cout ) º + I ( Cout ) = 0 (6.64)
Q

In the first example, since the reaction is first-order, the integral I(Cout) can be solved ana-
lytically. The analytical and numerical ways of solving for first-order reaction will be con-
sidered in the next section for pedagogical reasons. Thereafter, complex kinetic expression
that requires numerical solution is covered in Section 6.5.5.2. A more experienced reader
may skip Section 6.5.5.1 and go directly to Section 6.5.5.2.

6.5.5.1 First-Order Kinetics
When the reaction is a first-order reaction (r = kC), the integral is given by

1 Cout 1
I ( Cout ) = éë ln ( C ) ùû = ln ( Cout ) (6.65)
k 1 k

When substituted in Equation 6.63, we get a nonlinear equation in one unknown (Cout),
which can be solved using fzero, as shown in the next example.

Example 6.12  PFR Using Integral Equation Approach

Problem: Simulate the PFR using integral equation approach. The first-order reaction
rate is given by r = kC, with k = 0.5 s−1. The inlet concentration is 1 mol/m3, PFR vol-
ume is 0.125 m3, and flowrate is 0.1 m3/s.
Solution (Part-1): We will solve this problem using fzero. From the residence
time and rate constant, we know that the conversion lies somewhere between 1%
and 99%. The parameters are specified in the driver script, pfrIntegralSoln.m,
which uses fzero. The parameter definitions are similar to the ones we have seen in
Chapter 3.

% Script for simulation of a PFR

% using integral equation approach
Acs=0.25;
L=0.5;
modelParam.k=0.5;
modelParam.Q=0.1;
modelParam.V=L*Acs;

%% Solve and obtain outlet concentration

C0=[0.01, 0.99]; % Initial guess for fzero
Csol=fzero(@(Cout) pfrIntFun(Cout,modelParam),C0);
264   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

X=(1-Csol)/1; % Conversion
X=round(X*100,1); % ... in percentage
disp(['Conversion = ',num2str(X),'%']);

We can compute the true value of concentration and error in numerical computation as

Ctrue = exp(-V*k/Q);
err=abs(Csol-Ctrue);

The above driver calls the function pfrIntFun.m, which calculates g(Cout) from
Equation 6.64. This function is given below:

function gVal=pfrIntFun(Cout,par)
% To calculate g(Cout) for simulating a PFR
% using integral equation approach
% where, g = V/Q + I(Cout)
% V/Q is the residence time
% I is integral [dC/r] at given Cout

%% Calculating integral
intValue=log(Cout)/par.k;
%% Calculate g(Cout)
gVal=par.V/par.Q + intValue;

The conversion is found to be 46.5%. The error using the above approach is ~ O 10-16 . ( )
One of the important features of numerical techniques is that the function (g(Cout) or
I(Cout) in this example) does not need to be explicit; it can equivalently be implicitly cal-
culated. The design problem was solved in Chapter 3, wherein the volume was obtained
after calculating the integral using MATLAB function trapz.* Thus, the numerical
solution that employs trapz can be used instead of the analytical solution. This would
mean replacing the underlined sections of the function file pfrIntFun.m (in the code
given above) with a numerical approach that uses trapz. This is shown in the example
below.

Example 6.12  (Continued) PFR Using Integral Equation Approach

Solution (Part-2): The aim of the problem was to write a general code that computes
I(Cout) by evaluating the integral numerically and use this to compute g(Cout). This is
done by replacing the underlined lines of code with numerical integral. The driver

*  See Appendix D for more information on the trapezoidal rule for integration. The MATLAB function trapz that implements
the trapezoidal rule is also discussed in the appendix.
 Nonlinear Algebraic Equations   ◾    265

script, pfrIntegralSoln.m, remains unchanged. The actual pfrIntFun.m

function that we will use is given below:

function gVal=pfrIntFun(Cout,par)
% To calculate g(Cout) for simulating a PFR
% using integral equation approach
% where, g = V/Q + I(Cout)
% V/Q is the residence time
% I is integral [dC/r] at given Cout
%% Calculating integral using trapz
n=50; % number of intervals
h=(1-Cout)/n; % step-size for integration
C=1:-h:Cout;
r=par.k * C;
intValue=trapz(C,1./r);
%% Calculate g(Cout)
gVal=par.V/par.Q + intValue;

Compare this modified code with the previous one to notice that the underlined sec-
tion of the previous code (titled “Calculating integral”) is replaced with the
section titled “Calculating integral using trapz”). There is no other
change. With this change, the error in computing Cout is expected to be higher, since
it will be governed by the error in computing the integral. With n = 50 points used to
compute the integral using trapezoidal rule, the following results were obtained:

Conversion = 46.5%
>> disp(err)
9.5955e-06

It is also possible to check the effect of the number of intervals on the solution. When
the number of intervals was increased by one order of magnitude to n = 500, the error
in calculation of Cout decreased by two orders of magnitude. With n = 500

>> disp(err)
9.5967e-08

This observation may be attributed to the fact that the global truncation error in trap-
( )
ezoidal rule* is O h2 , where h = (Cin − Cout)/n.

The primary take-home message from this example is that a numerical technique is agnos-
tic to how g(Cout) was computed, either as a closed-form expression as per Equations 6.64
and 6.65, or whether integral required in g(Cout) is calculated numerically. Equipped with
this, we proceed to solve the original problem of simulating a PFR with complex kinetics.

*  See Appendix D for more information on the trapezoidal rule for integration. The MATLAB function trapz that implements
the trapezoidal rule is also discussed in the appendix.
266   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

6.5.5.2 Complex Kinetics
We are now ready to solve the original problem, which was to find the variation in out-
let concentration from a PFR as a function of length of the PFR, given the kinetic rate
expression:

kC
r=
1 + KrC2 (6.66)
-1 -2 6
where k = 2 s , K r = 1 mol × m

The nonlinear equation to be solved, (Cout) = 0 , is given by Equation 6.64, where the integral
I(Cout) is computed numerically using trapz:

Cout
dC
I ( Cout ) =
òr (C )
(6.67)


1  
trapz ( C ,1./r )

This is shown in the following example.

Example 6.13  PFR with LH Kinetics Using Integral Equation Approach

Problem: Modify Example 6.12 to solve the PFR with LH kinetics of Equation 6.66 to
obtain outlet concentration as a function of PFR length.
Solution (Part-1): First, let us consider the problem of finding outlet concentration
for 0.5 m length (volume = 0.125 m3). The driver script from Example 6.12 remains
unchanged, except for providing the correct rate constants:

modelParam.k=2;
modelParam.Kr=1;

In the function file, the reaction rate term from first-order kinetics is modified for the
rate expression (6.66), as was covered in Chapter 3. The modified code is given below,
with the changes underlined:

function gVal=pfrIntFunLH(Cout,par)
% This function calculates g(Cout) for simulating
% a PFR using integral equation approach
% where, g = V/Q + I(Cout)
% V/Q is the residence time
% I is integral [dC/r] at given Cout
k=par.k;
Kr=par.Kr;
 Nonlinear Algebraic Equations   ◾    267

%% Calculating integral using trapz

n=500; % number of intervals
h=(1-Cout)/n; % step-size for integration
C=1:-h:Cout;
r=k*C ./ sqrt(1+Kr*C);
intValue=trapz(C,1./r);
%% Calculate g(Cout)
gVal=par.V/par.Q + intValue;

The solution obtained using the above code is same as that obtained in Chapter 3:

Conversion = 87.8%

Now that the above code gives the appropriate conversion from PFR, we now need to mod-
ify the driver script. We will solve the integral equation problem for 10 different lengths
(L=0:0.05:5), store the solution in a vector (XOUT in the following script), and plot the
conversion vs. length. The resulting script is given below.

Example 6.12  (Continued) PFR Using Integral Equation Approach

% Obtaining conversion vs. length of PFR
% using integral equation approach
Acs=0.25;
L=0:0.05:0.5;
modelParam.k=2;
modelParam.Kr=1;
modelParam.Q=0.1;

%% Solve for various reactor lengths

XOUT=zeros(size(L)); % For storing results
C0=[0.01, 0.99]; % Initial guess for fzero
for i=2:length(L)
modelParam.V=L(i)*Acs;
Csol=fzero(@(Cout) pfrIntFunLH(Cout,modelParam),C0);
X=(1-Csol)/1; % Conversion
X=round(X*100,1); % ... in percentage
XOUT(i)=X;
end
plot(L,XOUT,'-bo');
xlabel('PFR length (m)'); ylabel('% conversion');

The results are shown in Figure 6.7. These results are the same as those obtained for
the same problem using the ODE-solving approach in Chapter 3. This demonstrates
the validity of the integral equation solving approach shown here.

I will end this section with some perspective about this problem. Simulating the behavior
of reacting species in a PFR is more conveniently handled using ODE solution techniques.
268   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

100

80

% Conversion
60

40

20

0
0 0.1 0.2 0.3 0.4 0.5
PFR length (m)

FIGURE 6.7  Conversion vs. length of PFR for LH kinetics using integral equation solving approach.

The  intent of this case study was to demonstrate alternative routes to solving the same
­problem. However, more importantly, it was to introduce readers to the fact that nonlin-
ear equation solving techniques are more general than what we would typically catego-
rize as “root finding”; these methods can be used for problems that can be cast into the
form g(x) = 0, where one needs to find x that satisfies these equations. The nature of g(⋅)
need not be explicit; it could be implicitly specified or obtained as a solution using another
numerical procedure. Finally, this case study also introduces the reader to integral equa-
tions. Although uncommon in chemical engineering, integral equations sometimes arise in
some problems involving radiation.

6.6 EPILOGUE
Solving ODEs and nonlinear algebraic equations form two of the most important classes of
examples of interest to chemical engineers. While Chapter 3 focused on ODEs, this chapter
focused on solving nonlinear equations of the form

g ( x ) = 0 (6.1)

I used the same approach in this chapter as in Chapter 3. An example of finding the molar
volume of a real gas using EOS was used to motivate the problem. This is an example of a
single-variable nonlinear equation solving problem.
Thereafter, several methods for solving algebraic equations were discussed in Section 6.2.
Starting with single-variable problem, theoretical results for selected numerical methods
were discussed. Rather than focusing on derivations, the aim of this chapter was to high-
light the practical implications in solving problems of interest. Numerical methods for solv-
ing general algebraic equations of the type (6.1) fall into two categories: bracketing methods
and open methods. In the case of the former, two initial guesses always “bracket” a solution,
whereas this requirement is not applicable for open methods.
 Nonlinear Algebraic Equations   ◾    269

MATLAB provides several algorithms for solving nonlinear equations. The two more
popular and versatile algorithms provided in MATLAB are fzero and fsolve. The
former is a single-variable solver that preferably uses a bracketing method, whereas the
latter is a multivariable general purpose solver. The single-variable bracketing meth-
ods were introduced in Section 6.2 to help readers make informed choices while using
fzero algorithm. Newton-Raphson and its variants, which are the most popular non-
linear equation solving algorithms, were discussed in some detail. This highlights features
and limitations of nonlinear equation solving algorithms and several variations used to
address those limitations.
Solving coupled nonlinear equations for large-dimensional problems can sometimes be
a tough problem to tackle. A few practical guidelines that I personally follow for MATLAB
are summarized below.

(A) Single-variable problem: fzero is my preferred algorithm for single-variable prob-

lems. It is more robust when two permissible initial guesses are provided, although it
works with a single initial guess as well.
The multivariable problems can be tougher, with fsolve being the primary
­algorithm geared toward solving nonlinear equations.

(B) Choosing appropriate step tolerances: Convergence metrics is an important point that
needs to be stressed in this summary. The importance of using solver options was
introduced in Section 6.4. Convergence is verified using tolerance on the step

x( ) - x( ) < e
i +1 i
(6.48)

or the change in function values

( ) ( )
f x( ) - f x( ) < d
i +1 i

(6.49)

The default values for both the tolerances in MATLAB are 10−6. In the EOS e­ xample,
since the molar volume was ~1.6 × 10−4, a more stringent stopping criterion for ε
(tolX optimizer option in MATLAB) was used. Similar care is required with respect
to the stopping criterion δ as well (tolFun optimizer option in MATLAB).
(C) Choosing appropriate function tolerances: Consider the following:

>> fsolve(@(x) (x-1)^3, 2)

Equation solved.
<...>
ans =
1.0390
270   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

0.5

g(x) = (x–1)3
0
0.5 1 1.5
x
–0.5

–1

FIGURE 6.8  g(x) vs. x for g(x) = (x − 1)3.

where a rather “simple” problem of solving g(x) ≡ (x − 1)3 = 0 gives an unexpected

result. The solver has converged because the default function tolerance of 10−6 is
met, even though there is ~3.9% error in the x⋆ value. The reason for this behavior
can be traced to the nature of g(x) plotted in Figure 6.8. Since the function value
changes slowly near the solution, gradient-based methods such as Newton-Raphson
or fsolve face issues close to the solution.
Two options* can be used to address the issue of this premature convergence: (i)
specifying a more stringent function tolerance and/or (ii) trying to solve βg(x) = 0
instead. The optimization option

>> opt=optimset('tolFun',1e-10);

will set a more stringent error tolerance, whereas

>> fsolve(@(x) 1e6*(x-1)^3, 2, opt)

finally gives the expected result.

(D) Verifying if converged solution is “reasonable”: The next question that comes up
is how do we know if the convergence is reasonable for a general function g(x)? A
reasonable rule of thumb is that we usually have some idea of the expected solution
value, which is often provided as an initial guess, xguess. One can evaluate g(xguess) and
( ( ))
choose a value for d ~ O 10-5 g x guess or lower. While this provides a reasonable
starting point, it is not guaranteed to work. For example, at the solution x=1.039,
the value of g(x) = 5.94 × 10−5 seems reasonable. However, when the solver is exe-
cuted with tolFun=1e-8, the solution changes to x=1.017; further reducing
tolFun=1e-10, the solution changes further to x=1.0077. Although the value of

*  Several users implicitly do not trust fsolve for its “inability” to solve such apparently simple problems. A problem that is
easy to solve for humans may not be easy for numerical technique. Problems of the nature g(x) = (x − 1)n or g(x) = xn − 1 are
textbook examples for exercising caution while using gradient-based solvers (Newton-Raphson, secant, or fsolve). This
book is intended to equip readers to understand why the method appears to fail and how to make it work.
 Nonlinear Algebraic Equations   ◾    271

g(x) computed was small, experimenting with different values of tolFun indicates
whether solution returned by fsolve is reasonable.*
(E) When solver does not converge: Solver may not converge even after attempting to solve
the problem with several different initial guesses. In such a case, the problem may be
reformulated. For example, material balance equation in CSTR
é æ E ö ù
0 = F ( C A0 - C A ) - êk0 exp ç - ÷ CA ú V (6.58)
ë è RT ø û

may be rearranged as

æ E ö æ CA ö
0 = 1 - k0 texp ç - ÷ç ÷ (6.68)
è RT ø è C A0 - C A ø

Alternatively, the model may be non-dimensionalized by defining ξ = CA/Cref and

θ = T/Tref. Converting variables into non-dimensional form and reformulating the
balance equations is a popular method to attempt, if the original function shows dif-
ficulty converging.
(F) Writing one’s own code when all else fails: When all else fails, writing one’s own mod-
ified Newton-Raphson code (see Section 6.3.3) can be attempted. Alternatively, or
additionally, analytically computed Jacobian may be provided to the solver. Analytical
Jacobian can sometimes prove useful in convergence of system of equations that are
otherwise difficult to converge. When I have chosen to write my own code, I have used
an appropriate under-relaxation factor in the range 1 2 to 1 16.

This brings us to the end of this chapter, where we focused on solving a generic system of
equations. Discretization of ODE-BVPs (boundary value problems) or partial differential
equations (PDEs) result in a set of nonlinear equations with a specific structure. Methods
that exploit the special structure and iterative methods that build upon the concept of
under-relaxation will be the focus of Chapter 7.

EXERCISES
Problem 6.1 Peng-Robinson Equation of State

RT a
P= - (6.50)
V - b V (V + b ) + b (V - b )

is another EOS that overcomes some of the limitations of RK-EOS dis-

cussed in this chapter. It is especially accurate in predicting properties of

*  Changing the tolFun will only affect the results when the function tolerance criterion causes fsolve to converge
(i.e., change in the function value is less than the function tolerance). If instead fsolve convergence is due to other rea-
sons, it is sufficient to verify if the function value at the solution, g(x⋆) is lower than a desired threshold.
272   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

nonpolar molecules and is able to predict liquid-phase properties accurately

as well. Use the PR EOS to obtain the molar volume for given T= 340 K and
P = 100 bar. You may choose the parameter values of a = 0.364 and b = 3 × 10−5.
Problem 6.2 Use fixed point iteration to solve the problem in Example 6.3 and compare
with the results discussed in Section 6.2.3.
Problem 6.3 Wegstein’s method is a numerical method used by several commercial
process simulation packages such as Aspen Plus. Wegstein’s method is an
enhancement of the fixed point Iteration to solve problems of the form

x = G ( x ) (6.18)

Starting with the initial condition, x(0), the next iteration value is obtained as
x(1) = G(x(0)). Thereafter, subsequent iteration values are obtained as
i +1 i
( )
x ( ) = qx ( ) + (1 - q ) G x ( )
i

G ( x ) - G ( x( ) )
(i ) (6.69)
i -1
S
q= , S=
S -1 x( ) - x( )
i i -1

Use Wegstein’s method to solve the problem in Example 6.3.

Problem 6.4 Consider Equation 6.69 of Wegstein’s method.
Easy: Show that when q is a constant, Equation 6.69 is fixed point iteration
with relaxation.
Medium: When S is replaced by the slope, dG/dx, show that Wegstein’s
method in one variable is equivalent to Newton-Raphson for g(x) = G(x) − x.
Problem 6.5 The terminal settling velocity of a particle is given by the following force
balance:
1 2 2
rv CD = d p ( r p - r ) g
2 3
where the drag coefficient is given by
ì 24
ï Re if Re £ 1
ï
24 4
CD = í + 0.33 if 1 < Re £ 1000
ï Re Re
ï0.44 if 1000 < Re
î

Compute the terminal settling velocity of a spherical particle of diameter

2 mm falling through water (ρ = 1000 kg/m3, μ = 8 × 10−4 kg/m · s). The den-
sity of the particle is ρp = 2400 kg/m3.
 CHAPTER 7

Special Methods for Linear

and Nonlinear Equations

7.1 GENERAL SETUP
Numerical methods for solving algebraic equations were covered in Chapter 6, wherein a
generic problem of finding root(s) of the following set of equations was discussed:

g ( x ) = 0 (7.1)

where
x ∈ R n is an n-dimensional column vector
g : R n → R n is an n-dimensional vector function

A specific case is when the above system of equations is linear. One could then write
g = Ax − b, and the equations to be solved are a set of linear equations:

Ax = b (7.2)

with
A ∈ R n´n is a matrix
b ∈ R n is a column vector

The standard methods for solving linear equations that are based on Gauss Elimination are
introduced in Appendix C. A significant amount of time is devoted to Gauss Elimination
and related methods in typical numerical techniques books. Since MATLAB® provides
powerful tools for solving linear equations, we are simply going to use them in this book.
The methods for nonlinear equations in Chapter 6 and linear equations in Appendix
C are general-purpose methods. These methods do not make any assumption about the
structure of the function g(x) or the matrix A, respectively. However, in a large number of

273
274   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

engineering problems of interest, g(x) and/or A have a particular sparse structure. These
structures of the functions/matrix can be exploited to solve the problems efficiently. This
chapter focuses on problems where g(x) and/or A have banded structures.

7.1.1 Ordinary Differential Equation–Boundary Value Problems

We will specifically look at examples of ordinary differential equation–boundary value
problems (ODE-BVPs) in this chapter and solve them using a finite difference approach.
A general second-order ODE-BVP is given by

d 2f æ df ö
a = f ç x , f, (7.3)
dx 2
è dx ÷ø

Two conditions are required for solving the above problem. If the two conditions are pro-
vided at the same initial location, the above can be converted into a set of two first-order
ODE-IVP. However, there are several occasions when the conditions for the above are spec-
ified at two different boundaries. This leads to ODE-BVP.
The boundary conditions are of three types:

Dirichlet boundary condition, where the value of variable ϕ is specified at a location:

1.

f ( x0 ) = a (7.4)

Neumann boundary condition, where the derivative ϕ′ is specified at a location:

2.

f¢ ( x0 ) = b (7.5)

Mixed boundary condition:

3.

f¢ ( x0 ) = af ( x0 ) + b (7.6)

Either of these boundary conditions is applied at each end of the computational domain.

7.1.2 Elliptic PDEs
Another set of problems that have qualitatively similar numerical features are elliptic PDEs,
which were introduced in Chapter 4. Systems that are governed by elliptic PDEs are those
where diffusive behavior is important, and therefore, conditions at all the boundaries affect
the solution value at any point within the domain. Owing to these common physical fea-
tures, a similar approach to solving and analyzing these systems can be used. A typical
elliptic PDE in 2D is given by

¶2f ¶2f æ ¶f ¶f ö
Gx 2
+ G y 2
= f ç x ,y ,f, , ÷ (7.7)
¶x ¶y è ¶y ¶y ø
 Special Methods for Linear and Nonlinear Equations   ◾    275

The above PDE is solved subject to two boundary conditions in each direction. As in the
case of ODE-BVP, these may be Dirichlet (Equation 7.4), Neumann (Equation 7.5), or
mixed (Equation 7.6) boundary conditions.
If convection dominates in one of the directions (e.g., Γx ≈ 0), the problem reduces to par-
abolic PDE; if diffusion is negligible in both directions, we get first-order hyperbolic PDEs.
Methods for solving hyperbolic and parabolic PDEs were discussed in Chapter 4.

7.1.3 Outlook of This Chapter

Before starting with the numerical techniques, I would like to draw the attention of the
readers to one difference between handling of sparse and banded systems in this book.
In standard numerical techniques textbook, the tridiagonal methods (Section 7.2) are dis-
cussed in the Linear Equations section immediately after Gauss Elimination, almost exclu-
sively in the context of linear equations. Iterative methods for solving linear equations
(Section 7.3), such as Gauss-Siedel, are traditionally discussed independently of iterative
nonlinear equations methods. Since this book takes a practical outlook toward solving
engineering problems, banded methods and iterative methods are clubbed together in this
“Special Methods” chapter.
The next section introduces the reader to problems involving such banded structures,
followed by so-called direct methods to solve the problems. Direct methods are related
to Gauss Elimination (see Appendix C), but where the banded structure of matrix A is
exploited to solve the linear problem (7.2) more efficiently. Thereafter, Section 7.3 discusses
iterative methods for solving such problems, where both linear as well as nonlinear equa-
tions of the form (7.1) will be discussed. Finally, Section 7.4 expands the linear banded
diagonal methods to specific examples of nonlinear equations. Finally, case study exam-
ples are discussed in Section 7.5. Advanced readers interested in learning MATLAB-based
problem solving for chemical engineers may directly skip to this section for examples.

7.2 TRIDIAGONAL AND BANDED SYSTEMS

7.2.1 What Is a Banded System?
Consider the linear equation (7.2). The matrix A is said to be sparse if only a small fraction
of its elements Ai,j are nonzero, whereas the rest of them are zero. Furthermore, it is said to
be banded if these nonzero elements occur “close” to the diagonal, that is, Ai,i ± ℓ are nonzero.
In this case, ℓ is the bandwidth of the system.* Let us take a closer look at what this means
for ith equation:

Ai ,i - xi - +  + Ai ,i xi +  + Ai ,i +  xi +  = bi (7.8)

Thus, the elements in the ith equation depend only on the previous and subsequent ℓ ele-
ments. Extending this idea to nonlinear equations, the ith function gi(x) is such that it
depends only on (xi − ℓ,  … , xi + ℓ), and it does not depend on (x1,  … , xi − ℓ − 1) or (xi + ℓ + 1,  … , xn).
Alternatively, the Jacobian matrix, at any x ∈ ℛn, has the sparse structure with bandwidth ℓ.

*  The number of subdiagonal and superdiagonal elements need not be equal. I have taken the two to be equal for ease of
discussion. The band could span i − ℓsub to i + ℓsuper for ith row.
276   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

7.2.1.1 Tridiagonal Matrix
A tridiagonal matrix is a matrix with ℓ = 1, that is, a matrix where only the diagonal element,
one subdiagonal element, and one superdiagonal element are nonzero. An example of a
tridiagonal system was seen in Chapter 4, when we implemented method of lines, which
used the finite difference formula on the spatial derivative ∂/∂z and ∂2/∂z2.
Sometimes, it becomes important to view the structure of a banded/sparse matrix while
solving or debugging a problem. MATLAB provides a command, spy(A), that can be
used to visually inspect the structure of a matrix. This generates a plot with n rows and
columns, with the nonzero elements of A indicated with markers on the plot. I will use this
command to investigate some of the common banded structures we are likely to encounter
in chemical engineering problems.
Figure 7.1 shows some common sparse structures. Tridiagonal and banded structures
were discussed earlier. For the specific band-diagonal example in the figure, ℓ = 3. The third
common example is that of block-diagonal structure. This is quite similar to the band-diag-
onal structure but with some additional elements zero as well. A closer look at Figure 7.1
(bottom left) reveals that the overall structure contains a single block that is repeated four
times. The reason it is called block-diagonal is because one can imagine a 4 × 4 block, each
block containing a matrix. Only the diagonal blocks are nonzero, whereas the others are
a matrix of zeros. These repeating diagonal blocks have full or sparse structures. Finally, a
multibanded structure is self-explanatory in that it contains additional nonzero bands, as
seen in Figure 7.1.

7.2.2 Thomas Algorithm a.k.a TDMA

I will follow the same pattern in this chapter as well: Rather than a general description
of the Thomas algorithm, or the tridiagonal matrix algorithm (TDMA), we will first

(a) (b)

(c) (d)

FIGURE 7.1  Some of the common sparse structures, examined by MATLAB® spy command.
(a) Tridiagonal, (b) banded, (c) block-diagonal, and (d) multiband.
 Special Methods for Linear and Nonlinear Equations   ◾    277

discuss an example and use it to set up the problem. Thereafter, the TDMA will be dis-
cussed in the context of this problem.

7.2.2.1 Heat Conduction Problem

Heat conduction in a 1D structure is a commonly used example in various disciplines of
engineering and physics. Metallic fin or mesh structures are routinely used for improved
heat dissipation. You would have seen such structures in car radiators, old refrigerators,*
CPU fans with heat sinks in a computer, etc. For the sake of simplicity, let us model a single
rod in this assembly. The idealized model consists of a single metal, which has its one end
connected to the hot equipment and the other end exposed to atmosphere such that it dis-
sipates heat to the surroundings. This is schematically shown in Figure 7.2.
The heat transfer with heat loss in this rod is modeled as
d 2T
k = h¥ av (T - T¥ ) (7.9)
dz 2

T ( 0 ) = T0 , T ( L ) = T¥ (7.10)

where
T is the temperature at any location in °C
T∞ is the temperature of the ambient
k is the thermal conductivity of the rod
h∞ is the heat loss coefficient
av is the external area of the rod per unit volume

For a cylindrical rod, av = 2/r. The above problem is an ODE-BVP, since the conditions are
specified at two separate boundary points, z = 0 and z = L. Before moving to the numerical
solution, let us discuss the true solution that can be obtained analytically since the above is
a linear ODE.

T0
T∞

T∞

1 2 3 4 n n+1

FIGURE 7.2  Heat conduction in a metal rod with heat loss to the surroundings and the domain with
finite difference discretization.

*  The modern refrigerators use evaporative cooling, the model for which would be somewhat more complex than what we
need in this chapter.
278   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

7.2.2.1.1  Analytical Solution  The above problem can be solved analytically by defining a devia-
tion variable, θ = (T − T∞), which results in the following ODE-BVP:

d 2 q h¥ av
- q=0
dz 2  k (7.11)
m2

q ( 0 ) = q0 , q ( L ) = 0

The above is a linear homogeneous second-order ODE, which is a standard problem in an

undergraduate calculus course. The general solution to the above ODE is*

q = C1 sinh ( mz ) + C2 cosh ( mz ) (7.12)

The solution to the ODE-BVP of Equation 7.11 is given by

q = q0
(
sinh m ( L - z ) ) (7.13)
sinh ( mL )

which can be expressed in terms of the original variables:

T = T¥ + (T0 - T¥ )
(
sinh m ( L - z ) ) (7.14)
sinh ( mL )

The numerical solutions can be compared against the above analytical solution of the
ODE-BVP. In order to solve the original problem (7.9) numerically, the domain is
­discretized into n-intervals using the finite difference approach. Figure 7.2 shows the dis-
cretized domain. Since the array indices in MATLAB start with 1, the vertices of the
discretized domain are numbered from i = 1 to i = (n + 1). The interval size is given by
Δ = L/n, and application of the central difference formula (see Appendix B) results in the
following equations:

Ti +1 - 2Ti + Ti -1
k = h¥ av (Ti - T¥ ) , i = 2 to n (7.15)
D2

The two boundary conditions are applied at i = 1 and i = (n + 1). Defining parameter
β = h∞avΔ2/k, the resulting (n + 1) linear equations are given by

T1 = T0
Ti +1 - 2Ti + Ti -1 = b (Ti - T¥ ) , i = 2 to n (7.16)
Tn+1 = T¥

*  Please refer to any standard engineering math text for the derivation of the solution for this and related problems.
 Special Methods for Linear and Nonlinear Equations   ◾    279

7.2.2.1.2  Tridiagonal Matrix Equation  The above set of equations can be written in the standard
linear equations form by defining the solution vector x = [T1 T2 ⋯ Tn Tn + 1]T:

é1 0 0   0 0 ù é T1 ù é T0 ù
ê úê ú ê ú
ê1 - ( 2 + b ) 1   0 0 ú ê T2 ú ê -bT¥ ú
ê0 1 - (2 + b)   0 0 ú ê T3 ú ê -bT¥ ú
ê úê ú=ê ú (7.17)
ê      úê  ú ê  ú
ê0 0 0  1 - ( 2 + b ) 1 ú ê Tn ú ê -bT¥ ú
ê úê ú ê ú
êë0 0 0  0 0 1 úû êëTn+1 úû êë T¥ úû
     
A x b

The above problem can be solved by specifying the matrix A and vector b and solving the
resulting equations in a standard manner: X = A\b. This is demonstrated in the next example.

Example 7.1  Conduction with Known Boundary

Temperatures: Standard Solution
Problem: Heat conduction in a steel rod is given by Equation 7.9. The rod, 2.5 m long,
is maintained at 100°C and 30°C at the two ends. The thermal conductivity of steel is
15 W/m · K, heat loss coefficient is 2 W/m2 · K, area per unit volume is 10 m−1, and the
ambient temperature is 30°C. Convert the above ODE-BVP into a set of linear equa-
tions and solve them using MATLAB linear equation solver.
Solution: The first step is to define the matrix A and vector b, as given in Equation 7.17,
and hence solve the original ODE-BVP. The MATLAB script is given below:

% Heat conduction in a rod with

% heat loss to the surroundings
%% Model Parameters
hinf=2.0; abyV=10;
ks=15; L=2.5;
Ta=30; % Ambient T
T_0=100; % T(z=0)
T_L=Ta; % T(z=L)
%% Discretization & Solution
n=40;
delta=L/n;
beta=hinf*abyV/ks * delta^2;
Z=[0:delta:L]';
m=sqrt(hinf*abyV/ks);
Ttrue=Ta+(T_0-Ta)*sinh(m*(L-Z))/sinh(m*L);

%% Numerical solution and comparison

A=zeros(n+1,n+1);
b=zeros(n+1,1);
280   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

A(1,1)=1; b(1)=T_0;
for i=2:n
A(i,i-1)=1;
A(i,i)=-(2+beta);
A(i,i+1)=1;
b(i)=-Ta*beta;
end
A(n+1,n+1)=1; b(n+1)=T_L;
X=A\b;
plot(Z,Ttrue,'-k',Z,X,'-.m');
err=max(abs(Ttrue-X)./Ttrue);

The results are plotted in Figure 7.3. The solid (black) line is the true solution, whereas
the two lines are the solutions for n = 5 and n = 40 nodes, respectively. The latter solu-
tion closely matches the true solution. The solution with n = 5 nodes is also of reason-
able accuracy.
The relative errors in temperature values were also calculated. Starting with n = 5, the
number of nodes was doubled until reasonable solution was obtained. The errors were

n err
5 0.0060
10 0.0015
20 3.8759e-04
40 9.7041e-05

The solution with n = 20 and n = 40 nodes are both reasonably accurate. It may also
be of interest to the reader to note that each time the step-size is halved (i.e., the
number of nodes is doubled), the error decreases by a factor of 4. This is because
( )
the O h2 accurate central difference formula governs the overall errors in this
problem.

100

80
Temperature (°C)

60

40

0 0.5 1 1.5 2 2.5

Distance, L (m)

FIGURE 7.3  Temperature profile in a rod with heat conduction and heat losses. Dirichlet boundary
conditions are applied, that is, the temperatures at the two ends of the rod are specified.
 Special Methods for Linear and Nonlinear Equations   ◾    281

The standard method of solving a general linear equation was used in the previous
e­ xample. This method works, and for a small-dimensional system as the one in Example 7.1,
the computational requirements are manageable. However, for larger-dimensional systems
and in cases where the problem needs to be solved multiple times, solving the full problem
is very inefficient. There are several methods that exploit the banded structure of matrix A
to solve the linear equation more efficiently. The TDMA, which is applicable to tridiagonal
systems, will be discussed in the following text.

7.2.2.2 Thomas Algorithm
Thomas algorithm, or TDMA, can be used to efficiently solve a linear system of equations
of the type (7.2), where A has a tridiagonal structure. A tridiagonal structure is when only
three diagonals of matrix A are nonzero:

éd1 u1 0  0 0 ù é b1 ù
ê ú ê ú
ê l2 d2 u2  0 0 ú ê b2 ú
ê0 l3 d3  0 0 ú ê b3 ú
ê úx = ê ú (7.18)
ê      ú ê  ú
ê0 0   dn-1 un-1 ú êbn-1 ú
ê ú ê ú
êë 0 0   ln dn ûú êë bn úû

Let the three diagonals be represented as vectors l, d, u. Thus, any equation may be written as

li xi -1 + di xi + ui xi +1 = bi (7.19)

As in the case of Gauss Elimination (see Appendix C), the TDMA aims to convert matrix A
into a lower triangular matrix using row operations, starting with the first row:

d1 x1 + u1 x2 = b1 (7.20)

In the first step, this is the pivot row and d1 is the pivot element. The following two-row
operations are done: (i) divide the entire row with the pivot element, and (ii) use the pivot
row to make subdiagonal element in the first column 0. These operations yield

x1 + u1/d1 x2 = b1/d1 (7.21)

 
u1 b1

The first row operation requires only two computations on the first row: u1 = u1/d1 and
b1 = b1/d1, and the diagonal element is then set to unity, d1 = 1. The only nonzero element in
the pivot column is the element l2, while all other elements are already zero. Thus, the row
operation with the row R1 as the pivot row is R2 = R2 - l2 R1. The only computations required
282   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

in this row are d2 = d2 - l2u1 and b2 = b2 - l2b1. Thus, at the end of the first sequence of opera-
tions, we have the first two rows as

é1 u1 0 0  0 b1 ù
ê ú
ê0 d2 u2 0  0 b2 ú (7.22)
ê       úû
ë

and the remaining are unchanged.

In the second step, row R2 becomes the pivot row, with d2 as the pivot element:

d2 x2 + u2 x2 = b2 (7.23)

This modified row has the exact same form as Equation 7.20. Hence, the exact same proce-
dures are to be repeated. Generalizing, the operations involved in the ith step are

Ri
Ri ¬ , Ri +1 ¬ Ri +1 - li +1Ri (7.24)
di

I have dropped the over-bars and replaced the equality with an assignment operator “←”
to indicate that the right-hand side replaces the values on the left-hand side. Recall that the
above two operations have two calculations each:

ui ¬ ui /di , bi ¬ bi /di , di ¬ 1 (7.25)

di +1 ¬ di +1 - li +1ui , bi +1 ¬ bi +1 - li +1bi , li +1 ¬ 0 (7.26)

The above calculations are repeated for all pivot rows, that is, i = 1 to (n − 1).
The number of mathematical operations required for TDMA is as follows: Equation 7.25
requires two division operations (the third one is simply an assignment since the result
di ← 1 is known a priori), whereas Equation 7.26 requires two multiplication and two sub-
traction operations (again li + 1 ← 0 is known a priori). Thus, the total number of operations
in the forward elimination steps is 4(n − 1) multiplication/division and 2(n − 1) addition/
( )
subtraction operations. This is significantly lower than O n3 operations required in Gauss
Elimination.
At the end of elimination operations, the equations are converted to the following form:

é1 u1 0  0 0ù é b1 ù
ê ú ê ú
ê0 1 u2  0 0ú ê b2 ú
ê0 0 1  0 0ú ê b3 ú
ê úx = ê ú (7.27)
ê     ú ê  ú
ê0 0   1 un-1 ú êb ú
ê ú ê n-1 ú
êë0 0   0 dn ûú êë bn úû

 Special Methods for Linear and Nonlinear Equations   ◾    283

Now that the equations are in lower triangular form, the solutions can be obtained using
back-substitution. Starting for the last row, the back-substitution method (again see
Appendix C and compare with full back-substitution that follows Gauss Elimination) first
provides the solution xn:

xn = bn /dn (7.28)

The next equation is

xn-1 + un-1 xn = bn-1 (7.29)

Also notice that all the rows, starting from the second-last row, have the same structure.
Thus, the following back-substitution steps are used to obtain the solution:

xi = bi - ui xi +1 , i = ( n - 1) to 1 (7.30)

Thus, the overall back-substitution steps require n multiplication/division steps and (n − 1)
addition/subtraction steps. The next example shows implementation of TDMA.

Example 7.2  Heat Conduction Using TDMA

Problem: Solve the problem in Example 7.1 using TDMA.
Solution: The driver script in Example 7.1 needs to be suitably modified to extract
the vectors l , d , u. This is left as an exercise to the reader. Thereafter, the following
TDMA function, thomasSolve.m, is used to obtain the solution:

function x=thomasSolve(l,d,u,b)
% Implementation of Thomas algorithm
% BACKGROUND
% ----------
% Solves the equation of the form
% Ax = p
% Where A is a tri-diagonal matrix:
% [d(1) u(1) ]
% [l(2) d(2) u(2) ]
% [ l(3) d(3) u(3) ]
% [ ... ... ... ]
% [ ... ... ... ]
% [ l(n-1) d(n-1) u(n-1)]
% [ l(n) d(n)]
% The function takes in three vectors for A:
% l (n*1) sub-diagonal vector
% d (n*1) diagonal element vector
% u (n*1) super-diagonal vector
284   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

% and (n*1) vector b and returns solution x

% ==============================================

% Check vector lengths

n=length(d);
if (length(l)~=n)
error('Vectors should be of same length');
end
if (length(u)~=n)
error('Vectors should be of same length');
end
if (length(b)~=n)
error('Vectors should be of same length');
end

% Forward elimination
for i=1:n-1
% Divide row by diagonal
u(i)=u(i)/d(i);
b(i)=b(i)/d(i);
d(i)=1;
% Get zeros in pivot column
d(i+1)=d(i+1)-u(i)*l(i+1);
b(i+1)=b(i+1)-b(i)*l(i+1);
l(i+1)=0;
end

% Back-substitution
x=zeros(n,1);
x(n)=b(n)/d(n);
for i=n-1:-1:1
x(i)=b(i)-u(i)*x(i+1);
end

Solving the above equations results in the exact same solution as that obtained in
Example 7.1, albeit with lower computational effort.

A key element of Gauss Elimination is pivoting. Pivoting is a procedure where a pivot

row is exchanged with a row below it such that the pivot element becomes the largest ele-
ment (in terms of its absolute value) in that column. In contrast, pivoting is not used in
TDMA since it will break the nice tridiagonal structure of the problem. This works well
in practice because often the diagonal elements are dominant elements for a large number
of problems of practical interest. For example, in Equation 7.17, not only is the diagonal
element di  = − (2 + β) the largest element, the matrix A is, in fact, diagonally dominant.
Even when the diagonal element is not largest, TDMA usually gives good performance
without pivoting.
 Special Methods for Linear and Nonlinear Equations   ◾    285

7.2.3 ODE-BVP with Flux Specified at Boundary

The problem introduced in Example 7.1 was an ODE-BVP with Dirichlet boundary condi-
tions since the temperature was specified at both ends. If the rod were insulated at one end
(or if heat flux was known), we will have an example of Neumann boundary condition at
that end, whereas balancing heat loss at the boundary with conductive heat transfer gives
rise to mixed boundary condition. For example, in Example 7.1, if the end of the rod (z = L)
is insulated:

dT
=0 (7.31)
dz z =L

whereas if it loses heat to the surroundings, the following mixed boundary condition is
obtained:

dT
-k = h¥ (TL - Ta ) (7.32)
dz z =L

For implementing the boundary conditions at the boundary, two approaches can be used:
(i) three-point backward difference formula, which is used to discretize Equations 7.31 and
7.32, or (ii) ghost-point approach. We will use the latter in this example. Recall that the
discretized equation for the (N + 1)th node is

Tn+2 - ( 2 + b )Tn+1 + Tn = -bTa (7.33)

As discussed in Chapter 4, this introduces a “ghost-point” Tn + 2 outside the solution domain.
The central difference formula applied to the boundary condition will be used to rewrite
Equation 7.33. In case of an insulated boundary, Equation 7.31 reduces to Tn+2 = Tn. On the
other hand, substituting the central difference formula for Equation 7.32 yields

h¥ ( 2D )
Tn+2 - Tn =
-k
(Tn+1 - Ta ) (7.34)

h¥ ( 2D )
Tn+2 = Tn -
k
(Tn+1 - Ta ) (7.35)

Substituting the above in Equation 7.33 yields the following:

2Tn - ( 2 + g )Tn+1 = - gTa

h (7.36)

where g = ¥ 2D + D 2av
k
(
)
286   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The equation above replaces the last equation in Equation 7.16. The resulting system of
linear equations is

é1 0 0   0 0 ù é T1 ù é T0 ù
ê ú
ê1 - ( 2 + b ) 1   0 0 ú êê T2 úú êê -bT¥ úú
ê0 1 - (2 + b)   0 0 ú ê T3 ú ê -bT¥ ú
ê úê ú=ê ú (7.37)
ê       úê  ú ê  ú
ê0 0 0  1 - (2 + b) 1 ú ê Tn ú ê -bT¥ ú
ê úê ú ê ú
êë0 0 0  0 2 - ( 2 + g ) úû êëTn+1 úû êë - gT¥ úû
       
A x b

Note that only the last row of matrix A has changed compared to Equation 7.17. Let us solve
this problem in the next example.

Example 7.3  Heat Conduction with Mixed Boundary Condition

Problem: Solve the problem of heat conduction in a rod from Example 7.1, where one
end of the rod is held at 100°C and the other end is governed by the mixed boundary
condition given in Equation 7.32.
Solve: The problem to be solved is shown in Equation 7.37. The code for this using
MATLAB’s inbuilt linear equation solver is given below*:

% Heat conduction in a rod with heat losses

% using mixed boundary condition at one end
% Model Parameters
hinf=2.0;
abyV=10;
ks=15;
L=2.5;
Ta=30; % Ambient T
T_0=100; % T(z=0)
% Discretization
n=20;
delta=L/n;
beta=hinf*abyV/ks*delta^2;
gamma=hinf/ks*(abyV*delta^2+2*delta);
Z=[0:delta:L]';

%% Solving using matrix inverse

A=zeros(n+1,n+1);

*  A more appropriate way to solve this problem is to use the TDMA code from Example 7.2. However, the reader is urged to
solve this using TDMA as an exercise (and compare with results in Example 7.3). The TDMA code from Example 7.2 takes
in the three diagonal elements of the matrix A and the vector b as four vectors, l,d,u,b.
 Special Methods for Linear and Nonlinear Equations   ◾    287

b=zeros(n+1,1);
A(1,1)=1; b(1)=T_0;
for i=2:n
A(i,i-1)=1;
A(i,i)=-(2+beta);
A(i,i+1)=1;
b(i)=-Ta*beta;
end
A(n+1,n) =2;
A(n+1,n+1)=-(2+gamma);
b(n+1)=-Ta*gamma;
T=A\b;
plot(Z,T); hold on
xlabel('distance, L (m)'); ylabel('temperature (^oC)')
%% Solving using TDMA
T1=newThomasSolve(A,b);
% <newThomasSolve.m is left as student exercise>
plot(Z,T1,'ro');

Figure 7.4 shows the variation in temperature profile for an axial rod with mixed
boundary condition. The end temperature is slightly higher than 30°C that was
assumed in the previous example.
Finally, Figure 7.5 shows the structure of matrix A, investigated using the MATLAB
spy command. As is clear from the figure, the matrix A indeed has a tridiagonal
structure.

The solution is repeated for different values of thermal conductivity, k = 5,15,50 W/m · K.

Figure 7.6 shows the effect of thermal conductivity on the temperature profile in the rod.
The temperature in the rod becomes more uniform as the thermal conductivity is increased
from 5 to 50 W/m · K. Higher thermal conductivity also causes greater heat transfer through
the rod, which is then lost to the surroundings.

100
Temperature (°C)

75

50

30
0 0.5 1 1.5 2 2.5
Distance, L (m)

FIGURE 7.4  Temperature profile in the rod with heat transfer to the surroundings. The line shows
solution using the general linear equation solved (A\b in MATLAB®), whereas the circles show the
solution using the TDMA solver from Example 7.2.
288   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

10

15

20

0 10 20
nz = 60

FIGURE 7.5  The structure of matrix A observed through MATLAB® spy(A) command.

100
Temperature (°C)

75
50 W/m · K

50
15 W/m · K

5 W/m · K
30
0 0.5 1 1.5 2 2.5
Distance, L (m)

FIGURE 7.6  Temperature profiles for different values of thermal conductivity.

7.2.4 Extension to Banded Systems

An example of banded system will be considered in case studies. Let us now consider a
band-diagonal system of equations. If the storage space for storing matrix A is not an issue,
it will be easier to solve a band-diagonal system as a specific implementation of Gauss
Elimination. For ease of discussion, matrix A with equal sub- and superdiagonal elements
is considered. The method can be easily extended to a system with a different number of
sub- and superdiagonal elements. This method is a modification of Gauss Elimination, dis-
cussed in Appendix C.
In the kth sequence of steps, Ak,k is the pivot element. The first step is to divide the
first row with A1,1. Thereafter, row-1 is used to make zeros in subdiagonal elements of
the pivot column. Unlike Gauss Elimination, there are only ℓ nonzero elements on the
 Special Methods for Linear and Nonlinear Equations   ◾    289

pivot row, and only ℓ rows have nonzero elements in the pivot column. Thus, the first
row operation is executed as follows:

Ak ,k +i
Ak ,k +i ¬ , i = 1 to  (7.38)
Ak ,k

bk
bk ¬ , Ak ,k ¬ 1 (7.39)
Ak ,k

Note that Equation 7.38 is implemented for only ℓ elements and not for all elements since
the remaining elements of the row are already zero. Since only ℓ subdiagonal elements are
nonzero, the row operations for eliminating subdiagonal elements in the pivot column need
to be done for only ℓ operations:

Rk +i ¬ Rk +i - Ak +i ,k Ri , i = 1 :  (7.40)

At this stage, it should be noted that the only nonzero elements in the kth row are elements
Ak,k to Ak,k + ℓ. Thus, the row operations need to be performed for only these elements and
not all. Thus, the expansion of Equation 7.40 in terms of individual elemental operations is

For i = 1 :  a k +i ,k = Ak +i ,k (7.41)

A( k +i ),( k:k +  ) ¬ A( k +i ),( k:k +  ) - a k +i ,k Ak ,( k:k +  ) (7.42)

bk +i ¬ bk +i - a k +i ,k bk (7.43)

Note that Equation 7.41 is different from standard Gauss Elimination (Appendix C) because
we had already used Equation 7.39 to ensure Ak , k ← 1.
Writing a code for the above operations is left as an exercise for the reader. An example
of band-diagonal system will be taken in Case Studies section.
Block-diagonal system: The block-diagonal systems can be treated as band-diagonal. For
the example in Figure 7.1, the bandwidth is ℓ = 2 for superdiagonals and ℓ = 1 for subdiago-
nals. The procedure described above can be used for a block-diagonal system as well.

7.2.5 Elliptic PDEs in Two Dimensions

Heat conduction in a 2D geometry is a standard problem that leads to the following elliptic
PDE:

0 = kÑ2T + S (T ) (7.44)
290   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

which, when written in a rectangular coordinate system in 2D, becomes

æ ¶ 2T ¶ 2T ö
0 = k ç 2 + 2 ÷ + S (T ) (7.45)
è ¶x ¶y ø

The model needs to be solved subject to boundary conditions. Since it is a second-order

PDE in both dimensions, boundary conditions at four boundaries are required to solve the
problem. These may be the Dirichlet boundary condition (Equation 7.4) if temperature
is specified, the Neumann boundary condition (Equation 7.5) if flux is specified or the
boundary is insulated, or the mixed boundary condition (Equation 7.6) if heat loss is speci-
fied at the boundary.
The term S(T) is the source term; it is included to model any source or sink of heat within
the domain. Unlike the 1D model of Equation 7.9, heat loss typically appears as a boundary
condition and not a source term. Elliptic PDEs are also encountered in systems with flow:

sÑf = GÑ2 f + S ( f )

where
σ is the coefficient of convection
Γ is the diffusive coefficient

As long as the Péclet number, Pe = σL/Γ (where L is the characteristic length), is not very
large, diffusion may not be neglected and the PDE is elliptic in nature. Besides heat transfer
problems, elliptic PDEs are encountered in a large number of problems: diffusion in mul-
tiple dimensions, diffusion and reaction, momentum balance (Navier-Stokes), and so on.
Due to qualitative similarity in the behavior of elliptic PDEs, we take a similar approach
as the in previous section to solve them. The domain is discretized in both x and y direc-
tions. The temperature at any location (i, j) is related to its neighbors through the central
difference formula, which yields the following discretized equation:

Ti +1, j - 2Ti , j + Ti -1, j Ti , j +1 - 2Ti , j + Ti , j -1

0=k 2
+k + S (Ti , j ) (7.46)
Dx Dy 2

where Δx = L/nx and Δy = H/ny, where L and H are length and height of the domain, respec-
tively. Including the boundary nodes, this will lead to (nx + 1)(ny + 1) equations in as many
unknowns. The rest of the solution procedure follows on similar lines as discussed in the
previous sections.

7.3 ITERATIVE METHODS
I now switch my attention to a completely different class of numerical methods: iterative
methods. As seen in Chapter 6, iterative methods start with an initial guess of the solution
and use a sequence of equations to iteratively improve the solution. Fixed point iteration,
 Special Methods for Linear and Nonlinear Equations   ◾    291

Newton-Raphson, secant method, etc., from Chapter 6 are examples of iterative methods.
We now focus our attention back to iterative methods, for both linear and nonlinear systems.

7.3.1 Gauss-Siedel Method
Gauss-Siedel method (and related Jacobi method) is the linear equations equivalent of fixed
point iteration. In case of fixed point iteration, the nonlinear equation was modified appro-
priately, and this was then used as an update equation to iteratively improve the current
solution guess:

x( ) = h x( )
i +1 i
( )
The Gauss-Siedel works in a similar manner for linear systems. Consider the kth equation:

Ak ,k x k = bk - ( Ak ,1 x1 +  + Ak ,k -1 x k -1 + Ak ,k +1 x k +1 +  + Ak ,n xn ) (7.47)

Similar to the fixed point iteration, the above equation is used as an iterative update equa-
tion if the overall system of equations is linear. Based on how the update equation is used,
there are two possibilities: (i) the previous values x(I) is used for all the update equations in
the Jacobi method, or (ii) the most recent values are used for the update equations in the
Gauss-Siedel method.
First consider the Jacobi iteration. When Equation 7.45 is used to update xk, we have the
previous iteration values x k( +)1 ,¼, xn( ) because the updated values have not yet been calcu-
i i

lated. However, for the preceding elements, both the updated values, x1( ) , , x k( -1 ) , or the
i +1 i +1

(i ) (i )
previous iteration values, x1 , , x k -1 , are available. Jacobi iteration uses the previous itera-
tion values for all elements of x, thus resulting in the following update equations:

å
n
Ak , j x (j )
i
bk - j =1,

x k( ) =
i +1 j¹k
(7.48)
Ak ,k

Gauss-Siedel, on the other hand, uses the most updated values. Thus, x1( ) is computed
i +1

using x2( ) ,¼, xn( ). However, computation of x2( ) uses x1( ) since that is the most updated
i i i +1 i +1

value of iterated solution vector. Likewise, x k( ) is computed using x1( ) ,¼, x k( -1 ) (most
i+1 i +1 i +1

recently update values) as well as x k( ) ,¼, xn( ) (which are not yet updated). Mathematically,
i i

the updated equations for Gauss-Siedel are

å å
k -1 n
Ak , j x (j ) - Ak , j x (j )
i +1 i
bk -
x k( ) =
i +1 j =1 j = k +1
(7.49)
Ak ,k
292   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

In Chapter 6, I derived the error propagation equation for fixed point iteration in a single
variable. This can be extended to multivariate fixed point iteration as

¶h i ¶h i
ek( ) = k e1( ) +  + k en( )
i +1
(7.50)
¶x1 ¶xn

Extending the arguments from the single-variable case of Chapter 6, the criterion for
­convergence of fixed point iteration is

¶hk

å ¶x i
i
<1

(7.51)

This leads to the following diagonal dominance criterion for the Gauss-Siedel method:

Ak ,i
åA k ,k
<1
i ¹k (7.52)

Ak ,k > åi ¹k
Ak ,i

The following example, which can be worked out with hand calculations, demonstrates this
criterion for stability of the Gauss-Siedel method.

Example 7.4  Stability and Diagonal Dominance of Gauss-Siedel

Problem: Solve the following problem using Gauss-Siedel method, with x = [0 0]T
as the initial guess:

x1 + 2 x2 = 1

x1 - x2 = 4

Solution-1: The above system of equations is not diagonally dominant. The Gauss-
Siedel iterations for this system of equations are

x1( ) = 1 - 2 x2( )
i +1 i

x2( ) = x1( ) - 4
i +1 i +1

The first five iterations of Gauss-Siedel method give the following results:

0 1 7 -5 19 -29
0 -3 3 -9 15 -33
 Special Methods for Linear and Nonlinear Equations   ◾    293

As can be concluded from the above results, the iterations are diverging. Hence, the
equations can first be rearranged to make them diagonally dominant, followed by
using the Gauss-Siedel method.
Solution-2: The two equations are switched to make the system diagonally domi-
nant. With this change, the Gauss Siedel iterations are given by

x1( ) = 4 + x2( )
i +1 i

x2 =
1
2
(
1 - x1( )
i +1

)
The first five iterations for this diagonally dominant system of equations is given by

0 4.0000 2.5000 3.2500 2.8750 3.0625

0 -1.5000 -0.7500 -1.1250 -0.9375 -1.0312

Clearly, the above is converging to the solution, x = [3 -1]T . This example shows the
improved convergence behavior of the Gauss-Siedel method when the same system of
equations is rearranged in a diagonally dominant form.

Let us turn to the implications of the above observation to solving a sparse system of
­equations. The tridiagonal system of Section 7.2.2 already satisfies the diagonal dominance
condition. This is true for a large number of systems of practical interest.
Since only one subdiagonal and superdiagonal elements are nonzero, the Gauss-Siedel
iteration for the kth element becomes
(i +1) (i )
b -l x - uk x k +1
x k( ) = k k k -1
i +1
(7.53)
dk

The extension to the banded system, with a bandwidth of ℓ, is also straightforward:

å
 +1
A1, j x (j )
i
b1 -
x1( ) =
i +1 j =2

A1,1

å
 +1
b2 - A2,1 x1( ) - A1, j x (j )
i +1 i

(i +1) j =3
x 2 =
A2,2 (7.54)


å å
k -1 k +
Ak , j x (j ) - Ak , j x (j )
i +1 i
bk -
(i +1) j =k - j = k +1
x k =
Ak ,k


The next example demonstrates the use of Gauss-Siedel method for a heat conduction problem.
294   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 7.5  Gauss-Siedel Method for Tridiagonal System

Problem: Use the Gauss-Siedel method to solve Example 7.2.
Solution: Given below is the Gauss-Siedel code for the tridiagonal system:

% Heat conduction in a rod using Gauss-Siedel method

%% Model Parameters
hinf=2.0;
abyV=10;
ks=15;
L=2.5;
Ta=30; % Ambient T
T_0=100; % T(z=0)
T_L=Ta; % T(z=L)
%% Discretization
n=40;
delta=L/n;
Z=[0:delta:L]';
beta=hinf*abyV/ks * delta^2;
%% Numerical solution: Gauss-Siedel
A=zeros(n+1,n+1);
b=zeros(n+1,1);
A(1,1)=1; b(1)=T_0;
for i=2:n
A(i,i-1)=1;
A(i,i)=-(2+beta);
A(i,i+1)=1;
b(i)=-Ta*beta;
end
A(n+1,n+1)=1; b(n+1)=T_L;
T=T_L*ones(n+1,1);
aTol=1e-3;
maxIter=5000;
for iter=1:maxIter
Told=T;
T(1)=(b(1)-A(1,2)*T(2))/A(1,1);
for k=2:n
T(k)=(b(k)-A(k,k+1)*T(k+1)-A(k,k-1)*T(k-1))/A(k,k);
end
T(n+1)=(b(n+1)-A(n+1,n)*T(n))/A(n+1,n+1);
err=max(abs(T-Told));
if (err<aTol)
break
end
end
plot(Z,T);
 Special Methods for Linear and Nonlinear Equations   ◾    295

The above method took 486 iterations to converge to the desired tolerance. The solu-
tion obtained using this approach is close to the temperature values obtained using
the TDMA-based approach of the previous example.

The matrix A in this example was diagonally dominant, and the criterion in Equation 7.50
is satisfied. If the system is not diagonally dominant, it is possible to “slow down” the itera-
tions using an under-relaxation factor. Conversely, an over-relaxation ­factor may be used to
“speed up” the convergence. These relaxation methods are introduced next.

7.3.2 Iterative Method with Under-Relaxation

In Chapter 6, the line-search parameter was introduced in Newton-Raphson to improve its
convergence properties. Relaxation methods, discussed here, have the same idea. Instead of
taking a full step toward the solution, we take a partial step. If Δx is the full step taken in the
direction of the solution, then the next iteration value is obtained as

x ( ) = x ( ) + wDx
i +1 i
(7.55)

The update equation (7.46) in Jacobi iteration can be used to define Δxk:

å
n
Ak , j x (j )
i
bk - j =1,

Dx k( ) = - x k( )
i +1 j¹k i
(7.56)
Ak ,k

Thus, Jacobi iteration with relaxation is written as

å
n
Ak , j x (j )
i
bk - j =1,

x k( ) = (1 - w) x k( ) + w
i +1 i j¹k
(7.57)
Ak ,k

Here, ω is known as a relaxation parameter. The value of parameter ω is kept between

0 and 2. When the value of ω is less than unity, the method is called the Jacobi under-relax-
ation method. In contrast, the value of ω is chosen between 1 < ω < 2 to improve the speed
of convergence for a slowly converging system.
Likewise, the Gauss-Siedel method with relaxation is given by

å å
æ k -1 n
i ö
Ak , j x (j ) - Ak , j x (j ) ÷
i +1
ç bk -
x k( ) = (1 - w) x k( ) + w ç
i +1 i j =1 j = k +1
÷ (7.58)
è Ak ,k ø

The term successive over-relaxation is used for the Gauss-Siedel method with the relaxation
factor, 1 < ω < 2.
296   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

7.4 NONLINEAR BANDED SYSTEMS

A second-order 1D ODE discussed so far is of the form

d 2f æ df ö
a = f ç x , f, (7.59)
dx 2
è dx ÷ø

Here α is a coefficient, which itself can be a function of ϕ and/or x.

Typical chemical process simulation problems involve diffusive/conductive as well as
convective transport terms. Such systems are governed by a specific type of ODE-BVP:

d 2f df
a 2
- u - f ( x, f) = 0 (7.60)
dx dx

The above ODE is nonlinear if either α or u (or both) depend on ϕ or if f (x, ϕ) is

nonlinear.

7.4.1 Nonlinear ODE-BVP Example

Consider the heat conduction problem of Section 7.2.2. Since the balance is for a solid rod,
u = 0. The term f(x, ϕ), called the source term

f ( x , T ) = h¥ av (T - T¥ ) (7.61)

is linear. For a narrow range of temperature (303 K ≤ T ≤ 373 K), the thermal conductivity
was considered constant. This led to a linear ODE-BVP with linear boundary conditions,
as seen in Equation 7.11. Discretizing using finite difference approximation resulted in a
tridiagonal set of linear equations, as described in the chapter so far.
At times, the thermal conductivity may not be a constant but expressed as a power law or
a polynomial function of temperature:

k = k0 + k1T + k2T 2 + k3T 3 , or k = aT h (7.62)

Compared to problems involving temperature-dependent coefficients, the most common

form of nonlinearity in process simulation examples arises when the source term f(x, ϕ) is
nonlinear. For example, if one end of the rod was at a very high temperature, then radiation
becomes important. Radiation flux is given by the following fourth-order term:

(
Flux = es T 4 - T¥4 ) (7.63)

where
ε is the emissivity factor
σ = 5.67 × 10−8 W/m2 · K4 is Stefan’s constant

In fact, nonlinear source terms are common in the majority of chemical engineering exam-
ples, due to nonlinear heat loss as radiation, a nonlinear reaction or heat release term, bilinear
(or nonlinear) interaction/adsorption term in two-phase systems, etc.
 Special Methods for Linear and Nonlinear Equations   ◾    297

When the nonlinear differential equation(s) described here are discretized, we obtain a
set of nonlinear algebraic equations. These equations have a tridiagonal (sparse) structure,
which can be exploited for efficient solving of the nonlinear equations. Modifications to the
TDMA, Gauss-Siedel, or Jacobi method and fsolve options are discussed in this section.
The nonlinearities are of two types: (i) variable diffusive/convective coefficients and (ii)
source term nonlinearity. The latter will be discussed at length in this section. The methods
discussed are rather general and are often applicable when coefficients are varying as well.
However, an example of variable coefficient will be left as an exercise for the reader.

7.4.1.1 Heat Conduction with Radiative Heat Loss

Let us focus back on the heat conduction problem with radiation. The ODE-BVP model for
this system is given by

d 2T

k
dz 2
(
= esav T 4 - T¥4 )

(7.64)

T ( 0 ) = T0 (7.65)

T ( L ) = T¥ (7.66)

Discretizing the above using finite difference approximation, as before

esD 2av 4
Tk -1 - 2Tk + Tk +1 =
k
( )
Tk - T¥4 , k = 2 to n (7.67)
  
b(Tk )

Unlike the previous example, β(T) is a nonlinear function of T. The discretized boundary
conditions are

T1 = T0
(7.68)
Tn+1 = T¥

Thus, we can form the following tridiagonal system of nonlinear equations:

é1 0 0   0 0 ù é T1 ù é T0 ù
ê úê ú ê ú
ê1 -2 1   0 0 ú ê T2 ú êb (T2 ) ú
ê0 1 -2   0 0 ú ê T3 ú êb (T3 ) ú
ê úê ú=ê ú (7.69)
ê      ú ê  ú ê  ú
ê0 0 0  1 -2 1 ú ê Tn ú êb (Tn ) ú
ê úê ú ê ú
êë0 0 0  0 0 1 úû êëTn+1 úû êë T¥ úû
    
A x b( x )

In the next couple of sections, we will discuss numerical techniques to solve this problem.
298   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

7.4.2 Modified Successive Linearization–Based Approach

Since the above is a set of nonlinear equations, an iterative method needs to be used to solve
it. Recall that in fixed point iteration, we rewrite the original Equation 7.1 as

i
( )
x( ) = G x( )
i +1
(7.70)

The above is used as an update equation. In the same manner, it is easy to rewrite
Equation 7.66 as

( )
x ( ) = A -1 b x ( )
i +1 i
(7.71)

Instead of inverting the matrix A, a TDMA solver can be used to solve the problem (7.66)
with a fixed value of b(i) to obtain x(i + 1), substitute this value to obtain b(i + 1) = b(x(i + 1)) and
iterate until convergence, that is, ‖x(i + 1) − x(i)‖ < Etol.
It is also possible to combine the above approach with under-relaxation. The above
TDMA-based successive substitution is a rather naïve way to solve a nonlinear system of
equations, and it may not work for examples with highly nonlinear source term. In such
cases, TDMA with under-relaxation may be used, where the updated equation becomes

i
( )
x ( ) = (1 - w) x ( ) + wA -1 b x ( )
i +1 i
(7.72)

In the above, the same relaxation factor ω was used for all variables xk. However, it is pos-
sible to choose different values of ω for different elements of x:

i
( )
x ( ) = ( I - W ) x ( ) + WA -1 b x ( )
i +1 i

(7.73)
(
W = diag ëéw1 w2  wn+1 ùû )
Unlike the standard fixed point iteration, the above methods do not have a general require-
ment that guarantees convergence. So, this is a rather heuristic combination of linear equa-
tion solving with method of successive substitution. The next example demonstrates the use
of this approach to heat conduction with radiative heat loss.

Example 7.6  Heat Conduction with Radiative Heat Loss

Problem: Solve the problem of heat conduction in a metal rod that loses heat to sur-
roundings by radiation. The model is described by Equation 7.61 and the two ends of
the rod are kept at 600 K and 300 K, respectively. Solve this for two values of emissiv-
ity, ε = 0.1 and ε = 0.9.
Solution: First we will solve this using successive substitution employing a TDMA-
based solution approach. The matrix A is constructed according to Equation 7.66,
 Special Methods for Linear and Nonlinear Equations   ◾    299

and vector b(x(i)) is computed at the current guess of temperature. The Thomas solver
explained earlier is used to obtain the next guess, and the process is repeated iteratively.

% Heat conduction in a rod with radiation heat loss

%% Model Parameters
epsi=0.1;
sigma=5.67e-8;
abyV=10;
ks=15;
L=2.5;
Ta=300; % Ambient T
T_0=600; % T(z=0)
T_L=Ta; % T(z=L)
%% Discretization
n=50;
delta=L/n;
Z=[0:delta:L]';
betaFactor=epsi*sigma*delta^2*abyV/ks;

%% Iterative solution with TDMA

iv=ones(n,1);
A=-2*eye(n+1)+diag(iv,1)+diag(iv,-1);
A(1,:)=[1,zeros(1,n)];
A(n+1,:)=[zeros(1,n),1];
T=T_L*ones(n+1,1);
maxIter=5000;
tol=1e-3;
for iter=1:maxIter
b(1,1)=T_0;
b(2:n) = betaFactor*(T(2:n).^4-Ta^4);
b(n+1,1)=T_L;
Tnew=newThomasSolve(A,b);
TSTORE(:,iter)=Tnew;
err=max(abs(Tnew-T));
T=Tnew;
if (err<tol)
break
end
end
plot(Z,T-273); hold on
xlabel('distance, L (m)'); ylabel('temperature (^oC)')

The above code took 30 iterations to converge to a solution, starting with initial guess
of T = T∞, for ε = 0.1. While the temperature could be expressed either in °C or K in
the convective heat loss case, we have to use K in this example. The temperature pro-
file is plotted as solid line in Figure 7.7. The temperature profiles with heat loss via
300   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

300 є = 0.1
є = 0.9
h∞ = 2

Temperature (°C)
None
200

100

0
0 0.5 1 1.5 2 2.5
Distance, L (m)

FIGURE 7.7  Heat conduction in a metal rod with heat loss to the surroundings through radiation
for two different emissivity values (ε = 0.1: solid; ε = 0.9: dashed). The temperature profile when heat
loss is only by convection is plotted as a dotted line for comparison. Also plotted is the case with no
heat loss (straight line).

convection (solved using code from Example 7.2) and with no heat loss are also plot-
ted as dotted line and solid straight line for comparison.
The above code does not converge for the more relevant emissivity value of ε = 0.9.
The temperature diverges and we get NaN as the resulting temperature profile. This is
because the fixed point iterations do not converge owing to the nonlinear radiation
term. Consequently, under-relaxation-based approach, shown in Equation 7.69, was
used with the under-relaxation factor ω = 0.25.
Modification of the code above for implementing this under-relaxation is left to the
reader (see Problem 7.3).

The above approach combined linear equation solving with successive linearization in a
heuristic algorithm. Alternatively, a regular fixed point iteration may be used, treating each
equation in Equation 7.66 as a regular nonlinear equation. Thus, the update expression

i
( )
x k( ) = Gk x ( )
i +1
(7.74)

can be written in a manner similar to the Gauss-Siedel iteration*:

xk (i +1)
=
( )
b x k( ) - Ak ,k -1 x k( -1 ) - Ak ,k +1 x k( +)1
i i +1 i

(7.75)
Ak ,k

or successive under-relaxation approach:

xk(i +1)
= (1 - wk ) x k + wk (i ) ( )
b x k( ) - Ak ,k -1 x k( -1 ) - Ak ,k +1 x k( +)1
i i +1 i

(7.76)
Ak ,k

*  In the same manner, Jacobi iteration or Jacobi under-relaxation may also be used.
 Special Methods for Linear and Nonlinear Equations   ◾    301

In either case, the iterations are repeated until convergence, that is, ‖x(i + 1) − x(i)‖ < Etol. This
is the fixed point iteration approach (either with or without under-relaxation), which has
been modified for the tridiagonal problem represented in Equation 7.66.
Previously, the diagonal dominance of matrix A guaranteed convergence for a linear
tridiagonal system. However, due to the nonlinear source term, the Gauss-Siedel iterations
for Equation 7.66 do not have convergence guarantees. If the Gauss-Siedel method diverges,
the successive under-relaxation approach may be used to improve the convergence behav-
ior of the system. The nonlinear heat conduction with a radiative heat loss problem is solved
using Gauss-Siedel (with under-relaxation) in the next example.

Example 7.7  Heat Conduction with Radiative Heat Loss Using Gauss-Siedel
Problem: Solve the problem from Example 7.6 using Gauss-Siedel method.
Solution: The code for Gauss-Siedel for this problem is given below:

% Heat conduction in a rod with radiation heat loss

%% Model Parameters
epsi=0.9;
sigma=5.67e-8;
abyV=10;
ks=15;
L=2.5;
Ta=300; % Ambient T
T_0=600; % T(z=0)
T_L=Ta; % T(z=L)
%% Discretization
n=50;
delta=L/n;
Z=[0:delta:L]';
betaFactor=epsi*sigma*delta^2*abyV/ks;

%% Solving using GS-Under-Relaxation

iv=ones(n,1);
A=-2*eye(n+1)+diag(iv,1)+diag(iv,-1);
A(1,:)=[1,zeros(1,n)];
A(n+1,:)=[zeros(1,n),1];
T=T_L*ones(n+1,1); % Initial guess
maxIter=50000;
tol=1e-3;
omega=1;
for iter=1:maxIter
b(1,1)=T_0;
b(2:n)=betaFactor*(T(2:n).^4-Ta^4);
b(n+1,1)=T_L;
Told=T; % For verifying convergence
for k=1:n+1
302   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

if (k==1)
dT=(b(1)-A(1,2)*T(2))/A(1,1);
elseif (k==n+1)
dT=(b(n+1)-A(n+1,n)*T(n))/A(n+1,n+1);
else
dT=( b(k)-A(k,k+1)*T(k+1)-...
A(k,k-1)*T(k-1) ) / A(k,k);
end
T(k)=(1-omega)*T(k) + omega*dT;
end
TSTORE(:,iter)=T;
err=max(abs(T-Told));
if (err<tol)
break
end
end

The above code gives the exact same results as those shown in Figure 7.7. It took 394
Gauss-Siedel iterations for convergence when ε = 0.9 and 1059 iterations when ε = 0.1.
These reports are for ω = 1 (i.e., without under-relaxation).
When the above code was modified for Jacobi iteration, the iterations did not con-
verge for ε = 0.9, whereas it took as many as 8089 iterations for convergence for ε = 0.1.
In order to improve convergence behavior, Jacobi under-relaxation was used. With the
under-relaxation factor of ω = 0.9, the method converged in 796 iterations for ε = 0.9.
The modification of the above code for Jacobi iterations is left as an exercise to the
reader.

7.4.3 Gauss-Siedel with Linearization of Source Term

The convergence of fixed point iteration for tridiagonal systems can sometimes be slow,
or the method may not be robust. Adjusting the relaxation parameter, as described in the
previous section, is one option to improve convergence behavior. Another option to do so
is by linearizing the source term. Before going to the tridiagonal example, let us consider a
single-variable case:

x = G ( x ) (7.77)

The function can be linearized around x(i) using Taylor’s series:

( ) ( )
G ( x ) » G x ( ) + G¢ x ( ) é x - x ( ) ù
i i
ë
i
û
= G ( x ( ) ) + x ( )G ¢ ( x ( ) ) + G ¢ ( x ( ) ) x
i i i i (7.78)
     
G0 G1
 Special Methods for Linear and Nonlinear Equations   ◾    303

Substituting in Equation 7.74 yields the following update equation:

G
x( ) = 0
i +1

1 - G1 (7.79)

( )
where G0 = G x ( ) - x ( )G ¢ x ( )
i i
( ) i
( )
and G ¢ x ( )
i

Using equivalence between this and the Newton-Raphson method from the previous
chapter, it can be shown that the linearization-based method has the quadratic rate of con-
vergence for problems in single variable. This is left as an exercise to the reader.
The same concept can be expanded to a multivariable case. The equation with a non-
linear source term (such as that in Equation 7.64) can be written in the general form of
Equation 7.19 as

lk x k -1 + dk x k + uk x k +1 = b ( x k ) (7.80)

Using a single-variable Taylor’s series expansion for linearizing the nonlinear source term
around xk yields

( ) ( )
b ( x k ) » b x k( ) + b¢ x k( ) é x k - x k( ) ù
i i
ë
i
û
= b ( x ( ) ) + x ( )b¢ ( x ( ) ) + b¢ ( x ( ) ) × x
i i i i
k k k k k (7.81)
     
b0 , k b1, k

Note that since single-variable Taylor’s series expansion is used, that is

( )
b¢ x k( ) =
i ¶b
¶x k x =x( )
i

(7.82)

Substituting this in Equation 7.77, the tridiagonal equation is written as

lk x k -1 + ( dk - b1,k ) x k + uk x k +1 = b0,k

( ) ( ) ( )
(7.83)
where b0,k = b x k( ) - x k( )b¢ x k( ) , b1,k = b¢ x k( )
i i i i

Thus, source term linearization often results in improved convergence properties by ensur-
ing the tridiagonal system is diagonally dominant. For small- to medium-size problems,
this approach may not provide significant benefits over the regular Gauss-Siedel approach.
However, this approach is quite popular in large-scale commercial solvers, as it tends to
make the iterative solver more robust without slowing down the rate of convergence.
304   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

7.4.4 Using fsolve with Sparse Systems

This brings me to the method of choice for a nonlinear banded system of equations: to use
fsolve. While the fsolve solver can be used as in Chapter 6, a full-order solver will
be used. However, it is possible to exploit the sparse/banded structure of the Jacobian in
fsolve using the option 'jacobPattern' and specifying the pattern of the Jacobian.
The syntax for this is

>> opt=optimoptions('jacobPattern',J);

The options are appropriately passed to fsolve, as discussed earlier.

We will extensively make use of fsolve in the case studies discussed in the next section.

7.5 EXAMPLES
7.5.1 Heat Conduction with Convective or Radiative Losses
The problem of heat conduction in a rod with convective or radiative heat losses was dis-
cussed earlier in this book. Recall that the problem solved in Example 7.1 was that of heat
conduction in a rod, modeled as the following ODE-BVP:

d 2T
k = h¥ av (T - T¥ ) (7.9)
dz 2

T ( 0 ) = T0 , T ( L ) = T¥ (7.10)

where
T is the temperature at any location in °C
T∞ is the temperature of the ambient
k is the thermal conductivity of the rod
h∞ is the heat loss coefficient
av is the external area of the rod per unit volume

This problem was modified in Section 7.2.3 by replacing the Dirichlet boundary condition
with either a Neumann or a mixed boundary condition. If the far end of the rod is insulated,
a Neumann boundary condition is used:

dT
=0 (7.31)
dz z =L

On the other hand, if it loses heat to the surroundings, a mixed boundary condition is used
instead:

dT
-k = h¥ (TL - Ta ) (7.32)
dz z =L

Example 7.3 solved the problem (Equation 7.9) with a mixed boundary condition at one
end of the rod.
 Special Methods for Linear and Nonlinear Equations   ◾    305

Both these problems were linear; Section 7.4 extended this to a nonlinear system.
Specifically, the problem of heat conduction with radiative heat losses was solved in
Example 7.6. The ODE-BVP model for this system, along with the relevant Dirichlet bound-
ary conditions, is given by

d 2T

k
dz 2
(
= esav T 4 - T¥4

) (7.64)

T ( 0 ) = T0 (7.65)

T ( L ) = T¥ (7.66)

The interested reader is referred to these sections for details on these three simulation case
studies on the 1D heat conduction problem.

7.5.2 Diffusion and Reaction in a Catalyst Pellet

A standard problem in reaction engineering is diffusion and reaction in a solid catalyst pel-
let. A reaction taking place in a spherical catalyst pellet of radius R is modeled as

De d æ 2 dC A ö
0= ç r dr ÷ - rA (7.84)
r 2 dr è ø

where
CA is the concentration of the reactant in the pellet
De is the effective diffusivity
rA is the rate of reaction

The above equation can be written as

d 2C A 2De dC A
De + - rA = 0 (7.85)
dr 2 r dr

We will consider two different cases for solving and analyzing the system: (i) first-order
reaction and (ii) Langmuir-Hinshelwood (LH) rate kinetics.

7.5.2.1 Linear System and Thiele Modulus

The above equation can be non-dimensionalized and written as

d 2 y 2 dy 2
+ -f y = 0 (7.86)
d x2 x d x

where
f2 = kR2 /De is known as the Thiele modulus
ψ = CA/CA0 is the dimensionless concentration
ξ = r/R is the dimensionless radius
306   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

( )
The boundary conditions are no-flux condition at the center éëC A¢ ùû = 0 and the con-
r =0
centration at the outer surface of the pellet is [CA]R = CA0. The interested reader may refer to
any reaction engineering text (see Fogler, 2008) to verify that the concentration at any point
in the pellet is given by

1 sin h ( fx )
y= (7.87)
x sin h ( f )

We will write a MATLAB code to simulate mass transfer and reaction in the spherical pellet
using TDMA and compare the results with the above solution. As Equations 7.85 and 7.86
are equivalent, either of them can be simulated to obtain the same results. We will simulate
the dimensionless model in this example, and the original model (Equation 7.84) will be
simulated in the next section.

Example 7.8  Reaction in Catalyst Pellet: Effect of Thiele Modulus

Problem: Solve Equation 7.86 for diffusion and reaction in a spherical pellet of radius
R  = 2 mm. Effective diffusivity of the species in the pellet is De = 10-5 cm2 /s , and
­reaction rate constant is k = 6.25 s−1. Also verify the effect of the Thiele modulus by
changing k.
Solution: The model is discretized as follows:

yi +1 - 2yi + yi -1 yi +1 - yi -1
2
+ - f2 k = 0 (7.88)
h xi h 

where h = 1/n, since we are working with dimensionless quantities, and ξi = (i − 1)/n.
Collecting appropriate terms together, the tridiagonal equation for the internal
nodes is

æ 1 1 ö æ 2 2ö æ 1 1 ö (7.89)
ç 2- ÷ yi -1 + ç - 2 - f ÷ yi + ç 2 + ÷ yi +1 = 0
èhxih ø
 èhø èhxih ø

b1 b2 b3 

At the first node, the ghost-point boundary condition yields ψi + 1 = ψ0. Thus, β1 is
not relevant and β3 = 2/h2.
The following code solves the ODE-BVP:

% Simulation of porous catalyst pellet

% as a function of Thiele Modulus
%% Model parameters
diffCoeff=0.25;
R=0.2;
 Special Methods for Linear and Nonlinear Equations   ◾    307

k=6.25;
C_A0=5e-5;
phi=sqrt(k/diffCoeff)*R;
%% Discretization and Precomputing
n=20;
h=1/n; % Dimensionless
xi=0:h:1; % Dimensionless

%% Coefficients for various terms

beta1=1/h^2 - 1./(xi*h);
beta1(1)=0; beta1(end)=0; % Boundaries
beta2=-2/h^2 - phi^2;
beta2=beta2*ones(1,n+1); % At center
beta2(end)=1; % Outer surface
beta3=1/h^2 + 1./(xi*h);
beta3(1)=2/h^2; beta3(end)=0; % Boundaries
%% Solving and displaying results
b=[zeros(n,1); 1];
C_A=thomasSolve(beta1,beta2,beta3,b);
psi=sinh(phi*xi)/sinh(phi)./xi; % Analytical
plot(xi,C_A,’-b’, xi,psi,’r.’);

The results are shown in Figure 7.8. Solid lines represent the numerical solution, and
dots represent the analytical result as per Equation 7.87. The effect of varying the
Thiele modulus is seen in the figure. Since the Thiele modulus is the ratio of reac-
tion rate to diffusion rate, large values of the modulus result in diffusion limitation.
Conversely, when ϕ ≲ 1, diffusion is fast and there is no diffusion limitation in the
system.

1
φ=1

0.8

0.6 φ=2
CA/CA0 (–)

0.4

0.2 φ=4

φ = 10
0
0 0.5 1
r/R (–)

FIGURE 7.8  Simulation of reaction and diffusion in a spherical pellet for various values of the
Thiele modulus. Lines show numerical results, and symbols show the analytical solution.
308   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

7.5.2.2 Langmuir-Hinshelwood Kinetics in a Pellet

The catalytic reaction is often given by Langmuir-Hinshelwood rate kinetics. As before, the
reaction rate will be given by

kC A
r= (3.92)
1 + K r C A2

This problem will be solved using the dimensional Equation 7.85 in the CGS system.
The  concentration at the surface of the pellet is CA0 = 5 × 10−5 mol/cm3, the reaction rate
constant is 100 s–1, and the constant Kr = 109 cm6/mol2. We will solve this using fsolve.
The equations after discretization are given by

De D
2 ( i +1
C - 2Ci + Ci -1 ) + e ( Ci +1 - Ci -1 ) - r ( Ci ) = 0, for i = 2 to n
h ri h

De
( 2Ci +1 - 2Ci ) - r (Ci ) = 0, for i = 1
h2

Cn+1 - C A0 = 0 (7.90)

An important aspect while writing codes is to benchmark them with known solutions.
Since the ODE-BVP with LH kinetics is complex, it is difficult to benchmark them. So, we
will take an indirect approach here. We will write the code for the original problem and
execute it with Kr = 0. With this change, the LH kinetics will be equivalent to the first-order
reaction that we saw in Example 7.7. After comparing these results with those from the
previous numerical code, we will analyze the effect of various parameters. The next example
demonstrates this approach.

Example 7.9  Diffusion and Reaction with Langmuir-Hinshelwood Kinetics

Problem: Solve the problem for the spherical pellet of Equation 7.85, with reaction rate
given by the Langmuir-Hinshelwood model of Equation 3.92.
Solution: First, we will write the MATLAB function to compute the residuals as
per Equation 7.90. This function file thieleLHfun.m is given below:

function gval=thieleLHfun(Y,par)
%% Getting parameters
n=par.n;
h=par.h;
k=par.k;
Kr=par.Kr;
Da=par.diffCoeff;
 Special Methods for Linear and Nonlinear Equations   ◾    309

%% Building the model

gval=zeros(n+1,1);
for i=1:n
C=Y(i);
% Reaction term
rRxn=k*C/sqrt(1+Kr*C^2);
% Diffusion terms
if (i==1)
diffTerm=Da/h^2*(2*Y(i+1)-2*Y(i));
else
diffTerm=Da/h^2*(Y(i+1)-2*Y(i)+Y(i-1)) ...
+ Da/((i)*h*h)*(Y(i+1)-Y(i-1));
end
gval(i)=diffTerm-rRxn;
end
gval(n+1)=Y(n+1)-par.C0;

The driver script will be written in a similar manner as before, using fsolve to obtain
the solution as the concentration profile.
% Simulation of porous catalyst pellet
% with Langmuir-Hinshelwood kinetic model
%% Model parameters
R=0.2;
n=100;
h=R/n;
catParam.R=R;
catParam.n=n;
catParam.h=h;
catParam.diffCoeff=0.25;
catParam.k=100;
catParam.Kr=1e10;
catParam.C0=5e-5;
%% Initializing and Solving
Yguess=catParam.C0*ones(n+1,1);
opt=optimset(‘tolx’,1e-12,’tolfun’,1e-12);
Ysol=fsolve(@(Y) thieleLH1(Y,catParam), Yguess);
%% Plotting the results
xi=0:1/n:1;
psi=Ysol/catParam.C0;
plot(xi,psi,’-.r’);
xlabel(‘r/R (-)’); ylabel(‘C_A/C_{A0} (-)’);
Figure 7.9 shows the results of benchmarking the nonlinear code, by changing the
underlined line of code to vary Kr. The results with Kr = 0 are compared with the first-
order reaction case (with ϕ = 4). The numerical results from the nonlinear solver
match the analytical solution very well.
310   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

0.8

0.6
CA/CA0 (–)
Kr = 1e10

0.4

Kr = 1e9
0.2
φ=4
0
0 0.5 1
r/R(–)

FIGURE 7.9  Benchmarking of code with LH kinetics with Kr = 0 (solid line) by comparing it with
the analytical solution for ϕ = 4 (symbols). The effect of varying Kr is also shown.

Figure 7.9 also presents the effect of varying Kr on the concentration profile in the pel-
let. Note that the baseline case considered in Chapter 3 was Kr = 1 m6/mol2, which equals
Kr = 1012 cm6/mol2. At this value of Kr, the diffusion is very fast, and nearly the entire pellet
concentration is the same as the surface concentration. This is because of the small pel-
let size. For larger pellets (or smaller pores, which reduces De ), mass transfer effects gain
importance. However, with highly porous catalyst particles of size ~1 mm, internal diffu-
sion may usually be assumed to be fast.
Finally, Figure 7.10 shows the effect of concentration at the pellet surface on concen-
tration profiles inside the pellet. Four cases are considered, with CA0 calculated using the
ideal gas law at 300 K and partial pressure, pA, in the gas phase being 1, 2, 5, and 10 bar.

pA0 = 10 bar
0.8

0.6
CA/CA0 (–)

pA0 = 5 bar

0.4
pA0 = 2 bar

0.2
pA0 = 1 bar

0
0 0.5 1
r/R (–)

FIGURE 7.10  Effect of varying the concentration at the catalyst surface.

 Special Methods for Linear and Nonlinear Equations   ◾    311

As the concentration increases, the inhibition term (denominator in the kinetic rate
expression) increases and the pellet increasingly becomes reaction-limited.
The above example brings us to the end of this section. Irrespective of the coordinate
system, the key approach in solving ODE-BVPs, elliptic PDEs, and other similar problems
remains the same: using appropriate numerical differentiation to convert the differential
equations into a set of algebraic equations and solving these equations either directly or by
exploiting their sparse structure.

7.6 EPILOGUE
This chapter dealt with numerical techniques for solving linear or nonlinear equations with
sparse structure. This implies that the matrix A in the linear equation

Ax = b

or the Jacobian, in case of the nonlinear function, J = ∇g(x) has a banded structure, as
described in Figure 7.1. A banded system of equations most commonly arises in process
simulation due to the discretization of BVPs.
In the case of linear system of equations, we focused on two “special” methods to effi-
ciently solve the linear equations: (i) the TDMA and (ii) the Gauss-Siedel method. From a
numerical techniques perspective, we discussed how TDMA (or a banded solver) is more
efficient than a general-purpose Gauss Elimination–based solver. Gauss-Siedel is intro-
duced as one of the key iterative methods for linear systems.
From a nonlinear systems perspective, a method of successive substitution was intro-
duced, which iteratively employs a TDMA algorithm to solve a tridiagonal set of model
equations. This method was heuristically motivated and is straightforward to use; however, it
may not provide a desirable convergence behavior when solving several nonlinear problems.
The Gauss-Siedel method, on the other hand, was introduced for both linear and non-
linear equations. This iterative method is a general-purpose method, but it is also easy to
exploit banded structure of matrix A to improve the computational requirement on Gauss-
Siedel. This method benefits from the fact that the band-diagonal matrix obtained after
finite difference discretization is often diagonally dominant. Convergence properties can
further be improved using the under-relaxation approach or source term linearization.
Finally, we introduced the option 'jacobPattern' in MATLAB’s fsolve solver.
Based on the discussion in this chapter and experience, I make the following recommen-
dations: (i) TDMA or banded solver for linear systems, (ii) fsolve as a method of choice
for nonlinear banded systems, and (iii) Gauss-Siedel with appropriate under-relaxation if
the problem does not give the desired results with fsolve.

EXERCISES
Problem 7.1 Consider a nonlinear equation x = G(x), which is to be linearized and solved
using fixed point iteration. The linearized equation is given by

x = G0( ) + G1( ) x
i i

312   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

( ) i i
( ) i i
( )
G0( ) = G x ( ) - x ( )G¢ x ( ) , G1( ) = G¢¢ x ( )
i i

Show that solving the fixed point iteration of a linearized model at each
iteration

G0( )
i
x( ) =
i +1

1 - G1( )
i

is equivalent to using the Newton-Raphson method for the original problem.

Problem 7.2 The code for TDMA solver thomasSolve.m was given in Example 7.2.
This code takes vectors l,u,d,b and solves the tridiagonal linear equa-
tions problem and returns the solution x. In the other examples, we created
matrix A and vector b. Convert the thomasSolve code into a new func-
tion newThomasSolve, which would take tridiagonal matrix A and vector
b as inputs and return x.
Problem 7.3 Modify the code from Example 7.6 to implement the TDMA-based suc-
cessive substitution method with under-relaxation. Solve for ω = 0.25 and
ω = 0.1.
Problem 7.4 Modify the Gauss-Siedel code from Example 7.7 for Jacobi iterations with
and without under-relaxation. Hence, solve the heat conduction problem.
 CHAPTER 8

Implicit Methods
Differential and Differential
Algebraic Systems

8.1 GENERAL SETUP
The underlying theme of this chapter is implicit methods for solving differential equations.
Examples of systems covered in this chapter include ordinary differential equations (ODEs)
that are stiff in nature, partial differential equations (PDEs) that require implicit time step-
ping, and systems governed by differential algebraic equations (DAEs, such as differential
equations with algebraic constraints). However, DAEs will remain a major focus of this
chapter.
This is an advanced chapter that builds upon the analyses of ODEs in Chapter 3, PDEs
in Chapter 4, linear system dynamics in Chapter 5, and algebraic equations in Chapter 6.
The final case study of Chapter 3 presented an example where ode45 is unable to con-
verge for default ODE solver options. This is an example of a stiff system of ODE-IVP. The
Crank-Nicolson method was introduced in Chapter 4 for solving hyperbolic PDEs, but we
deferred it until this chapter. Finally, DAEs, which consist of both differential and algebraic
equations, are a class of problems of interest to chemical engineers. Traditionally, these
three topics are covered separately in textbooks. Since a unifying theme in this broad spec-
trum of topics is the use of implicit methods, I present a unified coverage in this chapter.
The remainder of this section will provide more details on each of the three topics. Since
ODE-IVP and PDEs were covered at length in Chapters 3 and 4, respectively, most of this
chapter will be devoted to DAEs.

8.1.1 Stiff System of Equation

Stiffness is a property of a single ODE or a system of ODEs where fast and slow dynamics
appear simultaneously. Stiff ODEs are difficult to solve using explicit Runge-Kutta (RK)
methods. For example, the simulation of a chemostat in Section 3.5.4 showed that when
the value of saturation constant Ks was changed from 0.25 to 0.005, ode45 gave unstable

313
314   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

response for the latter value. I mentioned in the example that this unstable behavior of
ode45 was because the set of ODEs becomes stiff.
This issue and its implication on numerical methods are analyzed presently.
A linear approximation of this nonlinear chemostat model around its steady state was
obtained in Chapter 5. The linearized model is given by

d
y = Jy (8.1)
dt

T
where y represents deviation variables, that is, y = ëéS - Sss X - Xss ùû , where Sss and Xss
are the steady state exit concentrations of the substrate and biomass, respectively. For the
stiff ODE case (i.e., Ks = 0.005), the steady state concentrations are Sss = 0.002 mol/L and
Xss = 3.749 mol/L. Under these conditions, the Jacobian is

é -201.7 -0.133ù
J =ê ú (8.2)
ë 151.2 0 û

The eigenvalues of the Jacobian are −201.6 and −0.1, and the ratio of the two eigenvalues is
~2000. The system is stable because the two eigenvalues are negative.
Recall that the transient solution of a system y′ = λy is y(t) = y0eλt. We discussed in Chapter
5 that, for a linear ODE, each eigenvalue governs the dynamic response of the system along
the corresponding eigenvector. The larger the eigenvalue, the faster is the response. Thus, the
eigenvector corresponding to λ1 =  −201.6 is the fast eigenmode. The time required to attain
steady state is ~50 min, since it is determined by the slow eigenvalue, λ2 =  −0.1. Compared
to the overall process dynamics, the dynamics along the first eigenvector is almost instanta-
neous. The phase-plane plot for this system is shown in Figure 8.1. Note that the dynamics
along the direction v1 ≡ [−0.8; 0.6] stabilize rapidly, and the system then moves along the
slow eigenvector v2 ≡ [0.0007; 1].

Fast Slow
y2

y1

FIGURE 8.1  Phase-plane plot for a moderately stiff system obtained by linearizing the chemostat
bioreactor model at its steady state value.
 Implicit Methods   ◾    315

The upper limit on the step-size for an explicit ODE-IVP method is determined by the
largest eigenvalue. For example, the largest step-size for Euler’s explicit method is given by
h < 2/λ1. Thus, the step-size, h, needs to be less than 0.01, for Euler’s explicit method to be
stable. However, the time to reach steady state is ~50 min, since it is governed by the slower
λ2. Therefore, at least 5000 steps will be required by an explicit solver to reach the final solu-
tion. In fact, for the above example, ode45 required ~12,000 steps.
An implicit solver, ode15s, on the other hand, required only 93 steps. I will use Figure 8.1
to qualitatively explain the “mechanism” behind this observation. In the first 0.05 s, the sys-
tem responds along the first eigenvector (dashed line marked as “fast”), and the solver reaches
the slow eigenvector (dashed line marked as “slow”). The solver takes small steps during this
phase for accuracy. Now the response along eigenvector v1 has settled, and the system now
moves along the slow eigenvector v2. It is now possible to take larger steps, and still maintain
the desired accuracy. This is exactly what ode15s does. In contrast, ode45 takes a very
large number of steps because there is a stringent upper limit on step-size for stability.
The analysis of the original nonlinear chemostat from Section 3.5.4 follows the same
arguments as above, but is complicated by the nonlinear reaction term. After the evolution
of the system along the fast eigenvector, the solver attempts to take larger steps. Unlike the
linear case, ode45 does not account for the rapidly changing nonlinear reaction term and
fails to converge. Thus, the presence of fast and slow dynamics simultaneously made the
implicit ode15s the preferred solver for stiff ODEs.

8.1.1.1 Stiff ODE in Single Variable

Let us consider the system

y ( t ) = e -1000t + e -t

which also has fast and slow dynamics, simultaneously. Differentiating

y ¢ = -1000e -1000t + ( -1000 + 999 ) e -t

gives us the ODE

dy
= -1000 y + 999e -t , y ( 0 ) = 2 (8.3)
dt

Solving the above ODE using ode45 takes 12000 steps, whereas ode15s takes only 67
steps. The cause for this is the same as the multivariable case: λ =  − 1000 dictates the step-
size while e−t determines the time required for the dynamics to settle to a steady state.
The original chemostat problem of Section 3.5.4 showed how a stiff system of ODEs can
make an explicit solver unstable. Several examples of practical interest may be significantly
more stiff than chemostat. I used this section to define stiffness and to demonstrate it from
a practical perspective. As in Chapter 3, we will devote Section 8.2 to implicit methods for
solving ODEs.
316   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

8.1.2 Implicit Methods for Distributed Parameter Systems

The Crank-Nicolson method is an implicit method for solving hyperbolic and parabolic
PDEs. A generic hyperbolic PDE discussed in Chapter 4 is given by

¶f ¶f
+u = S ( f) (8.4)
¶t ¶z

Finite difference approximation is used in both spatial and temporal directions. The
spatial domain is split in n intervals and the interval size is D z = L n ; a step-size of
Δt is used in time, and ϕp,i represents the solution at time p and location i. The solution is
known at all locations at time p, and this information is used to obtain the solution at
next time, p + 1.
The Crank-Nicolson method was derived in Chapter 4. A central difference formula is
used for the spatial derivative and an implicit formula similar to the trapezoidal rule is used
in time. This results in the following implicit formula for the Crank-Nicolson method:

f p +1,i - f p,i u æ f p,i +1 - f p,i -1 f p +1,i +1 - f p +1,i -1 ö 1

+ ç + ÷ - ( Sp,i + Sp +1,i ) = 0 (8.5)
Dt 2è 2D z 2D z ø 2

The Crank-Nicolson method will be demonstrated in Section 8.3.

8.1.3 Differential Algebraic Equations

This brings us to the third set of problems: differential algebraic equations or DAEs, which form
a major focus of this chapter. Consider a system whose behavior is defined by n-­dependent
variables, Y ∈ R n. Some dependent variables are governed by differential equations:

d
y = f ( t ,y ,x ) (8.6)
dt

where y ∈ R nd and YT = éë y T x T ùû . The system is underdefined and needs additional

(n − nd) equations. In the case of DAEs, these additional equations are algebraic:

0 = g ( y ,x ) (8.7)

The variables, y, that appear in differential form in Equation 8.6 are differential variables,
whereas the remaining variables, x, are algebraic.
DAEs of the form of Equations 8.6 and 8.7 form one class of DAEs, known as semiexplicit
DAEs. A general form for representing DAEs is

F ( t,Y ,Y ¢ ) = 0 (8.8)
 Implicit Methods   ◾    317

While several numerical methods are available to solve the above general form of DAE, we
will restrict ourselves to semiexplicit DAEs in this chapter.
Typically, fully implicit methods are used to solve DAEs. Some of the popular, so-called
linear multi-step methods will be discussed in Section 8.2. Analysis and classification of
DAEs and their implementation in MATLAB will be discussed in Section 8.4.

8.2 MULTISTEP METHODS FOR DIFFERENTIAL EQUATIONS*

Due to their importance in modeling physical phenomena, differential equations have
received a lot of attention. All ODE-solving methods work thusly: Given the values of
dependent variables yk at any time k and the functional form of the differential equation,
how does one efficiently compute the value yk+1 at the next time instance?
Various classes of techniques have been developed for solving ODEs. Explicit methods
are easier to use and provide good accuracy. They are however unsuitable for highly stiff
problems, problems with algebraic constraints, and in problems involving convection
without attenuation. The RK class of methods, discussed in Chapter 3, form an important
class of explicit ODE-solving methods. The distinguishing feature of RK methods is that
the slope of the curve y(t) is computed as a weighted average of function values c­ omputed
at various points between k and (k + 1). It involves projecting the solution within this time
interval and using that information to improve the accuracy of the technique.
When reaching the solution y(k) at time k, we have computed an entire history of solu-
tions, y0, y1, …, yk. RK methods, however, do not use this historical information in comput-
ing the next solution. Multistep methods, on the other hand, use the past information to
compute the solution at the next time-step. The update equation for solving an ODE using
a general linear multistep method is written as

y k +1 = ëéa1 y k + a2 y k -1 +  + an y k ±n+1 ùû + b0 hf ( t k +1 ,y k +1 )

+ h éëb1 f ( t k ,y k ) +  + bm f ( t k -m+1 ,y k -m+1 ) ùû (8.9)

The above equation leads to an explicit method if b0 = 0; if b0 is nonzero, then the method
is implicit. The most popular multistep methods are the following:

• Adams-Moulton (AM) methods are implicit methods, with aj = 0.

• Adams-Bashforth (AB) methods are explicit methods, with aj = 0 and b0 = 0.
• Backward difference formula (BDF) methods are implicit methods, with bj = 0 (j ≥ 1).

While there are other solvers, we will primarily focus on these three classes of methods.
I will end this discussion by mentioning one more key property of multistep methods.

*  This section is added for completeness. It may be skipped without any loss in continuity.
318   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Non-self-starting property: The term “multistep” implies that the information at past n
points is used for computing the next point, yk+1. Let us say that we are at the initial time
t0 with y0 as the initial value. In order to compute the next solution, y1, we need the previ-
ous data points y0, y−1, and so on. Since the values y−1 (and earlier) are not available, it is
not feasible to directly compute y1. Thus, the higher-order multistep methods are non-
self-starting; they require a procedure to compute past values and start the ODE solution.
I will now briefly summarize the three classes of methods. The focus of this chapter is
not on numerical techniques per se; rather, we are interested in using differential equa-
tion solvers in MATLAB® for solving problems of practical interest. A brief discussion
of these methods is provided to equip readers to make an educated choice of solvers in
one’s work.

8.2.1 Implicit Adams-Moulton Methods

The core idea behind Adams’ family of methods (both Adams-Moulton as well as Adams-
Bashforth) is that the function f(t, y) is approximated as an interpolated polynomial
( )
f t ,y ( t ) . Thus

k +1 ( k +1)h

ò dy = ò f ( t,y ( t)) dt
k kh
(8.10)

The left-hand side evaluates simply as (yk + 1 − yk). The polynomial on the right-hand side
varies depending on the number of past terms included in interpolation, giving rise to dif-
ferent Adams-Moulton methods of varying order.
The first-order method, AM-1, is simply the Euler’s implicit method since it uses a single
point, f = f k +1, for interpolation, resulting in

y k +1 = y k + hf k +1 (8.11)

where a shorthand notation

fi  f ( t i ,yi ) (8.12)

is used to represent the data point.

The second-order method, AM-2, uses a linear interpolation between fk + 1 and fk:

( k +1)h
æ f k +1 - f k ö

y k +1 = y k +
ò
kh
ç fk +
è h
( t - kh ) ÷ d t
ø

(8.13)
 Implicit Methods   ◾    319

Solving this, we get

æ ( k +1)h ö
æ f k +1 - f k ö ç é t2 ù ( k +1)h ÷
y k +1 = y k + éë f k h ùû + ç ÷ç ê 2 ú - kh é t ù
ë û kh ÷ (8.14)
è h ø ë û kh
è ø

The last term in the brackets expands as

æ ( k + 1)2 - k 2 ö
h ç
2
-k÷
ç 2 ÷
è ø

Since this evaluates to h2/2, the final equation for AM-2 method is given by

h

y k +1 = y k +
2
( )
f ( t k ,y k ) + f ( t k +1 ,y k +1 )

(8.15)

The second-order Adams-Moulton method is also known as the trapezoidal rule since it
looks like the trapezoidal rule from numerical integration (see Appendix E).

8.2.2 Higher-Order Adams-Moulton Method

A formal derivation of Adams-Moulton methods, including error analysis, can be more
conveniently from polynomial interpolation formulae. Let us consider the derivation of
AM-2 method again, using Newton’s backward difference formula. Refer to Appendix D,
where we derived Newton’s forward difference formula; the backward difference formula
works in a similar manner. Nondimensional time, α, is a real valued parameter defined as

t - t k +1
a= (8.16)
h

Thus, tk + 1 → (α = 0), tk → (α =  − 1), tk − 1 → (α =  − 2), and so on. In the case of AM-2 method,
a second-order polynomial is used. Using Newton’s backward difference formula

a ( a + 1) ( a + n - 1)
f B ( t ) = f k +1 + aÑf k +1 +  + Ñn f k +1 + RB (8.17)
n!

where

a ( a + 1) ( a + n )
RB = hn+1 f n+1 ( x ) (8.18)
(n + 1)!
320   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

AM-2 method is derived with n = 1, that is, by retaining the first two terms in Equation 8.17.
Thus, the equation for AM-2 is given by substituting this in Equation 8.10. Since dτ = h dα

a ( a + 1) 2
0
é ù

ò
y k +1 = y k + h ê f k +1 + aÑf k +1 +
ê
-1 ë
2
h f ¢¢ ( x ) ú da
úû
(8.19)

Using the definition of ∇fk + 1, we get

é é a2 ù
0
h2 é a3 a2 ù ù
0

y k +1 = y k + h f k +1 éëa ùû -1 + ( f k +1 - f k ) ê ú + f ¢¢ ( x ) ê + ú ú
0
ê
ê 2
ë û -1 2 ë 3 2 û -1 ú
ë û
é æ 1ö h 2
æ 1 ö ù
= y k + h ê f k +1 + ( f k +1 - f k ) ç - ÷ + f ¢¢ ( x ) ç - ÷ ú (8.20)
ë è 2 ø 2 è 6 øû

Thus, the AM-2 method with the local truncation error is given by the following equation:

h æ h3 ö
2
( )
y k +1 = y k + f ( t k ,y k ) + f ( t k +1 ,y k +1 ) + ç - f ¢¢ ( x ) ÷
12
(8.21)
  è  ø
AM-2
( )
O h3

Thus, AM-2 has a local truncation error as shown above. As we observed in Chapter 3, the
global truncation error (GTE) in the ODE solver drops by one order, making AM-2 method
( )
O h2 accurate with respect to the GTE.
Higher-order Adams-Moulton formulae are derived by progressively including an addi-
tional term in the backward difference formula of Equation 8.17. The first few Adams-
Moulton formulae are given in Table 8.1. Note that the AM-n method is nth order accurate
since the GTE is ~O hn . ( )
8.2.3 Explicit Adams-Bashforth Method
Explicit Adams-Bashforth methods follow a similar principle as Adams-Moulton methods,
except that b0 in Equation 8.9 is 0, making them explicit ODE-solving methods. Thus, a

TABLE 8.1  Coefficients for Adams-Moulton Methods

Method b0 b1 b2 b3 b4 GTE

AM-2 1/2 1/2 ( )

O h2
AM-3 5/12 8/12 −1/12 O (h ) 3

AM-4 9/24 19/24 −5/24 1/24 O (h ) 4

AM-5 251/720 646/720 −264/720 106/720 −19/720 O (h ) 5

Only methods up to AM-5 are shown. Interested readers are referred to numerical ODE
texts for coefficients of higher-order methods.
 Implicit Methods   ◾    321

Newton’s backward difference polynomial is fitted to the past n points. Readers can easily
notice that the first-order Adams-Bashforth method (AB-1) is simply the explicit Euler’s
method. As in Adams-Moulton methods, the following real variable will be defined for
deriving Adams-Bashforth formulae:

t - tk
a= (8.22)
h

A backward interpolating polynomial is fitted to the data fk, fk − 1,  … , fk − n + 1 and substituted

in Equation 8.10 to obtain

ò
y k +1 = y k + f B ,k ( a ) h da
0
(8.23)

Clearly, since the polynomial is fitted to the past data points

a ( a + 1) ( a + n - 1)
f B ( t ) = f k + aÑf k +  + Ñ n f k + RB (8.24)
n!

The mathematical contrast between AB-n and AM-n methods will be evident on comparing
Equation 8.16 with (8.22) and Equation 8.17 with (8.24). The practical contrast indeed is
that they are explicit and implicit methods, respectively. Notice also that integrating from k
to k + 1 implies integrating from α = 0 to 1, in AB-n method. Substituting and integrating,
we get

é 1
é a2 ù h2 é a2 a3 ù ù
1

y k +1 = y k + h ê f k éëa ùû 0 + ( f k - f k -1 ) ê ú + f ¢¢ ( x ) ê + ú ú
1
(8.25)
ê ë 2 û0 2 ë 2 3 û0 ú
ë û

Thus, the AB-2 method is given by the following formula:

h æ 5h3 ö
2
( )
y k +1 = y k + 3 f ( t k ,y k ) - f ( t k -1 ,y k -1 ) + ç f ¢¢ ( x ) ÷ (8.26)
   è1 2
 ø
AB -2
( )
O h3

Since the right-hand side does not depend on (k + 1), AB-2 is an explicit method. AB-2 is
not a self-starting method because y1 depends on y−1, and hence the method can only start
from computing y2 onward.
Higher-order AB-n methods include a larger number of terms in the formula as well as
yield higher accuracy. These are summarized in Table 8.2.
322   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

TABLE 8.2  Coefficients for Adams-Bashforth Method from Orders 2–5

Method b0 b1 b2 b3 b4 b5 GTE

AB-2 0 3/2 −1/2 ( )

O h2
AB-3 0 23/12 −16/12 5/12 ( )
O h3
AB-4 0 55/24 −59/24 37/24 −9/24 O (h )
4

AB-5 0 1901/720 −2774/720 2616/720 −1274/720 251/720 O (h )

5

Interested readers are referred to numerical ODE texts for coefficients of higher-order methods. Since
AB-n methods are explicit, the coefficient b0 is zero.

8.2.4 Backward Difference Formula

The backward difference formula (BDF) methods work in a different way than Adams’ fam-
ilies of ODE solvers. In Adams methods, a polynomial was fitted to past function values,
fi. Instead, in BDF, a polynomial is fitted to the past solution values yi and yet-to-be-deter-
mined value yk + 1. Thus, an nth-order polynomial is fitted to the past n points* to obtain an
interpolating polynomial, y B. The BDF is derived by differentiating this polynomial and
substituting it in the ODE.
For example, the first-order BDF uses the data points yk + 1, yk to obtain the polynomial as

y k +1 - y k
y B = y k +1 +
t k +1 - t k
(t - t k +1 ) (8.27)

Clearly, y B¢ is just the slope of the above line and the denominator is simply h. Thus, we
obtain the first-order BDF as simply the Euler’s implicit formula:

y k +1 - y k
= f ( t k +1 ,y k +1 )
h (8.28)
i.e., y k +1 = y k + h ( t k +1 ,y k +1 )

How does one derive higher-order BDF? They are derived in quite a similar manner as the
Adams-Moulton method, except that (i) y B ( t ) is fitted instead of f B ( t ), and (ii) the deriva-
tive y B¢ is substituted in the original ODE instead of integrating f B . The derivation of error
for first-order BDF is left as an exercise.
Second-order Newton’s backward difference formula is given by

a ( a + 1) a ( a + 1) ( a + 2 )
y B ( t ) = y k +1 + aÑy k +1 + Ñ2 y k +1 + h3 y ¢¢¢ ( x ) (8.29)
2 6

*  Recall that nth-order polynomial requires (n + 1) points: yk + 1 and the previous n points.
 Implicit Methods   ◾    323

Since
dy 1 dy
=
dt h da
(8.30)
1æ 2a + 1 2 h3 ö
y B¢ = ç Ñy k +1 +
hè 2
Ñ y k +1 +
6
(
3a2 + 6a + 2 y ¢¢¢ ( x ) ÷ )
ø

Note that the derivative is computed at time (k + 1), that is, α = 0. Substituting in the ODE
yields
3
( yk +1 - yk ) + 12 ( yk +1 - 2 yk + y(k -1) ) + h3 y ¢¢¢ ( x ) = hf ( t k +1 ,y k +1 ) (8.31)

Rearranging, we get the BDF-2:

4 y k - y k -1 2h 2h3
y k +1 = + f ( t k +1 ,y k +1 ) + y ¢¢¢ ( x ) (8.32)
 3 3   9

BDF -2
( )
O h3

It is often customary to write the BDF as

4 y - y k -1 2h 2h3
y k +1 - k = f ( t k +1 ,y k +1 ) + y ¢¢¢ ( x ) (8.33)
 3  3  9
BDF - 2 O ( h3 )

Table 8.3 shows various BDFs of various orders.

One of the most popular numerical methods for solving stiff ODEs and DAEs is Gear’s
method, which uses BDF of varying orders, from first to fifth order. BDF methods are popu-
lar for solving highly stiff problems because they have good stability (up to fifth-order),
reasonably high accuracy, and capability to solve differential equations with algebraic con-
straints. In case of DAE problems, the differential equations retain the entire formula from
Table 8.3, whereas the left-hand side is zero for algebraic equations.

TABLE 8.3  Formula for BDF Methods with Various Accuracy

Method b0 a1 a2 a3 a4 a5 a6 GTE

BDF-2 2/3 4/3 –1/3 ( )

O h2
BDF-3 6/11 18/11 –9/11 2/11 O (h )
3

BDF-4 12/25 48/25 –36/25 16/25 –3/25 O (h )

4

BDF-5 60/137 300/137 –300/137 200/137 –75/137 12/137 O (h )

5

BDF-6 60/147 360/147 –450/147 400/147 –225/147 72/147 –10/147 O (h )

6

Most commercial solvers used BDF methods of orders 1–5. Methods beyond BDF-6 are not used
since they are not zero stable.
324   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

NUMERICAL DIFFERENCE FORMULA (NDF)–BASED SOLVERS

NDF is a modification of the BDF method for solving ODEs and DAEs. Let us take a closer
look at BDF. The qth-order term of the polynomial expansion of Equation 8.29 is given by

Ñqyk +1
Pq = a ( a + 1) ( a - q + 1) (8.34)
q!

and yB = åqn =0 Pq . Recall that in deriving the BDF, we differentiated yB since we required

éd ù
êë dt yB úû
( k +1)

in the derivation of BDF. Moreover, at (k + 1), α = 0. Differentiating Equation 8.34, we get

d Ñqyk +1
Pq = é( a + 1) ( a + 2) ( a - q + 1) + ( terms with a ) ùû (8.35)
da q! ë

Since we compute the above at α = 0, all the terms in α disappear. The remaining term in the
bracket at α = 0  is (q − 1)!. Thus

éd ù 1 æ Ñq yk +1 ö
P = ç ÷ (8.36)
êë dt úû
q
h è q ø
( k +1)

Thus, the BDF of nth-order may also be written as

n
Ñqyk +1

åq =1
q
= hf ( tk +1,yk +1 )

(8.37)

NDF method is a modification of the above:

å
Ñqyk +1
q
(
= hf ( tk +1,yk +1 ) + kg y k +1 - y k( +)1
0
) (8.38)
q =1

where
κ is a constant
γ = [1 + (1/2) +  ⋯  + (1/n)] and
yk( +)1 is an initial guess of the solution
0

The final term on the right-hand side is added to improve the convergence behavior of the
numerical method.
MATLAB’s ode15s solver uses a combination of BDF and NDF.
 Implicit Methods   ◾    325

8.2.5 Stability and MATLAB® Solvers

8.2.5.1 Explicit Adams-Bashforth Methods
The stability of explicit Euler’s method was discussed in Chapter 3. For an ODE, y′ =  − ay,
the stability requirement for Euler’s explicit method was 0 ≤ ah < 2. The analysis of linear
ODEs was extended to multivariable systems in Chapter 5. Using the same analogy, the
stability condition for explicit Euler’s method for multivariable system is

-2 < lh £ 0 (8.39)

where λ denotes eigenvalues of the multivariable system. The largest eigenvalue determines
the limit on step-size, h. Eigenvalues can be complex numbers. Thus, if we plot λh on a
complex plane, the stability region for Euler’s explicit method is a circle in the left-half
plane, with the circle intersecting the real axis at −2.
A narrow stability region limits the applicability of the ODE solver, as observed for Euler’s
explicit method. Unfortunately, the stability region for Adams-Bashforth methods shrinks
with the increasing order of the method. Thus, higher-order Adams-Bashforth methods
are not very stable. While their higher accuracy can be exploited for nonstiff systems, they
are unsuitable for stiff ODEs and DAEs. They can be used as an alternative to RK methods
when a high degree of accuracy is required.

8.2.5.2 Implicit Euler and Trapezoidal Methods

Euler’s implicit method is highly stable. It is said to be A-stable, which implies that it is stable
for all values of λh in the left-half plane. In other words, ODE solution using Euler’s implicit
method is stable for any h > 0 if the original ODE itself was stable. However, it is not very use-
( )
ful in practice since it is ~O h1 accurate. The trapezoidal method, with its stability region
spanning the left-half plane, is also A-stable and hence preferred over Euler’s implicit method.

8.2.5.3 Implicit Adams-Moulton Methods of Higher Order

Trapezoidal method is AM-2 method. While it has a wide range of stability, it is only O h2 ( )
accurate. However, as the order of Adams-Moulton methods increases, the stability region
decreases. The stability region of AM-n method, though, is significantly broader than the stabil-
ity region of AB-n methods. Thus, higher-order AM-n methods present in a trade-off between
accuracy and stability of the method. The use of variable-order AM solvers is, therefore, popular.

8.2.5.4 BDF/NDF Methods
Both BDF-1 (implicit Euler’s method) and BDF-2 are A-stable. Like AM-n method,
the stability region of BDF-n also shrinks as the order n increases. Stability regions for
BDF-3 and BDF-4 are also very large, but shrink for BDF-5 and BDF-6. Interestingly,
BDF methods beyond the sixth order are not zero-stable.* Consequently, BDF beyond
BDF-6 cannot be used. In fact, most commercial solvers use BDF methods of order
BDF-1 to BDF-5.

*  Zero stability implies that a numerical technique is stable as h → 0. This is a very important property as a very small step-size
may be needed for higher accuracy. Hence, a method that is not zero stable is not useful in practice.
326   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

8.2.5.5 MATLAB® Nonstiff Solvers

The default and most popular ODE-IVP solver in MATLAB, ode45, uses an adaptive step-
( )
size fourth-order RK method, with GTE ~O h 4 . As discussed in Chapter 3, ode45 uses a
combination of RK-4 and RK-5 methods for step-size adaptation.
ode23 is the other RK solver. It uses a combination of second- and third-order Bogacki-
Shampine formulae. It has a GTE ~O h2 .( )
The popularity of ode45 is due to its high accuracy. Adaptive step-sizing is seamless in
RK methods, making ode45 very efficient and accurate for nonstiff problems.
MATLAB provides ode113, a variable order solver that uses Adams-Bashforth-
Moulton (ABM) methods of orders 1 to 13. Variable order implies that the order of the
ABM solver is varied based on stability and accuracy. High-order RK methods are not
popular because the effort in computing f(t, y) at multiple locations increases rapidly
for higher-order methods. However, multistep methods rely on already computed past
data. Thus, there is only a modest increase in computational requirement in higher-order
ABM methods. If very high accuracy is needed and the system is nonstiff, ode113 may
be used.
In my experience, the primary choice of nonstiff ODE-IVP solver is ode45.

8.2.5.6 MATLAB® Stiff Solvers

MATLAB also provides a few stiff solvers. The most popular and versatile of them is
ode15s, which uses a combination of orders 1–5 NDF or BDF solvers. ode15s is a vari-
able order solver, which means that the order of the solver is varied from first to fifth order
based on the stability and accuracy of the solution. It attempts to use constant step-sizes,
only changing the step-size if the best method does not provide adequate accuracy. It is also
capable of solving moderately stiff index-1 DAE problems as well. BDF and NDF methods
are indeed very popular for solving stiff ODEs and DAE problems.
There are some stiff problems that ode15s is unable to solve. In some examples,
ode23s may be used. It is a second-order Rosenbrock solver. I did not cover Rosenbrock
solvers in our discussions. I often get asked whether ode23s is better than ode15s. It
is a different category of solvers, so one cannot conclude whether it is “better” or “worse”
than ode15s.
However, since ode15s is a higher-order solver and BDF/NDF methods are robust, it
is a preferred choice over all other stiff solvers. One may use ode23s if ode15s does not
work.
Finally, we come to two solvers that use the trapezoidal rule: ode23t (trapezoidal rule)
and ode23tb (trapezoidal rule followed by BDF-2). Since the trapezoidal rule is A-stable,
these methods may be used for highly stiff problems if both ode15s and ode23s fail.
( )
The disadvantage of these two methods is that they are only O h2 accurate. It should be
noted that A-stable does not mean unconditionally stable; these methods may still fail to
converge due to strong nonlinearity, physical constraints, and error propagation at very
small values.
In my experience, the primary choice of nonstiff ODE-IVP solver is ode15s.
 Implicit Methods   ◾    327

8.3 IMPLICIT SOLUTIONS FOR DIFFERENTIAL EQUATIONS

This section will demonstrate the application of the AM-2 (trapezoidal) method to solve
stiff ODE problems (Section 8.3.1) and also demonstrate the Crank-Nicolson method for
hyperbolic PDEs (Section 8.3.2). Recall that I had mentioned in Chapter 4 that Crank-
Nicolson method for hyperbolic and parabolic PDEs is equivalent to using the trapezoidal
method in time. I have therefore included these two examples in this chapter.

8.3.1 Trapezoidal Method for Stiff ODE

The AM-2 trapezoidal method is given by

h æ h3 ö
2
( )
y k +1 = y k + f ( t k ,y k ) + f ( t k +1 ,y k +1 ) + ç - f ¢¢ ( x ) ÷
12
(8.21)
  è  ø
AM-2
( )
O h3

At time k, the solution yk is known and yk+1 is the unknown quantity to solve for. Thus, this
is a nonlinear equation, the solution of which is the value yk+1. Rewriting the above equation
in the form used in Chapter 6 gives

é h ù
ë 2
( )
y k +1 - ê y k + f ( t k ,y k ) + f ( t k +1 ,y k +1 ) ú = 0 (8.40)
  û
g ( y k +1 )

The stiff ODE (8.3) in single variable will be solved using AM-2 method in the next exam-
ple. The function f(t, y) in the above equation is simply the ODE function in y′ = f(t, y) and h
is the step-size, exactly as was seen in the explicit methods in Chapter 3.

Example 8.1  Implicit Trapezoidal Method for Stiff ODE in Single Variable
Problem: Solve the ODE-IVP in Equation 8.3 using the AM-2 trapezoidal method.
Compare the results with ode45.
Solution: The function f(t, y) =  − 1000y + 999e−t will be defined using MATLAB
anonymous function definition:

f=@(t,y) -1000*y+999*exp(-t);

This ODE function is used to obtain g(yk + 1) in Equation 8.40. If the current value yk is
known at time tk, then

fk=f(tk,yk);

will give the value f(tk, yk), which is a known quantity. This quantity can be precom-
puted and used in g(yk + 1) defined in Equation 8.40. If we denote yk + 1 as variable yNew,
then function g(yk + 1) ≡ g(yNew) is given by the following function:
g=@(yNew) yNew-yk - h/2*(fk+f(tNew,yNew));
328   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Note that tk, yk, and fk are known since they are the past values; while tNew,
the time point at which yNew is calculated is also known (tNew=tk+h). Thus, the
unknown is yNew. We will use fsolve to find the root of Equation 8.40.
The function f(t,y) remains the same throughout the simulation, whereas the
function g(yNew) changes at each time point: The function is updated with most
recent values of tk, yk, and fk. The complete code for this problem is given below:

% Solving single ODE using

% Adam-Moulton Second Order (Trapezoidal)
y0=2;
t0=0; tN=1;
f=@(t,y) -1000*y+999*exp(-t);

%% Solving using ode45 for comparison

[tSol,ySol]=ode45(f,[t0 tN],y0);
plot(tSol,ySol); hold on
xlabel('t'); ylabel('y(t)');

%% Setting up AM-2 Trapezoidal method

h=1e-3;
n=(tN-t0)/h;
tALL=0:h:tN;
yALL=zeros(1,n+1); yALL(1)=y0;

%% Solving using AM-2 Trapezoidal method

for k=1:n
% Current time-point
yk=yALL(k);
tk=tALL(k);
fk=f(tk,yk);
% Next time-point
tNew=tALL(k+1);
% Defining g(yNew)
g=@(yNew) yNew-yk - h/2*(fk+f(tNew,yNew));
% Solve and store results
yNew=fsolve(g,yk);
yALL(k+1)=yNew;
end
plot(tALL,yALL,'--');

Figure 8.2 shows the results from the AM-2 trapezoidal method at two different step-
sizes. Since the fast dynamics stabilize within t = 0.003, a small step-size is required
for accuracy. When h=0.01 was used as the step-size, oscillatory behavior was
observed initially. Thus, h=0.001 was required for stability. With this step-size,
AM-2 required 1000 iterations. Despite being an adaptive step-size solver, ode45
required 1229 iterations.
 Implicit Methods   ◾    329

2
ode45
AM-2 (h = 0.001)
1.5 AM-2 (h = 0.01)

y(t)
1

0.5

0
0 0.5 1
t

FIGURE 8.2  Comparison of AM-2 trapezoidal method (with two different step-sizes) and ode45
solution for stiff ODE (8.3) in single variable.

8.3.1.1 Adaptive Step-Sizing
Adaptive step-size methods exist for trapezoidal and other Adams-Moulton methods.
These can be used to give better accuracy. The faster dynamics, in this example, have a time
constant of 0.001 (since λ = 1000). An adaptive step-size ode45 was unable to take large
steps. We now investigate whether it is possible to increase step-size of AM-2 method and
achieve stable performance. Adaptive step-size AM-2 methods are beyond the scope of this
text. But I will give a flavor of adaptive step-sizing in using this example.
An “adaptive step-sizing” will be implemented in an ad hoc manner. We know that a
small step-size is needed for accuracy until the fast dynamics settle down, after which we
are at liberty to increase the step-size* for implicit AM-2 method. We will use this knowl-
edge for the next simulation, which shall be performed in three steps:

• Run the code in Example 8.1 with h=0.0005 for 20 iterations to yield solutions of
the ODE until tN=0.01.
• Now that the solutions at t = 0 and t = 0.01 are available, use a larger step-size of
h=0.01 for the next 10 iterations.
• Now with the solutions at t = 0 and t = 0.1, use a still larger step-size of h=0.1 for the
remaining 10 iterations until we reach tN.

The results from this procedure are not shown since they exactly overlap with the solution
from AM-2 with a step-size of h=0.001. No oscillatory behavior is obtained, even in the
third stage. With this procedure, an excellent solution can be obtained within 40 iterations.

*  If we were using an explicit method, such as explicit Euler or RK-2, stability requirement will still limit us from using a
large step-size. For example, RK-2 method will require h ≤ 2λ, that is, (h < 0.002) for stability. Implicit method such as
trapezoidal method allows a larger h.
330   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

MATLAB’s ode15s, ode23s, ode23t, and ode23tb are all adaptive step-size solv-
ers. Adaptive step-size implicit solvers can be used to obtain accurate solutions with good
computational efficiency.

8.3.1.2 Multivariable Example
We are now equipped to solve the bioreactor example from Section 3.5.4 using the AM-2
trapezoidal rule. The case with smaller value of saturation coefficient, Ks = 0.001, was stiff
and resulted in an unstable solution with ode45. The same example (with same values of
coefficients and initial condition) will now be simulated using the AM-2 ­trapezoidal rule.
The function funMonod.m remains the same as in the previous example. The anony-
mous function f can be defined as

f=@(t,y) monodFun(t,y,monodParam);

Since MATLAB naturally works with vectors, the definition of the function “g” remains
unchanged. Since the nonlinear functions to be solved are represented by g(yk + 1) = 0, one
simply needs to ensure that g(y) takes a 3 × 1 vector argument yNew and returns a 3 × 1
­vector. Thus, g(yNew) is defined as

g=@(yNew) yNew-yk - h/2*(fk+f(tNew,yNew));

This is exactly the same as before. The only difference is that yNew, yk, and fk are all 3 × 1
vectors. The actual code for this example is left as an exercise.
Figure 8.3 compares the simulation results using the AM-2 trapezoidal method
and  ode15s. The two results are very close to each other. Since the trapezoidal
method is implicit, it captures the sharp change in process trends observed ~19 h. A step-
size of h=0.05 was used for the trapezoidal method; a lower value of h gives unstable
results.

4
[S],[X],[P] (mol/L)

3 Solid: ode15s
Dashed: AM-2

0
0 5 10 15 20 25
Time (h)

FIGURE 8.3  Bioreactor with Monod kinetics simulated using AM-2 trapezoidal method (dashed
lines). The solution using ode15s is plotted as solid lines for comparison.
 Implicit Methods   ◾    331

8.3.2 Crank-Nicolson Method for Hyperbolic PDEs

Various numerical techniques to solve hyperbolic PDEs of the form

¶f ¶f
+u = S ( f) (8.4)
¶t ¶z

were discussed in Chapter 4. The most versatile method is to convert the above PDE into a
set of ODEs in time by discretizing the spatial derivative. With the spatial domain split in
n intervals, with interval size Δz = L/n, the ODE for the solution variable at the ith location
is given by

d
fi = -Ci ( f ) + S ( fi ) (8.41)
dt

The convection term, uϕz, is represented with finite difference approximation. The above
expression for Ci ( ×) is written in a very general form. In reality, Ci ( ×) does not depend on an
entire vector ϕ but only on a few terms ϕi − ℓ,  … , ϕi,  … , \ phii + ℓ (as we had seen in the previ-
ous chapter). For example, if central difference formula is used, then ℓ = 1 and

fi +1 - fi -1
Ci ( f ) = u (8.42)
2D z

Let the right-hand side of Equation 8.41 be represented as fi(ϕ). Thus, the set of ODEs
obtained after discretization in space is given by

é f1 ( f ) ù
ê ú
d ê f2 ( f )ú
f= (8.43)
dt ê  ú
ê ú
êë fn ( f ) úû

One of the options for solving the above set of ODEs is the AM-2 trapezoidal method. If Δt
is the time-step size and ϕp represents the solution vector at time p, then

Dt

fp +1 = fp +
2
(
f ( fp +1 ) + f ( fp ))
(8.44)

The ith equation above is given by

Dt

f p +1,i = f p,i +
2
(
fi ( fp +1 ) + fi ( fp )

) (8.45)
332   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Substituting the central difference formula for Ci ( ×) from Equation 8.42 in the above equa-
tion yields us the Crank-Nicolson equation:

Dt æé f p +1,i +1 - f p +1,i -1 ù é f p,i +1 - f p,i -1 ù ö

f p +1,i = f p,i + ç ê Sp +1,i - u ú + ê S p ,i - u ú÷ (8.46)
2 èë 2D z û ë 2D z û ø

This can be more conveniently arranged in the form of Equation 8.5:

f p +1,i - f p,i u æ f p,i +1 - f p,i -1 f p +1,i +1 - f p +1,i -1 ö 1

+ ç + ÷ - ( Sp,i + Sp +1,i ) = 0 (8.5)
Dt 2è 2D z 2D z ø 2

Thus, the Crank-Nicolson method may be visualized as an implicit trapezoidal method

implementation of a PDE with central discretization in space. This derivation also allows
the users to extend the Crank-Nicolson method to higher-order formulae. To summa-
rize, at this stage, I have done two things: introduced the Crank-Nicolson method as
second-order in time and second-order in space implicit method, and reinterpreted
it as an implicit in time implementation of the method of lines approach. The final
order of  ­business is to solve the example of a transient plug flow reactor (PFR) from
Chapter 4, which yields a hyperbolic PDE. Recall that the PFR model that was solved
in Chapter 4 is

¶C A ¶C
+ u A = -r
¶t ¶z (8.47)
C A ( t = 0 ) = C A0 , C A ( t ,z = 0 ) = C A,in

A first-order reaction, with r = kCA and k = 0.2 min−1, takes place in the reactor.

Example 8.2  Solving a PFR Problem Using the Crank-Nicolson Method

Problem: Solve the PFR problem from Equation 8.47. The inlet velocity is u = 0.1
m/min, length of the PFR is 0.5 m, and inlet concentration is 1 mol/L. The initial
­concentration is the same as 1 mol/L.
Solution: Let us define individual terms in the overall equation. The convection
term, given by Equation 8.42, is

ì ( u/2D z ) ( f p,i +1 - f0 ) i = 1
ï
Cp,i = í ( u/D z ) ( f p,i - f p,i -1 ) i = n (8.48)
ï u/2D f
î( z ) ( p ,i +1 - f p ,i -1 )

whereas the reaction term is rp, i = kϕp, i. A function file can be written to return the
reaction and convection terms for all locations, given the vector ϕp at any time p.
 Implicit Methods   ◾    333

(i) The function to calculate Cp,i and rp, i (pfrDiscreteFun.m) is given below:

function [reac,convec] = pfrDiscreteFun(Phi,par)

% This function calculates two key terms of PFR
% model: reaction and convection terms
%% Get the parameters
deltaZ=par.deltaZ;
n=par.n;
k=par.k;
C0=par.Cin;
u=par.u0;

%% Computing individual values

reac=zeros(n,1);
convec=zeros(n,1);
% First node
reac(1)=k*Phi(1);
convec(1)=u/(2*deltaZ) * (C(2)-C0);
% Other internal nodes
for i=2:n-1
reac(i)=k*Phi(i);
convec(i)=u/(2*deltaZ) * (C(i+1)-C(i-1));
end
% End-node
reac(n)=k*Phi(n);
convec(n)=u/deltaZ * (C(n)-C(n-1));

Since the Crank-Nicolson method uses a single previous value ϕp to compute

ϕp + 1, the above functions will be calculated at the new (guess) point and the
previous solution. Using the definitions of convection and reaction terms in
Equation 8.48, the Crank-Nicolson equation may be written as

( f p+1,i - f p,i ) + D2t ( éëCp,i + rp,i ùû + éëCp+1,i + rp+1,i ùû ) = 0 (8.49)


g ( fp +1 )

Since rp and Cp are computed at known (previous) values of ϕp, they can be cal-
culated once and passed to the function g(ϕ) as constants.
Let us use phi to represent the previous solution, ϕp, and Y to represent the
function argument in Equation 8.49, that is, g(Y). The MATLAB function that
calculates g(Y) consists of the following calculation:

g ( Y ) = (Y - f ) +
Dt
(
éf old ù + éf new ù
2 ë û ë û )
f old = éëCp + rp ùû , f new = éëCp +1 + rp +1 ùû
334   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

(ii) The function to calculate g(Y) is given below:

function gVal = pfrCrankNicolFun(Y)

%% Function to calculate g(Y)
[reacNew,convecNew]=pfrDiscreteFun(Y,par);
fNew=reacNew+convecNew;
gVal = (Y-Phi) + deltaT/2*(fNew+fOld);
end

The above function, pfrCrankNicolFun, will be supplied to fsolve solver

to obtain the root, ϕp + 1. The variable fOld (underlined above) is the value fold
above, which is calculated at ϕp, i. Since it remains constant within the fsolve
iterations, it is calculated outside the pfrCrankNicolFun function.
(iii) Function for time stepping in Crank-Nicolson: pfrCN_Stepper is a func-
tion that will take (tp, yp) as input arguments and return the next iteration value
(tp + 1, yp + 1). It will invoke fsolve, with g(Y) provided by pfrCrankNicol-
Fun, as given below:

function [tNew,PhiNew]= pfrCN_Stepper (t,Phi,par)

% Function file for transient PFR problem
% to be solved using Crank-Nicolson Method
%% Perform time-stepping
deltaT=par.deltaT;
tNew=t+deltaT;

% Get function values at previous time

[reacOld,convecOld]=pfrDiscreteFun(Phi,par);
fOld=reacOld+convecOld;
% Use old value as the initial guess
Yguess=Phi;
% Call fsolve for one-step of Crank Nicolson
opt=optimoptions(@fsolve);
PhiNew=fsolve(@(Y) pfrCrankNicolFun(Y),Yguess,opt);

function gVal = pfrCrankNicolFun(Y)

%% Function to calculate g(Y)
[reacNew,convecNew]=pfrDiscreteFun(Y,par);
fNew=reacNew+convecNew;
gVal = (Y-Phi) + deltaT/2*(fNew+fOld);
end
end

The above function is self-explanatory, where the steps shown in various equa-
tions are implemented sequentially. Since pfrCrankNicolFun is an embed-
ded function, the variables in pfrDiscreteFun are accessible to it; thus,
allowing us to avoid transferring the values fOld, Phi, and par to this function.
 Implicit Methods   ◾    335

(iv) Overall driver function for solving the PFR problem follows a similar structure as
before. The function, pfrCN_Stepper, is called at each time-step to compute
ϕp + 1 in a loop, starting from the initial condition:

% Simulating transient PFR using Crank-Nicolson

%% Model Parameters
modelParam.k=0.2;
modelParam.u0=0.1;
C0=1;
modelParam.Cin=C0;
modelParam.L=0.5;
%% Initializing the PFR
n=25; h=modelParam.L/n;
phi=ones(n,1)*C0;
t=0; tN=10;
dt=0.1;
modelParam.n=n;
modelParam.deltaZ=h;
modelParam.deltaT=dt;
% For storing results
Z=[0:h:h*n];
T=zeros(tN/dt+1,1);
PHI=zeros(n+1,tN/dt+1);
PHI(:,1)=[C0;phi];

% Jacobian pattern for efficient fsolve

Jvec=ones(n-1,1);
Jpat=diag(Jvec,-1)+eye(n)+diag(Jvec,1);
modelParam.Jpat=Jpat;
%% Solving the PFR using Crank-Nicolson
for p=1:tN/dt
[tNew,phiNew]= pfrCN_Stepper(t,phi,modelParam);
T(p+1)=tNew;
PHI(:,p+1)=[C0;phiNew];
t=tNew;
phi=phiNew;
end

%% Plotting results
% Steady state plot
CModel=C0*exp(-modelParam.k/modelParam.u0*Z);
C_ss=PHI(:,end);
figure(1)
plot(Z,C_ss); hold on
plot(Z,CModel,'.');
xlabel('Length (m)'); ylabel('C_A (mol/L)');
336   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

% Exit concentration vs. time

figure(2)
plot(T,PHI(end,:)); hold on
xlabel('time (min)'); ylabel('C_A (mol/m^3)');

The underlined part of the code above will be discussed later.

The steady state results for Δt = 0.1 (solid line) are compared with the ana-
lytical solution (symbols) in Figure 8.4. The steady state results are reproduced
with sufficient accuracy. The discretization in time was verified by running the
code at another step-size of Δt = 0.2, which is double the original step-size. The
steady state results are not shown because the two curves lie exactly on top of
one another. Figure 8.5 shows the comparison for transients in the outlet con-
centration (dashed line represents Δt = 0.2). The results indicate that the chosen
step-sizes give adequate accuracy for this system.

0.8
CA (mol/L)

0.6

0.4

0.2
0 0.2 0.4 0.6
Length (m)

FIGURE 8.4  Steady state results using the Crank-Nicolson method, and comparison with analytical
solution (as symbols; see Chapter 4 for derivation).

0.8
CA (mol/m3)

0.6

0.4

0.2
0 5 10
Time (min)

FIGURE 8.5  Transient variation in outlet concentration for two different step-sizes: Δt = 0.1 (solid
line) and Δt = 0.2 (dashed line).
 Implicit Methods   ◾    337

8.3.2.1 Exploiting Sparse Structure for Efficient Simulation

The 14th line in pfrCN_Stepper code above (see item (iii) in Example 8.2) was

opt=optimoptions(@fsolve);

This structure opt can be used to provide various options for fsolve. Since Equation 8.5
resulting from the Crank-Nicolson method is tridiagonal, one of the methods discussed
in the previous chapter can be used to improve the computational efficiency by exploiting
the sparse nature of Equation 8.5. This can be done by providing “JacobPattern” option for
fsolve. The above underlined code is modified as

opt=optimoptions(@fsolve,'jacobPattern',par.Jpat);

The variable Jpat was defined in the driver script (see underlined part) as

Jpat=diag(Jvec,-1)+eye(n)+diag(Jvec,1);

Recall from Chapter 7 that the above command indicates to the solver that the problem has
a tridiagonal structure. The sparsity pattern can be verified using spy(Jpat).
The original code was executed again with Δt = 0.01 (to highlight the computational
gains clearly). Without Jacobian pattern, it took 33.7 s for the 1000 steps to reach tN = 10.
With the Jacobian pattern included, the computation time reduced* to 29.8 s. The computa-
tion time can be reduced even further by suppressing the display at the end of each iteration
using

opt=optimoptions(opt,'display','none');

A combination of specifying Jacobian pattern and suppressing display resulted in a three-

fold reduction of computation time to 11.2 s.
This concludes our discussion on the Crank-Nicolson method. A key outcome from the
stiff system and Crank-Nicolson examples in Section 8.3 was to demonstrate the use of
implicit method for solving ODEs. We now turn our attention to using implicit solvers for
DAEs in the remainder of this chapter.

8.4 DIFFERENTIAL ALGEBRAIC EQUATIONS

DAEs were briefly introduced in Section 8.1.3 as system models that have both an algebraic
and a differential equation representation:

æ dY ö
F ç t ,Y , =0 (8.8)
è dt ÷ø

*  fsolve uses various different algorithms; only some of these can exploit Jacobian pattern. The codes were run on Macbook
Pro with 2.6 GHz Intel i5 processor, running MATLAB R2016a.
338   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

where Y ∈ R n. Fully implicit methods are used to solve the generic DAE of the form above.
Rather than discussing a general form of DAEs as above, this chapter focuses on the most
important class of DAEs for chemical engineers—semiexplicit DAEs:

d
y = f ( t ,y ,x ) (8.6)
dt

0 = g ( t,y ,x ) (8.7)

As described before, y ∈ R nd are differential variables since they are governed by ODEs,
whereas the remaining variables, x ∈ R n-nd , are algebraic. When nd = 0, we have a purely
algebraic system of equations, whereas when nd = n, we have ODEs. Since these were cov-
ered in Chapters 6 and 3, respectively, we focus solely on DAEs.

8.4.1 An Introductory Example

Consider a continuous stirred tank reactor (CSTR) example that was solved in Chapter 3:

d F
C A = ( C A,in - C A ) - r ( C A )
dt V

C A ( 0 ) = C A 0 (8.50)

Here, CA is a differential variable. Since n = nd = 1, the above is an example of ODE-IVP.

Let us consider that the inlet concentration is not constant but varies according to some
function:

C A,in = x ( t ) (8.51)

There are two ways to solve this problem.

8.4.1.1 Direct Substitution
It is possible to substitute Equation 8.51 in Equation 8.50:

d F
dt
CA =
V
( )
x (t ) - CA - r (CA )

(8.52)

leading to ODE-IVP. This was an approach we took in Chapter 5. For example, we consid-
ered a case study of chemostat in Section 5.4 where inlet concentration varied with time,
whereas a boundary constraint in the form of PFR temperature profile was imposed in
Section 5.5. This approach may be used if algebraic variables are explicit functions of time
and/or differential variables, or if they can be converted to explicit functions with some
algebraic manipulations.
 Implicit Methods   ◾    339

8.4.1.2 Formulating and Solving a DAE

Rewriting Equation 8.51 as

0 = C A,in - x ( t ) (8.53)

g ( t ,C A ,C A , in )

The above equation along with Equation 8.50 defines DAE, with CA as the differential vari-
able and CA, in as the algebraic variable.

8.4.1.2.1  Case Where Algebraic Variable Is Specified Implicitly  Instead of being specified as
an explicit function, the differential variable, CA, in, may be specified implicitly in the form,
g(t, CA, CA, in) = 0. There are several instances when such a case arises. During the start-up of
a reactor, the inlet condition may need to be varied based on a certain desired profile, borne
out of some design optimization procedure. In highly exothermic systems or in bioreactors
to avoid toxicity, CA, in may be specified implicitly. For example

h
éë F ( C A,in - C A ) ùû + aC A,in = 0 (8.54)

for an arbitrary η ≠ 1 is a case where the DAE comprising Equations 8.50 and 8.54 needs to
be solved using a combined approach.

8.4.1.2.2  Case Where Algebraic Variable Is Specified Indirectly  There are several problems
where the algebraic constraints do not contain the algebraic variables, x. For example, the
inlet composition may be varied so that the exit concentration meets a specific profile. The
DAE consists of differential Equation 8.50 and algebraic Equation 8.55 below:

d F
C A = ( C A,in - C A ) - r ( C A ) (8.50)
dt V

0 = C A - x ( t ) (8.55)

Since CA appears in the differential equation, it is the differential variable; the algebraic vari-
able is CA, in even though it does not appear in Equation 8.55. Thus, the algebraic variable
gets specified indirectly due to the algebraic constraint in Equation 8.55.
Such cases are routinely seen in design optimization problems and (off-line) control
formulations. For example, during reactor start-up, the concentration or temperature of
CSTR may need to follow a certain trajectory; inlet concentration CA, in is determined by
solving the DAE (8.50) with (8.55). Another example is that of a surge tank or blender kept
upstream of a critical reactor or equipment. The aim of this tank or blender is to dampen the
variations and ensure the downstream reactor or equipment is provided the process stream
at desired conditions. This is achieved by varying the algebraic variable CA, in to achieve the
constraint in Equation 8.55.
340   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

8.4.2 Index of a DAE and More Examples

Three cases were discussed in the above example: Equation 8.50 was the differential equa-
tion and the possible algebraic constraints were

C A,in specified explicitly as in Equation 8.51

1.
C A,in specified implicitly in an algebraic equation (8.53) or (8.54)
2.
C A,in obtained indirectly by solving Equation 8.50 subject to constraint in (8.55)
3.

The first is an example of ODE if direct substitution approach is followed, the second is
index-1 DAE, and the third is a higher-index DAE (specifically, index-2).

DEFINITION: INDEX OF A DAE

The index of a DAE is defined as the number of times the algebraic equations need to be
differentiated in order to convert the DAE into ODEs.

There are several different definitions of index: differentiation index, perturbation

index, and tractability index. The above is convenient to use and relevant to solving DAEs
numerically.
The first case is where the inlet concentration is specified, as given in Equation 8.53.
Differentiating the equation yields us

d
C A,in - x¢ ( t ) = 0 (8.56)
dt

Since a single differentiation was required to convert the DAE into ODE, this is an example
of index-1 DAE.
The second case is where the outlet concentration is specified. Differentiating
Equation 8.55

d
C A = x¢ ( t ) (8.57)
dt

The variable CA, in is still an algebraic variable. Substituting Equation 8.50, we get

F
V
(CA,in - CA ) - r (CA ) = x¢ (t ) (8.58)

Differentiating this a second time

d V ¶r ¢
C A,in - C A¢ - C A = x¢¢ ( t ) (8.59)
dt F ¶C A
 Implicit Methods   ◾    341

d æ V ¶r ö
C A,in = x¢ ç 1 + ÷ + x¢¢ ( t ) (8.60)
dt è F ¶C A ø

Differentiating the algebraic equation twice converts the original DAE into a set of two
ODEs—Equations 8.50 and 8.60. Therefore, this is an example of index-2 DAE.

8.4.2.1 Example 2: Pendulum in Cartesian Coordinate System

We are all familiar with the pendulum model. It is a rather simple model in polar coordi-
nate system since there is a change in only one direction, θ. The force balance in Cartesian
coordinates results in a DAE as shown below:

x ¢¢ = -T sin q, y ¢¢ = g - T cos q (8.61)

Here, sin θ = x/L and cos θ = y/L. Let u represent the velocity in x-direction and v represent
the velocity in y-direction. Tension in the connecting string/rod is also unknown and is to
be found out. However, T is indirectly specified because of the constraint that the string
is rigid, and hence the pendulum traverses a circular path with constant radius. Thus, the
algebraic equation for pendulum is given by Equation 8.63 below and the differential equa-
tions (8.61) are written as a set of four ODEs in (8.62) below:

x¢ = u
Tx
u¢ = -
L (8.62)
y¢ = v
y ¢ = g - Ty /L

0 = x 2 + y 2 - L (8.63)

T
The overall solution vector is Y = ëé x u y v T ùû , tension T is the algebraic vari-
able, whereas the remaining four are differential variables. Clearly, this is an example of
higher-index DAE. Computing the index of the DAE is left as an exercise to the reader.

8.4.2.2 Example 3: Heterogeneous Catalytic Reactor

Previously, we simulated plug flow and packed bed reactors, where concentration was
assumed constant throughout any axial slice of the reactor. Heterogeneous reactor models
are models for catalytic reactors that explicitly account for molecular diffusion from the
bulk gas to the catalyst surface. The concentration at the catalyst surface is different from
the bulk concentration, and the rate of diffusion is given by the product of mass transfer
coefficient and concentration driving force:

J diff = k g ( C A - C As ) (8.64)
342   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The balance for bulk gas gives rise to the differential equation

dC A
u = -k g a ( C A - C As ) (8.65)
dz

whereas balance at the surface gives the algebraic equation

0 = k g a ( C A - C As ) - r ( C As ) a (8.66)

With this introduction, we now focus on methods to solve semiexplicit DAEs in MATLAB.
We further assume that the algebraic equation g is such that its Jacobian

¶g
¶x

is nonsingular. Most common DAE problems in chemical engineering are either in this
form or can be converted easily to this form.

8.4.3 Solution Methodology: Overview

The above example of heterogeneous catalytic reactor model will be used to demonstrate
various options for solving ODEs. Initially, while discussing solution methods, first-order
kinetics will be assumed:

dC A
u = -k g a ( C A - C As ) (8.65)
dz

0 = k g ( C A - C As ) - kC As (8.66)

The above problem can be easily solved because Equation 8.66 is linear in the algebraic
variable CAs. The first step in solving the DAE by hand is to obtain CAs for any given value of
concentration CA by solving Equation 8.66 analytically to yield

k g CA
C As = (8.67)
kg + k

Thus, the value of CAs can be known for any value of CA. Knowing the value of CAs, Equation
8.65 becomes

d 1 æ kk g ö
C A = - çç a ÷÷ C A (8.68)
dz u è k + kg ø

 Implicit Methods   ◾    343

The analytical solution of the DAE is therefore

1 æ kk g ö
C A ( t ) = C A 0 e - az , a = ç a÷
u çè k + k g ÷ø
(8.69)
kg
C As ( t ) = C a 0 e - az
kg + k

This solution will be used in subsequent examples to compare the solution obtained using
numerical approaches.
Since the reaction term, r(CAs), can be complex for most practical problems, numerical
techniques need to be general enough to solve in cases where Equation 8.66 cannot be rear-
ranged to give an explicit expression for CAs. Two approaches for solving the DAE will be
discussed presently: nested approach and combined approach.

8.4.3.1 Solving Algebraic Equation within ODE

Owing to the discussion in Chapter 3, we are familiar with methods to solve ODE of the
type (8.65), with the only challenge in case of DAE being that CAs is not known. Since the
above is an index-1 DAE, the algebraic equation can be solved to obtain the value of CAs
for any given value of CA. This was indeed the approach followed in analytical calculation
of CAs in Equation 8.67. This hand-computed expression in (8.67) will be replaced by a
numerically computed solution. Indeed, fsolve is an appropriate way to do so (though
any nonlinear equation solver may be used). Since the aim is to compute the value of x = CAs
for a given value of y = CA, the function g(y, x) in algebraic equation (8.7) is given by the
MATLAB function call:
@(Cas) funName(Ca,Cas,modelParam)

The above anonymous function call is passed to fsolve, which then computes CAs for the
specified value of CA, given the parameters in modelParam structure.
The versatility of numerical techniques is that the function to calculate the algebraic vari-
able need not be explicit x = ℊ(y); it can equally easily be presented as a numerical solution to
g(y, x) = 0. The following example demonstrates this nested approach of solving DAE.

Example 8.3  Heterogeneous PFR with Nested Approach

Problem: Solve the 1-D heterogeneous reactor model of Equations 8.65 and 8.66. The
reactor length is L = 1, the surface area to volume ratio is a = 100, and the inlet velocity is
u = 1. A first-order reaction A → B takes place with r = 0.02 CA. The mass transfer coef-
ficient is kg = 0.01. Obtain the axial profiles of concentration CA and CAs in the reactor.
Solution: The following function calculates the catalytic reaction rate:
%% Function to calculate reaction rate
function r=catalRxnRate(C,par)
r=par.k*C;
end
344   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Calculation of CAs by solving nonlinear equation: The nonlinear equation (8.66) will be
solved using MATLAB fsolve solver to compute CAs for any value of CA. This can
be compared with the analytically calculated CAs as per Equation 8.67. The function to
compute the algebraic function g(·) is given below:

%% Function for the algebraic model

function gVal=surfaceBal(CaBulk,Cas,par)
rxnTerm=catalRxnRate(Cas,par);
gVal=par.kg*(CaBulk-Cas) - rxnTerm;
end

In my experience, the underlined line of the code above is the source of a majority of
errors. The reaction rate is calculated at CAs; a common error is when the rate is calcu-
lated at CA instead. Another potential source of error is the order of input arguments.*
Please be careful when setting up the problem!
Let us now verify how this code works. Defining the parameters at the command line

>> par.k=0.01;
>> par.kg=0.02;
>> Ca0=1; CaTry=Ca0;

we solve to obtain CAs, 0 for a given value of CA, 0:

>> Cas0=fsolve(@(Cas) surfaceBal(Ca0,Cas,par), CaTry)

Cas0 =
0.6667

The analytically calculated CAs as per Equation 8.67 is 2/3, which is what we obtained. In
the fsolve call above, the underlined entity (Cas) is a variable that fsolve solves
for, and the result (Cas0) is the solution found for any given constant value of Ca0. To
summarize what fsolve does: (i) Ca0 is treated as a constant within the fsolve call,
(ii) the value of Cas is varied using the root-finding algorithm, (iii) the result Cas0 is
the solution that satisfies g(y, x) = 0 for that particular value Ca0, and (iv) CaTry is the
initial guess for the solver. If CA0 is changed to another value, CA, fsolve will find the
corresponding value of CAs as the root of the algebraic equation (8.66).
Function for differential equation with nested algebraic solver: The differential equa-
tion (8.65) will be provided to the solver. Let us say that CAs was calculated analytically
as per Equation 8.67. The ODE function would simply involve the following two lines:

Cas=kg/(k+kg) * Ca;
dC=-(kg*abyv/u)*(Ca-Cas);

*  This is another example why I personally recommend using the powerful anonymous function approach of MATLAB. In the
older versions of MATLAB, the first variable in the input arguments was the variable solved for by fsolve. The anonymous
function allows us to write a MATLAB function in a manner similar to how we write analytically.
 Implicit Methods   ◾    345

Since the code developed needs to be general for any other forms of reaction rate
r(C), the underlined line will be replaced by the fsolve solution described on
the previous page. The final function file used for the differential equation is given
below:

function dC=pfrNestedFun(t,Ca,par)
% Differential function for heterogeneous
% reactor using nested approach
k=par.k; kg=par.kg;
u=par.u0; abyv=par.abyv;

CaTry=Ca; % Guess value for fsolve

Cas=fsolve(@(Cas) surfaceBal(Ca,Cas,par), CaTry);
dC=-(kg*abyv/u)*(Ca-Cas);
end

Driver script and results: This completes the main part of our code. The driver script to
run this code and the results are given below:

% Driver script for 1D heterogeneous model

% for a reactor with first-order reaction
%% Model parameters
L=1;
Ca0=1;
u=1; modelParam.u0=u;
k=0.01; modelParam.k=k;
kg=0.02; modelParam.kg=kg;
abyv=200; modelParam.abyv=abyv;

%% Solving the DAE: Nested approach

[zSol,CaSol]=ode45(@(z,Ca)...
pfrNestedFun(z,Ca,modelParam),[0 L],Ca0);
plot(zSol,CaSol); hold on;

The computation of the CA values analytically is not shown in the code above.
Figure 8.6 shows the concentration profile calculated numerically (solid line) and is
compared with the analytically calculated value of CA as per Equation 8.69.

The nested approach is easy to follow and is a convenient learning tool. However, it is com-
putationally intensive since the nonlinear equation is solved at each integration step.

8.4.3.2 Combined Approach
The combined approach uses an appropriate implicit ODE-solving method to convert the
differential equations (8.6) into algebraic equations (as was done in Sections 8.2.1, 8.2.3,
and 8.3). Since the AM-2 trapezoidal method was used in Section 8.3.1, I will use it to
346   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Concentration, CA
0.75

0.5

0.25
0 0.5 1
Location, z

FIGURE 8.6  Solution of DAE for heterogeneous reactor using nested approach (solid line), and
comparison with the analytical solution (symbols).

illustrate the combined approach. The same arguments work for other implicit methods for
ODE-IVP also. Applying the trapezoidal method to Equation 8.6 yields

h
2ë
(
y k +1 = y k + éfk + f ( k + 1) h,y k +1 ,x k +1 ù
û ) (8.70)

where h is the step-size and fk = f(hh, yk, xk) is a known value. Equation 8.7 is written as

(
0 = g ( k + 1) h,y k +1 ,x k +1 ) (8.71)

The two sets of equations, written together as

é h
ê
F(Y)  ê 2ë
(
y k +1 - y k - éfk + f ( k + 1) h,y k +1 ,x k +1 )ùû ùú = 0 (8.72)
ú

(
êëg ( k + 1) h,y k +1 ,x k +1 ) úû

can be solved to obtain the solution Yk+1 at each time. Viewed thusly, both ODE and non-
linear algebraic equations may be considered as a subset of DAEs.

Example 8.4  DAE Using Implicit AM-2 Trapezoidal Rule

Problem: Solve the problem in Example 8.3 using the implicit AM-2 trapezoidal rule.
Solution: The function file developed in Example 8.3 will be used in this prob-
lem. As per Equation 8.72, two functions are needed: the algebraic function g(·)
and the differential function f(·). The algebraic function surfaceBal and cata-
lytic reaction rate calculation catalRxnRate will be used from the previous
example.
 Implicit Methods   ◾    347

Function to compute f(.) for the differential function: As per Equation 8.65, the dif-
ferential function is given by

kg a
f (CA ) = - (CA - CAs )
u

which is implemented in the function below:

%% Function for differential model

function fVal=gasBalance(Ca,Cas,par)
kg=par.kg; abyv=par.abyv;
u=par.u0;
fVal=-(kg*abyv/u)*(Ca-Cas);
end

AM-2 Solver for forward stepping: The solver that uses AM-2 trapezoidal rule will be
built on the same lines as Example 8.1. The first element of the vector F(Y) will use
the differential model above within an AM-2 discretization, whereas the second ele-
ment is the algebraic equation surfaceBal. Specifically, the two elements of F(Y)
will be

FVAL(1,1) = Ca-CaOld - par.h/2*(fNew+fOld);

FVAL(2,1) = surfaceBal(Ca,Cas,par);

where fNew is f((k + 1)h, yk + 1, xk + 1) and fOld is fk in Equation 8.70. As in Example 8.1,

an embedded function that calculates FVAL is passed to fsolve solver to obtain the
solution at the next location, Yk+1. The function is given below:

function [zNew,YNew]=pfrDAE_AM2(z,YOld,par)
% Function for single step for solving DAE PFR
% problem using AM-2 trapezoidal method
CaOld=YOld(1);
CasOld=YOld(2);
fOld=gasBalance(CaOld,CasOld,par);
% Compute next values using AM-2
zNew=z+par.h;
YNew=fsolve(@(Y) pfrAM2Fun(Y), YOld);

%% Function for AM-2 as per Eq. (8.72)

function FVAL=pfrAM2Fun(Y)
Ca=Y(1); Cas=Y(2);
fNew=gasBalance(Ca,Cas,par);
FVAL(1,1) = Ca-CaOld-par.h/2*(fNew+fOld);
FVAL(2,1) = surfaceBal(Ca,Cas,par);
end
end
348   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The driver script and results: Only the part of the driver script that solves the DAE
using AM-2 method is shown below. The script is self-explanatory.

%% Solving the DAE: Using AM-2 method

h=0.01; modelParam.h=h;
n=L/h; modelParam.n=n;
% Variables for storing results
Z=0:h:L;
Y=zeros(2,n); Y=[Y0, Y];
for k=1:n
[zNew,yNew]=pfrDAE_AM2(Z(k),Y(:,k),modelParam);
Z(k+1)=zNew;
Y(:,k+1)=yNew;
end
plot(Z,Y(1,:),'-.');

The results obtained in this example were the same as that in Example 8.4 (Figure 8.6).
Hence, they are skipped for brevity.

The above example showed the feasibility of using implicit method for solving a DAE. While
this approach indeed works very well, it is also possible to use MATLAB implicit ­solvers,
such as ode15s, to solve semiexplicit DAEs. This will be discussed in Section 8.4.4.

8.4.4 Solving Semiexplicit DAEs Using ode15s in MATLAB®

MATLAB solver ode15s uses fully implicit NDF and is therefore able to solve the DAE.
Specifically, ode15s has an option to provide the so-called mass matrix, M, which is an
n × n matrix. If the mass matrix is provided, it solves the ODE:

dY
M = F ( t ,Y ) (8.73)
dt

When M is an identity matrix (which is a default option in ode15s, when M is not speci-
fied), the above is an ODE-IVP. For a DAE consisting of nd differential equations and
na = n − nd algebraic equations, the mass matrix is

é In 0nd ´na ù
M=ê d ú (8.74)
ë0na ´nd 0na ´na û

where Ind is an nd × nd identity matrix and 0m × n is a zero matrix whose size is specified in the
subscript. The mass matrix is specified using the option 'Mass'.
 Implicit Methods   ◾    349

Example 8.5  Using ode15s to Solve DAE

Problem: Solve the problem in Example 8.3 using ode15s.
Solution: The DAE comprising Equations 8.65 and 8.66 may be written in the stan-
dard form required for ode15s as

é k a ù
é1 0 ù d é C A ù ê - g ( C A - C As ) ú
ê ú ê ú = u (8.75)
0 0 û dt ëC As û ê ú
ë
   êë k

g ( C A - C As ) - kC As ú
 û
M
f (Y)

The above equation is treated in a similar manner as the ODEs, the difference being
that an appropriate mass matrix is specified, and we have consistent initial conditions.
Since we have already created functions for gas and surface balance earlier, we will
simply use them. The function file for the DAE is given below:

function dY=pfrDAEFun(t,Y,par)
Ca=Y(1);
Cas=Y(2);
dY(1,1)=gasBalance(Ca,Cas,par); % Differential
dY(2,1)=surfaceBal(Ca,Cas,par); % Algebraic
end

Driver script: The mass matrix is specified in the driver script as follows:

MassMat=[1 0; 0 0];
opt=odeset('Mass',MassMat);

whereas the consistent initial condition for the algebraic variable is obtained by ­solving
the algebraic equation for inlet concentration, CA0:

Cas0=kg/(k+kg)*Ca0;

Thus, the overall driver script is given below (for the sake of completeness, the entire
script is given here):

% Driver script for 1D heterogeneous model

% for a reactor with first-order reaction
%% Model parameters
L=1;
Ca0=1;
u=1; modelParam.u0=u;
k=0.01; modelParam.k=k;
350   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

kg=0.02; modelParam.kg=kg;
abyv=200; modelParam.abyv=abyv;

%% Solving the DAE: ode15s approach

MassMat=[1 0; 0 0];
opt=odeset('Mass',MassMat);
Cas0=kg/(k+kg)*Ca0; % Consistent initial condition
Y0=[Ca0;Cas0];
[zSol,YSol]=ode15s(@(z,Ca) pfrDAEFun(z,Ca,modelParam),...
[0 L], Y0, opt);

%% Analyzing and plotting

plot(zSol,YSol); hold on
xlabel('Location, z'); ylabel('Concentration, C_A');

alpha=k*kg/(k+kg) * (abyv/u);
ZModel=[0:0.1:1]';
Ca_Model=Ca0*exp(-alpha*ZModel);
Cas_Model=kg/(k+kg)*Ca_Model;
plot(ZModel,[Ca_Model, Cas_Model],'o');

The results are shown in Figure 8.7. The solid line represents concentration CA and
the dashed line represents surface concentration CAs. The analytical solution is pro-
vided as symbols for comparison. The numerical results are very close to the analyti-
cal solution. Since kg ≈ k, the system is governed by both mass transfer and surface
reaction.

This completes our discussion on DAEs and numerical methods to solve the DAEs.
Specific case studies will be shown in the next section to demonstrate the principles
described in this chapter.

0.75
Concentration, CA

0.5

0.25

0.1
0 0.5 1
Location, z

FIGURE 8.7  Solution of the 1D heterogeneous reactor model using ode15s (lines), with analytical
solution (symbols) presented for comparison.
 Implicit Methods   ◾    351

8.5 CASE STUDIES AND EXAMPLES

8.5.1 Heterogeneous Catalytic Reactor: Single Complex Reaction
The 1D heterogeneous reactor model discussed in Example 8.5 considered a first-order
reaction to benchmark the various numerical solutions with analytical results. The model
will be extended to the case where the reaction rate is given by a complex kinetic rate
expression:

kC A
r (CA ) = (8.76)
1 + K r C A2

The 1D heterogeneous reactor model is given by the following equations:

dC A
u = -k g a ( C A - C As ) (8.65)
dz

0 = k g ( C A - C As ) - r ( C As ) (8.66)

The results of the 1D heterogeneous model will be compared with the PFR model from
Section 3.5.1. The reaction rate above is in terms of mol/(m2cat · s), which needs to be con-
verted to mol/(m3 · s) as required in the PFR model. Thus, the PFR model is given by

dC A
u = -a r (CA ) (8.77)
dz

The main difference between Equations 8.65 and 8.77 is that the reaction rate is computed
at the surface concentration CAs, in the former, and at bulk concentration CA, in the latter.

Example 8.6  Heterogeneous Reactor with Single Complex Reaction

Problem: Solve the 1D heterogeneous reactor model above for the reaction given by
( )
(8.76). The parameter values are k = 0.005 m3/ m2cat × s , Kr = 1 m6/mol2, a = 400 m2cat /m3,
and kg = 0.01 m/s.
Solution: Comparing with the first-order reaction, the only difference in the prob-
lem statement is that a Langmuir-Hinshelwood-Hougen-Watson (LHHW) model type
kinetic rate expression (8.76) is used in this example. Due to the modular approach
emphasized in this book, the only change from Example 8.5 is in the function that
calculates the rate of reaction:

function r=catalRxnRate(C,par)
k=par.k; Kr=par.Kr;
r=k*C/sqrt(1+Kr*C^2);
end
352   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Additionally, the parameter, Kr, must be specified in the driver script. No other
change is required. Note that the DAE was initialized in Example 8.5 by specifying

kg
C As ,0 = C A ,0 (8.78)
k + kg

In this problem, ode15s is able to solve the DAE even when the problem is initial-
ized as Y0 = [CA, 0;  CAs, 0]. Although this CAs does not provide consistent initial condi-
tion, the ode15s solver computes it internally before solving the DAE.
Figure 8.8 shows the results of heterogeneous reactor model. The solid and dashed
lines represent bulk concentration CA and surface concentration CAs, respectively. The
results from a PFR simulation (see Section 3.5.1 for details) are shown as symbols
for comparison. Due to mass transfer effects, the conversion from the heterogeneous
reactor model is less than that from a PFR, where complete mixing (uniformity) in the
radial direction is assumed.

The mass transfer affects the net rate of reaction, as evident from Figure 8.8. The effect of
mass transfer coefficient, kg, on reactant concentration along the length of the reactor is
shown in Figure 8.9. The bulk concentration CA is shown as solid line and the surface con-
centration CAs as dashed line for two different values of kg. As the mass transfer coefficient
increases, the bulk and surface concentrations get closer to each other.
Furthermore, conversion of A also increases with an increase in the value of kg. This is
evident in Figure 8.10, where bulk concentration is plotted for various values of kg. The
value of kg increases in the direction of the arrow. As the value of kg is increased, conversion
from the heterogeneous reactor model progressively increases (i.e., CA decreases), with the
results approaching that of the PFR. Indeed, when the Damköhler number Da ∼ k/kg ≪ 1,
the bulk concentration from the heterogeneous model closely follows that from the PFR.
The concepts developed in this example will be further used in Section 9.4 to solve the
problem of simulating methanol synthesis in a tubular reactor.

1
CA (PFR)
Concentration, CA (mol/m3)

0.8 CA (hetero)
CAs (hetero)
0.6

0.4

0.2

0
0 0.2 0.4 0.6
Location (m)

FIGURE 8.8  Simulation of heterogeneous reactor (lines) and comparison with PFR (symbols).
 Implicit Methods   ◾    353

kg = 0.05
0.5

Concentration, CA (mol/m3)
0
1

kg = 0.05
0.5

0
0 0.1 0.2 0.3 0.4 0.5
Location (m)

FIGURE 8.9  Bulk and surface concentrations (CA and CAs) for two different values of kg.

1
Concentration, CA (mol/m3)

0.8

0.6
Increasing kg
0.4

0.2

0
0 0.1 0.2 0.3 0.4
Location (m)

FIGURE 8.10  Effect of varying kg on bulk concentration, CA. The four lines in the direction of the
arrow represent kg = 0.005, 0.01, 0.02, and 0.5 m/s, respectively.

8.5.2 Flash Separation/Batch Distillation

A binary distillation column was simulated in Section 5.5.1, and a T–x–y curve for a mix-
ture of nitrobenzene and acetonitrile was generated in Section 6.5.2. Simulation of a binary
batch distillation will be considered in this case study. In the continuous distillation column
example, we assumed the relative volatility to be constant. This may not always be the case,
especially in the case of batch distillation. In this problem, we will simulate binary batch dis-
tillation of a mixture of benzene (B) and ethylbenzene (EB). Instead of assuming a constant
relative volatility, the vapor-liquid equilibrium information will be obtained through Antoine’s
coefficients (similar to the T–x–y problem). First, the overall model equations will be derived.
354   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

P, T

yB

F, zB
M, xB

FIGURE 8.11  Schematic of flash separation, which will be used to develop binary distillation model.

Due to familiarity with a single stage of distillation (from Chapter 5), let us consider the
overall process as shown in Figure 8.11. If M is the molar holdup in the distillation tank, and
D and B are the molar flowrates, then the overall balance is given by

d
M = F -D-L (8.79)
dt

whereas the balance on B is given by

d
Mx B = Fz B - Dy B - Lx B (8.80)
dt

We have assumed that both the liquid and vapor phases are well mixed so that the outlet
conditions are the same as that existing in the flash/distillation tank. The mole fractions in
gas and liquid phases are in equilibrium. By Raoult’s law

pB = x B PBsat , pEB = (1 - x B ) PEB

sat
(8.81)

where Pi sat represents the saturation pressure of species i. The latter equation is for binary
mixture, as xEB = 1 − xB. The saturation pressure is related to the temperature by Antoine’s
equation:

Bi

( )
log10 Pi sat = Ai -
Ci + T
(8.82)

The mixture in the tank will be at its bubble point during the entire operation. For a given
liquid composition, xB, the temperature can be calculated as shown in Section 6.5.2. The
vapor is in equilibrium at that temperature and satisfies the following condition:

P = pB + pEB (8.83)
 Implicit Methods   ◾    355

P - x B PBsat - (1 - x B ) PEB
sat
=0 (8.84)
 
g (T )

and the vapor fraction of B is

x B PBsat
yB = (8.85)
P

The differential equations (8.79) and (8.80), the algebraic equation (8.84), and the expres-
sion (8.85) together form the model for any of these processes: continuous flash separation,
single-stage continuous distillation, and batch/semibatch binary distillation.
Batch distillation model can be further simplified because there is no feed or liquid out-
let. Thus

dM
= -D (8.86)
dt

whereas the balance on B is given by

d dM
M xB + xB = -Dy B
dt dt (8.87)
dx B D
= ( xB - yB )
dt M

The solution variables for the binary batch distillation are defined as

éM ù
ê ú
xB
Y =ê ú
êT ú
ê ú
êë y B úû

with the first two being the differential variables and the last two algebraic variables. Note
that Equation 8.85 is simply an expression for calculating yB. It is therefore not necessary to
include yB as an algebraic variable.
Antoine’s coefficients for B and EB are

AB = 4.7, BB = 1660, CB = -1.5

AEB = 4.1, BEB = 1419, CEB = -60.5

356   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 8.7  Binary Batch Distillation

Problem: Solve the binary distillation example for B-EB mixture. The distilla-
tion tank is charged with 100 mol of equimolar mixture initially. After the mix-
ture reaches the bubble point, heating is maintained such that the distillate is
obtained at a ­constant rate of D = 0.5 mol/min. Compute how distillation proceeds
in time.
Solution: We start with the core of the MATLAB function used for generating the
model equations as per Equations 8.84 through 8.87:

dPhi(1)=-D;
dPhi(2)=D/M*(xB-yB);
dPhi(3)=P - xB*PsatB-(1-xB)*PsatEB;
dPhi(4)=yB - xB*PsatB/P;

where D is the rate at which the distillate is drawn from the system. Antoine’s equa-
tion is used to compute PsatB and PsatEB, the saturation pressures of B and EB,
respectively, at the operating temperature, T. The operating temperature is equal to
the bubble point of the liquid in the distillation tank, whereas the operating pressure,
P, is taken as the atmospheric pressure.
The function file, batchDistFun.m, for this problem is given below:

function dPhi=batchDistFun(t,phi,par)
% Model for binary batch distillation
% of Benzene-Ethyl Benzene mixture
%% Model Parameters
P=par.P; % Operating pressure (bar)
D=par.D; % Distillate rate
% Antoine's coefficients
Ab=par.Ab; Bb=par.Bb; Cb=par.Cb;
Aeb=par.Aeb; Beb=par.Beb; Ceb=par.Ceb;
% Model variables
M=phi(1);
xB=phi(2);
T=phi(3);
yB=phi(4);

%% Model equations
PsatB=10^(Ab-Bb/(T+Cb));
PsatEB=10^(Aeb-Beb/(T+Ceb)); % Saturation P
dPhi=zeros(4,1);
dPhi(1)=-D;
dPhi(2)=D/M*(xB-yB);
dPhi(3)=P - xB*PsatB-(1-xB)*PsatEB;
dPhi(4)=yB - xB*PsatB/P;
 Implicit Methods   ◾    357

The above function requires pressure, distillate rate, and Antoine’s coefficients as the
model parameters. These will be defined in the driver script and passed to the func-
tion above. The driver script for batch distillation is given below:

% Binary batch distillation of benzene--ethylbenzene

%% Model parameters
distParam.D=0.5; % Distillate rate
distParam.P=1; % 1 bar pressure
% Antoine’s constants: Benzene
distParam.Ab =4.7; distParam.Bb =1660;
distParam.Cb =-1.5;
% Antoine’s constants: EB
distParam.Aeb=4.1; distParam.Beb=1419;
distParam.Ceb=-60.5;

%% Initializing / Solving the DAE

M0=100; xB0=0.5;
T0=378; % Guess T0 as avg. of B and EB boiling points
yB0=0.7;
Phi0=[M0;xB0;T0;yB0];
% Define mass matrix
massMat=diag([1 1 0 0]);
opt=odeset('Mass',massMat);
% Solve the DAE
[tSol,PhiSol]=ode15s(@(t,y) ...
batchDistFun(t,y,distParam),[0:5:100],Phi0,opt);
%% Getting output
% Liquid left behind in distillation tank
molesB_tank=PhiSol(:,1) .* PhiSol(:,2);
molesEB_tank=PhiSol(:,1) .* (1-PhiSol(:,2));
figure(1)
plot(tSol,molesB_tank,tSol,molesEB_tank);
xlabel('Time (min)'); ylabel('Moles left in tank');
% Temperature
figure(2);
plot(tSol,PhiSol(:,3));
xlabel('Time (min)'); ylabel('Temperature (K)');
% Distillate flow rate
distFlow_B=distParam.D*PhiSol(:,4);
distFlow_EB=distParam.D*(1-PhiSol(:,4));
figure(3);
plot(tSol,distFlow_B, tSol,distFlow_EB);
xlabel('Time (min)'); ylabel('Distillate flow rate');

As time progresses, the vapors in the tank are drawn out at the rate of D mol/min.
The  vapor phase is in equilibrium with the liquid in the tank. The vector Phi0
358   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

contains the guess for initial conditions. Since the boiling point of B is 80°C and that
of EB is 136°C, we chose 105°C = 378 K as the initial guess for the temperature. The
ode15s solver internally computed the correct initial conditions as

>> disp(PhiSol(1,:))
100.0000 0.5000 371.8551 0.8256

The first two elements are M = 100 and xB = 0.5, which are the initial conditions pro-
vided. The value of temperature that satisfies the algebraic Equation 8.84 is T = 371.86 K.
The corresponding value of yB = 0.826. Thus, the equimolar mixture of B and EB has its
bubble point at 372 K, and the vapor in equilibrium with the liquid contains 82.6% B.
When this vapor is drawn out, the distillate contains more amount of B and the
liquid left in the distillation tank is richer in EB. Thus, the bubble point temperature
increases, as shown in the top panel of Figure 8.12. Since both B and EB are drawn out
from the distillation tank, the amount of B and EB falls. The amount of B in the tank
equals MxB, whereas that of EB is M(1 − xB). After the 100 min distillation, 12.85 mol
of B and 37.15 mol of EB are remaining in the tank.
Since there is more B in the distillate than EB, the amount of B in the tank falls
faster than that of EB. Equivalently, the flowrate of B in the distillate stream is higher
than that of EB. D is the net distillate flowrate and the vapors exiting the distillation
tank are in equilibrium with the liquid in the tank, the flowrates of B and EB in the
distillate are DyB and D(1 − yB), respectively. Figure 8.13 shows the flowrates of B and
EB in the distillate.

385
Temperature (K)

380

375

370
50
EB
Moles left in tank

40

30
Benzene
20

10
0 50 100
Time (min)

FIGURE 8.12  Temporal variations in equilibrium temperature and the amount of B and EB left
behind in the distillation tank.
 Implicit Methods   ◾    359

0.5

0.4 Benzene

Distillate flowrate
0.3

0.2

0.1 EB

0
0 50 100
Time (min)

FIGURE 8.13  Flowrate of B and EB in distillate as a function of distillation time.

The total number of moles of B left in the distillation tank equals MxB = 12.85 mol. Since the
batch distillation process started with 50 mol each of B and EB, the rest 37.15 mol of B are
collected as distillate over the 100 min operation.
The flowrates of B and EB in distillate are plotted in Figure 8.13. The total number of
moles collected in the distillate over the 100 min operation is also equal to the area under
the respective curves. Using numerical integration (trapezoidal rule with trapz com-
mand), the amount of B in the distillate is computed as 37.13 mol.
Distillate flowrate was used as a design parameter. Distillate flowrate is increased to
1 mol/min by changing D = 1.0, which means that 50 mol of the mixture will be collected
in 50 min. Executing the above code for 50 min, one can observe that the same amount of
B (i.e., 37.15 moles) is distilled as before. Likewise, the temperature at the end of 50 min is
T = 385 K; this is the same temperature reached at the end of the batch distillation process
in Example 8.7.
Finally, I would like to draw attention to the initial conditions. The initial conditions are
specified for the differential variables, M and xB. Since the algebraic variables, T and yB, are
not free variables, but depend implicitly on M and xB, they cannot be chosen arbitrarily. In
general, it is a good idea to provide consistent initial conditions to the DAE solver ode15s.
This involves solving the algebraic Equation 8.84 to obtain T and using Equation 8.85 to
obtain yB. Since this problem was not very stiff, it worked even when the initial conditions
were arbitrary.
With this, we come to the end of the case studies for this chapter. Next section summa-
rizes the findings and provides some tips based on my experiences.

8.6 EPILOGUE
The focus of this chapter was solving various problems that require an implicit time-stepping
solver to determine how the solution evolves in time.
The trifecta of Chapters 3 and 4 and the current one covers problems involving differ-
ential equations that evolve in time. Chapters 3 and 4 focused on explicit time-stepping
approaches to solve differential equations: ODE initial value problems in Chapter 3, whereas
360   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

hyperbolic and parabolic PDEs in Chapter 4. That left us with three types of problems in
this chapter: stiff ODEs, hyperbolic/parabolic PDEs, and DAEs that have both differential
and integral components. The glue connecting these seemingly disparate examples was that
all of them require implicit-in-time solution procedure, which forms the central theme of
this chapter.
The ODE-BVPs (boundary value problems) and elliptic PDEs form the final set of
­differential equation problems. Discretization of the domain led to conversion of these
differential equations to linear or nonlinear equations. Methods to solve these equations,
which have special sparse matrix structure, were analyzed in Chapter 7.
I end this chapter with a brief from my personal experience. I have found one of the two
methods as most reliable in MATLAB: using ode15s as described in several examples in
this chapter or writing my own time-stepping solver based on the Crank-Nicolson method.
While ode15s has worked for me in a majority of examples,* there are typical stum-
bling blocks when one attempts to solve a new problem. Assuming that the code is free of
errors and typos, the first issue is “poor” problem formulation. Sometimes, reformulating
the problem in dimensionless or normalized quantities makes it numerically more tracta-
ble, for example, converting from partial pressures to mole fractions. Alternatively, a change
of coordinate system or a linear transformation may make the problem more tractable. It is
also possible to use a physical constraint to replace one of the ODEs. Problem 8.9 shows one
such example, where one may use an algebraic constraint in lieu of a differential equation.
The second issue may be poorly specified initial conditions (in case of DAEs). It is there-
fore a good strategy to solve the algebraic equations

g ( y 0 ,x 0 ) = 0

to obtain consistent initial conditions. Providing consistent initial conditions to a DAE

solver is always a recommended practice. It is sometimes beneficial to tweak the error tol-
erances to get ode15s to solve the problem.
At certain times, the PDEs or partial DAEs may still be unsolvable using ode15s to
solve the discretized ODEs. The Crank-Nicolson method implemented with my own code
is my alternative. Having said that, the ode15s–based approach has often given good per-
formance in my work.
This brings to a close this chapter on DAEs.

EXERCISES
Problem 8.1 Derive the error estimate for Euler’s implicit method using the procedure for
the Adams-Moulton method (Section 8.2.1) and BDF methods (Section 8.2.3).
This can be done by treating Euler’s implicit method as AM-1/BDF-1.

*  As explained in Chapters 3 and 4, and earlier in this chapter, ode45 is the preferred ODE-IVP solver. Thus, ode15s is a
“go-to solver” if I suspect a problem to be stiff or if the nature of the problem (PDE with highly nonlinear source term or
DAE) calls for an implicit solver.
 Implicit Methods   ◾    361

Problem 8.2 Solve the nonlinear chemostat problem from Section 8.3.1 using the second-
order Adams-Moulton method (also known as trapezoidal method). You
may modify the code from Example 8.1 or write a fresh code. The chemostat
model is

S¢ = D ( S f - S ) - rg
X ¢ = -DX + rg Yxs (8.88)
P ¢ = -DP + rg Yps

æ S ö
where rg = ç mm ÷ X , μ  = 0.5, KS = 0.005, Yxs = 0.75, and Yps = 0.65. The
m
è K S + S ø
feed concentration of the substrate is Sf = 5, and the dilution rate is D = 0.1 h−1.
The initial conditions at t = 0 are S(0) = 5, X(0) = 0.02, and P(0) = 0.
Problem 8.3 Modify the Crank-Nicolson solution of Example 8.2 for packed bed reactor
with axial dispersion from Section 4.4. The nondimensional model for the
packed bed reactor is given by

¶f ¶f 1 ¶ 2 f
+ = - Da × f
¶t ¶z Pe ¶z 2

where
ϕ = C/C0 is dimensionless concentration
τ = tu/L is dimensionless time
ζ = z/L is dimensionless length
Pe is Péclet number
Da is Damköhler number

The initial condition is [ϕ]τ = 0 = 1 and boundary conditions are ϕ(t, ζ = 0) = 1

é ¶f ù
and ê ú = 0. The parameter values are Pe = 1 and Da = 2 and residence
ë ¶z û t ,z =1
time is 10. Solve this problem using the Crank-Nicolson method and com-
pare with the solved example from Chapter 4.
Problem 8.4 What is the index of DAE for the model of pendulum in Cartesian coordi-
nates, discussed in Section 8.4.2 and Equations 8.62 and 8.63?
Problem 8.5 The following DAE represents an idealized separation process, where C is the
concentration of the solute being separated. The simplest representation that
retains the DAE nature of the complex dynamics is given by

dC
= -0.1x0.7
dt
362   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

x2 - 3.45 ( C - x ) = 0

with the initial condition C(0) = 1. Solve the above problem in two ways:
(i) Rewrite the second equation to get ξ = ξ(C) and substitute in the ODE.
(ii) Solve the DAE using ode15s and compare the results.
Problem 8.6 Repeat Example 8.7 for a transient flash separation process. Assume the tank
is initially at bubble point of equimolar benzene-ethylbenzene mixture. An
equimolar mixture enters the flash as feed at 10 mol/min. The amount of
vapor drawn is D = 5 mol/min and liquid drawn is B = 5 mol/min. Compute
the transient behavior of the binary flash column.
Problem 8.7 Repeat the above problem for various values of the distillate D = {1, 3, 5, 7, 9}
and with B = F − D.
Problem 8.8 Formulate and solve transient flash separation problem for a ternary mix-
ture of benzene-toluene-ethylbenzene. Antoine’s coefficients for toluene are
AT = 4.1, BT = 1344, and CT =  − 53.8.
Problem 8.9 The following reaction takes place in a batch reactor:

A ® B  C

where k1 = 0.01, k2 = 106, and k3 = 104. The reactor initially has CA0 = 1 mol/L of
species A, and no B or C. The mass balance equations lead to three ODEs in
three unknowns, CA, CB, and CC.
1. Solve the set of three ODEs simultaneously.
2. The three species also satisfy the condition: CA + CB + CC = CA0. Replace
the ODE for CB with the above algebraic constraint and solve the result-
ing DAE.
 CHAPTER 9

Section Wrap-Up
Nonlinear Analysis

This chapter will provide a wrap-up of concepts discussed in Section II of the book. The
concepts for solving algebraic and differential equations, covered in the preceding chapters,
will be used for simulation and analysis of nonlinear systems. The first three sections of this
chapter will focus on methods to analyze the dynamic behavior of nonlinear systems, and
the subsequent sections will focus on specific simulation examples of relevance to process
engineers.
The first three sections will use specific examples of nonlinear dynamical systems to
introduce the readers to nonlinear analysis techniques. Nonlinear systems display very rich
dynamic behavior. Strogatz’s book Nonlinear Dynamics and Chaos is an excellent intro-
ductory text on this topic. The linear stability analysis (Section 5.2) and the examples in
the next three sections cover some basic and important concepts of nonlinear analysis.
Specifically, this involves studying the stability, dynamics, and bifurcation behavior of non-
linear systems. The examples of nonisothermal continuous stirred tank reactor (CSTR) and
chemostat (from Chapter 3) that show multiple steady state behavior will be discussed at
length to introduce the turning point and transcritical bifurcations, respectively. The third
section will study systems with cyclic dynamics (limit cycle).
Finally, two simulation case studies will culminate this part of the book. A tubular/fixed
bed reactor has been discussed at several points throughout this text. An example of gas-
phase reactor with multiple species and multiple reactions will be discussed in Section 9.4.
Both steady state and dynamical models, in the presence of volume change due to reaction,
will be contrasted. The final section will solve the problem stated in the first chapter: to
compute trajectory of a cricket ball.

363
364   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

9.1 NONLINEAR ANALYSIS OF CHEMOSTAT:

“TRANSCRITICAL” BIFURCATION
The nonlinear model of chemostat and its numerical solution using ode45 was discussed
in Section 3.5.4, and the linear stability around its steady states was analyzed in Section 5.2.
A nonlinear analysis of the chemostat and an investigation of bifurcation behavior are con-
sidered in this section.

9.1.1 Steady State Multiplicity and Stability

The model for chemostat was written as

y ¢ = f ( y ) (9.1)

é mSX ù
é f1 ù ê D ( S f - S ) - K + S ú
where ê ú = ê ú (9.2)
ë f 2 û ê -DX + mSX Yxs ú
ëê K +S úû

At steady state, since y′ = 0, the steady state solutions can be found by solving the nonlinear
equations f(y) = 0. The standard method in undergraduate textbooks involves using the
second equation to get the two steady state values. Recall from Chapter 5 that these two
values are given by
DK
S= , X =0 (9.3)
mYxs - D
Here, we will follow a slightly different procedure that will allow us to qualitatively perform
the so-called bifurcation analysis later.
Adding (Yxsf1 + f2) at steady state gives us

0 = D ( S f - S )Yxs - DX (9.4)

Thus, the biomass concentration can be expressed in terms of substrate concentration at

steady state as

Xss = ( S f - S )Yxs (9.5)

Substituting this in the first equation gives

æ mS ö
f1,ss = ( S f - S ) ç D - Yxs ÷ (9.6)
è K + S ø

At steady state, since f1 = 0, the two solutions are given by

é DK ù
ê
y ss = ê m Y - D ú , y = éS f ù (9.7)
xs
ú ss ê ú
êë( f
S - S ) xs úû
Y ë0û

 Section Wrap-Up   ◾    365

The solutions in the above equation are the same as those obtained earlier in Equation 9.3.
Numerically, the two solutions exist for all conditions. However, negative values of either
substrate or biomass concentration are not physical. Thus, we will get nonphysical values
for steady state if 0 ≤ S ≤ Sf is not satisfied.
The linear stability analysis was performed in Chapter 3. The Jacobian was calculated as

é mXK mS ù
ê -D - - ú
(K + S)
2
K +S
ê
J =ê ú (9.8)
mXK mS ú
ê Y
2 xs
-D + Yxs ú
êë ( K + S ) K +S ú
û

The nominal value of the dilution rate was chosen as D = 0.1. The two steady states under
these conditions are

é0.091ù é5 ù
y ss = ê ú , y ss = ê ú (9.9)
ë 3.68 û ë0 û

whereas the eigenvalues of the Jacobian corresponding to the two steady states are

L = {-3.96, - 0.1} , L = {-0.1, 0.257} (9.10)

The linear stability analysis indicates that the first steady state is a stable node, whereas the
second is an unstable (saddle) node.
The linear stability analysis above provides a local dynamical behavior of the system in
the vicinity of the steady state. We will use these results to present analysis of the dynamic
behavior of the overall system, followed by the effect of varying the parameter (dilution rate,
in this example) on qualitative behavior of system dynamics.

9.1.2 Phase-Plane Analysis
A phase-plane plot is a plot that visually depicts dynamics of the nonlinear system on a 2D
plane, with the two state variables as the two axes. Starting at arbitrary initial points within
the space, the ordinary differential equations (ODE) will be solved to obtain variation in the
state variables with time. A trajectory in the 2D phase plane then tracks the dynamic evolu-
tion of the system starting from that particular initial condition. A phase-plane plot is a col-
lection of such trajectories, which thus maps out the system dynamics in a visual manner.
The substrate concentration can take values between 0 and Sf (=5), whereas the biomass
concentration takes values between 0 and 3.75. We will choose 25 points on a 5 × 5 grid in
the S–X plane as initial conditions, solve the ODE, and plot the trajectory on the phase plane.
The phase-plane plot is shown in Figure 9.1. The circles represent starting points (initial
conditions), and the stars represent the two steady states. Based on the linear stability analysis,
the first steady state is linearly stable, implying that all trajectories starting from the vicinity of
this steady state converge toward it. The second steady state (“trivial” steady state because X = 0
366   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Biomass, X
2

0
0 1 2 3 4 5
Substrate, S

FIGURE 9.1  Phase-plane plot of nonlinear chemostat. Circles represent initial points, and the two
stars represent the two steady states.

and no conversion of substrate) is a saddle node. Recall that the S-axis was the stable subspace
at the saddle node. Thus, if the initial condition lies on this axis, the nonlinear chemostat will go
to the trivial steady state; all other initial conditions in the S–X space will converge to the first
steady state. As can be seen from Figure 9.1, the nonlinear system shows these dynamic pat-
terns as well. Starting at X(0) = 0, all the trajectories converge to the trivial steady state. These
trajectories are shown by dotted lines. This axis remains the stable subspace for the nonlinear
system also. All other initial conditions converge to the first steady state. In fact, even the initial
conditions starting at a very small value of initial X(0) = 0.01 reach the first steady state. It is
also interesting to see that trajectories starting on the eigenvector v1 = [−0.8  0.6]T stay on the
eigenvector itself, while converging to the first steady state.
In summary, we have (i) obtained multiple steady states in chemostat, (ii) analyzed the
linear stability around each steady state, and (iii) used phase portrait to analyze the dynam-
ics of the nonlinear system. The next task is to determine how the steady states and stability
change with change in the operating parameters of the system.

9.1.3 Bifurcation with Variation in Dilution Rate

Bifurcation may be defined as a sudden change in behavior of a system with a small change
in the system parameter(s). When the parameter is varied smoothly, the system dynamics
also show a smooth change. However, at a certain point, there is an abrupt change in the
qualitative behavior of the system.
In the chemostat example, the dilution rate may be considered a key parameter.
Bifurcation analysis involves monitoring qualitative behavior with variations in the param-
eter to identify topological changes in the system dynamics. The two steady states in a che-
mostat are characterized by the following solutions:

é DK ù
ê
y ss = ê m Y - D ú , y = éS f ù (9.7)
xs
ú ss ê ú
êë( S f - S )Yxs úû ë0û

 Section Wrap-Up   ◾    367

The first steady state is physically relevant only when the two concentrations are posi-
tive. For example, when the dilution rate is increased to D > μYxs, substrate concentration
becomes negative. This value is not physically relevant. Although the system attains a physi-
cally irrelevant value, the numerical solution still exists.
Nonetheless, the system shows an interesting behavior numerically as well. Let ε be a small
positive number. According to Equation 9.7, when D = μYxs − ε, S is a large positive number.
However, when the dilution rate is increased slightly to D = μYxs + ε, S becomes a large negative
number. Thus, there is a discontinuity in the solution at D = μYxs. Thus, this point represents a
bifurcation point because there is a change in the qualitative behavior of the system.

DEFINITION
A bifurcation point is defined as the value of the bifurcation parameter where a qualitative
change in the behavior of the system is observed.

The discontinuity in the root is not the only change that happens in the system. Consider
the Jacobian at the second (trivial) steady state:

é mS f ù
ê -D -
K + Sf ú
J =ê ú (9.11)
ê mS f ú
ê 0 -D + Yxs ú
ë K + Sf û

This is just Equation 9.8, with Sss = Sf and Xss = 0. Since D > μYxs, the second diagonal term
is also negative. Thus, both eigenvalues are negative, and the trivial steady state becomes
stable. This is shown in the next example.

Example 9.1  Bifurcation Analysis

Bifurcation analysis of the chemostat will be performed by varying the dilution rate
from the original value D = 0.1 by 0.05 at each step. The two solutions and respective
eigenvalues will be monitored. The following code monitors the solution and eigen-
values. The code is run multiple times, each time changing the dilution rate:

mu=0.5; K=0.25;
Yxs=0.75; Sf=5;
D=0.1;
% First solution and Jacobian
S=D*K/(mu*Yxs-D); X=(Sf-S)*Yxs;
a1=mu*S/(K+S);
b1=mu*X*K/(K+S)^2;
J=[-D-b1, -a1;
b1*Yxs, -D+a1*Yxs];
368   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

sol1=[S;X];
l1=eig(J);
% Second solution
X=0; S=Sf;
a1=mu*S/(K+S);
b1=mu*X*K/(K+S)^2;
J=[-D-b1, -a1;
b1*Yxs, -D+a1*Yxs];
sol2=[S;X];
l2=eig(J);

The results from varying the dilution rate are presented in the table below:
D 0.1 0.2 0.3 0.35 0.4 0.45 0.5
SS-1 0.0909 0.286 1 3.5 −4 −1.5 −1
3.682 3.536 3 1.125 6.75 4.875 4.339
𝚲 −3.96 −1.54 −0.3 −0.35
−0.1 −0.2 −0.24 −0.01
SS-2 5 5 5 5 5 5 5
0 0 0 0 0 0 0
𝚲 −0.1 −0.2 −0.3 −0.35 −0.4 −0.45 −0.5
0.257 0.157 0.057 0.007 −0.043 −0.093 −0.143

The bifurcation point is somewhere between D = 0.35 and 0.4 (we know it is at 0.375).
The first steady state becomes unphysical. However, more importantly, the second
steady state exchanges stability; it goes from being unstable to stable when the dilution
rate is increased beyond the bifurcation point.

9.1.4 Transcritical Bifurcation
The bifurcation observed in a chemostat is known as transcritical bifurcation, and the point
D = 0.375 where the trivial solution becomes stable is the bifurcation point for the system (as
we will see in this section, the dynamic behavior of the chemostat is even more complex and
interesting!). The salient features of transcritical bifurcation are that both the solutions continue
to exist numerically on either side of the bifurcation point; however, there is an exchange of
stability in one or both types of solutions. Recall that the two types of solutions for a chemostat
are the regular solution (with generation of biomass) and the trivial solution (no conversion or
generation of biomass). At low values of dilution rate, the former is a stable solution whereas the
latter is unstable. At higher values of dilution rate, however, the trivial solution becomes stable.
A graphical method will be used to further demonstrate transcritical bifurcation. We will
do so in a single dimension since multiple dimensions are difficult to visualize. The treat-
ment here follows on the same lines as that in the nonlinear dynamics book by Strogatz;
however, I have extended his graphical to two dimensions and to a practical system of inter-
est to chemical engineers. At steady state

Xss = ( S f - S )Yxs (9.12)

 Section Wrap-Up   ◾    369

and

æ mS ö
f1 = ( S f - S ) ç D - Yxs ÷ (9.13)
è K + S ø

Let us say that the system was moved slightly from steady state point by introducing a very
small change from the steady state concentrations. We wish to analyze how the system
responds to this change. The form of the equation

æ mS ö
S¢ = ( S f - S ) ç D - Yxs ÷ (9.14)
è K + S ø

broadly gives qualitative insights into the dynamic response of the system in the vicinity
of the steady state. The points of intersection of this curve f1 ( S ) with the S-axis gives the
steady state solutions of the system. When f1 ( S ) > 0, S′ is positive and substrate concentra-
tion S will increase with time. Conversely, S will decrease with time when f1 ( S ) < 0.
Figure 9.2 shows the plot of f1 ( S ) vs. S for four different values of D. The top panel rep-
resents dilution rates below μYxs = 0.375, whereas the bottom panels represent dilution rates
exceeding this value. The arrows indicate the direction in which S would move for small
deviations from the steady state. If S′ is positive, the value of S increases. At D = 0.3, the two
steady states are S = 0.09 and S = 5. When the value of S is decreased slightly (or ­conversely,
X is increased slightly) from S = 0.09, the dynamics cause S to increase and reach steady
state. Likewise, increasing S slightly will again move the system back to the steady state.
This makes S = 0.09 a stable steady state. When the dilution rate is increased to 0.3, the

5 D = 0.3
S΄

D = 0.1

D = 0.45 D = 0.6
S΄

5 5
S S

FIGURE 9.2  Plot of f1 ( S ) vs. S for four different values of dilution rate, D. Arrows indicate the
direction in which S moves with time. Stable and unstable steady states are marked by a diamond
and a circle, respectively.
370   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

first steady state moves toward the second steady state. The steady state value of S keeps
increasing with D. At around D = 0.357, the second steady state almost reaches S = 5; when
D is increased further, the solution becomes nonphysical. From a numerical viewpoint, the
trivial steady state becomes stable at this bifurcation point.

THE RICHER WORLD OF BIFURCATION

This box may be skipped without loss in continuity of discussion.
In the previous discussion involving steady states and linear stability analysis of the
chemostat, we identified D = 0.375 as a bifurcation point. Physically, the first steady state
becomes meaningless because the first root gives S < 0. However, in the discussion above,
between 0.3571 < D < 0.375, the first root S > Sf; which results in X < 0 becoming a nonphysi-
cal solution. So, to summarize our discussion so far

(i) There exist two steady states for D < 0.3571. The first steady state is stable and the
trivial steady state is unstable.
(ii) Between 0.3571 < D < 0.375, the trivial steady state is the only physically relevant
steady state. Numerically, however, both the steady states continue to exist, though
the first one is nonphysical because S > Sf and X < 0.
(iii) For 0.375 > D, again the first steady state is nonphysical because S < 0.

This brings me to a nuance, which is skipped in the undergraduate material. We often make
the assumption that the saturation constant K ≪ Sf. In this case, washout is observed very
close to D > μYxs. However, for larger values of K (say 1.0), the washout will happen reason-
ably below the D = μYxs condition.
The question then remains, which of the two points, D = 0.3571, 0.375, is the bifurcation
point. In order to answer this question, let us look at the plot of f1 ( S ) at an intermediate value
of D = 0.36 shown in Figure 9.3.
When the dilution rate is increased from 0.3 to 0.36, the two steady states collide at
the bifurcation point D = 0.3571 and exchange stability and continue. This is a classic
example of transcritical bifurcation. The first steady state is stable and the trivial steady state
unstable (saddle node) below the bifurcation point. At this bifurcation, the two steady states
exchange stability. The first steady state becomes a saddle node, whereas the trivial steady
state becomes stable.
Another interesting phenomenon occurs as D is increased further and approaches 0.375.
As described before, between 0.3571 < D < 0.375, S is positive and X is negative. When the

D = 0.36

5 6

FIGURE 9.3  Plot of f1 ( S ) at an intermediate value of D = 0.36. The X-axis is zoomed in to

clearly show the points of intersection of the curve.
 Section Wrap-Up   ◾    371

value of D is increased beyond 0.375, the steady state S jumps to a large negative value, X
becomes positive, and the second solution becomes stable.
Let us analyze and verify the results using linear stability analysis in the table below:

D 0.3 0.36 0.4

SS-1 1 6.0 −4
3 −0.75 6.75
𝚲 −0.3 −0.36 −0.4
−0.24 0.0024 −0.06
SS-2 5 5 5
0 0 0
𝚲 −0.3 −0.36 −0.4
0.057 −0.0029 −0.043

Thus, the first steady state goes from stable to saddle node and back to stable when the dilu-
tion rate is increased across the two bifurcation points, D = 0.3571 and D = 0.375.

Figure 9.4 is the bifurcation plot for the system. It represents various steady states of
the system and how they vary with the dilution rate. This plot is thus a locus of all steady
state points as the dilution rate is varied. Solid lines represent stable nodes, and dashed
lines represent unstable (saddle) nodes. The locus of the first steady state is plotted as thick
lines. Before the bifurcation point, this steady state is stable. After the bifurcation point, this
steady state is only numerical; it does not have a physical meaning. It is shown in Figure 9.4
for the sake of completeness. The thin lines represent the trivial steady state. This is unstable
until the bifurcation point. At the transcritical bifurcation, the two steady states exchange
stability and the trivial steady state becomes stable beyond D > 0.3571.

10

5
Substrate, S

–5
0 0.1 0.2 0.3 0.4
Dilution, D

FIGURE 9.4  Bifurcation diagram for the chemostat. Thick lines represent the first steady state and
thin lines represent the trivial steady state. Solid lines imply stable and dashed lines unstable steady
state.
372   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

This is just a brief introduction to the wide world of nonlinear dynamics. The next exam-
ple, nonisothermal CSTR, displays another type of bifurcation behavior, called turning-
point bifurcation.

9.2 NONISOTHERMAL CSTR: “TURNING-POINT” BIFURCATION

A nonisothermal stirred tank reactor with a cooling jacket was modeled in Section 3.5.2.
The reactant concentration, reactor temperature, and temperature of the cooling fluid were
three state variables, that is, y = [CA  T Tj]T. The model equations are given by

dC A F
= ( C A,in - C A ) - rA (9.15)
dt V

dT
V rc p = F rc p (Tin - T ) + ( -DH ) rAV - UA (T - Tj ) (9.16)
dt

dTj
Vj r j c j = Fj r j c j (Tj ,in - Tj ) + UA (T - Tj ) (9.17)
dt

The existence of two qualitatively different steady states was briefly presented in Chapter 3.
In this section, a nonlinear analysis of this system will be presented. The standard multiple
steady state behavior observed in this system is categorized as turning-point bifurcation.
The qualitative features of this bifurcation will be analyzed, and the results contrasted with
the transcritical bifurcation from the previous section. Our analysis will follow a familiar
pattern from the previous section.

9.2.1 Steady States: Graphical Approach

A graphical method, similar to the one used in the previous section, will be used to find the
steady state solutions. The steady state solutions are the roots of the equation f(y) = 0. Like
before, the two state variables CA and Tj will be expressed in terms of T:

Tj =
( Fj r j c j )Tj,in + (UA )T (9.18)
Fj r j c j + UA

æ E ö
The reaction is first order so that r = k0 exp ç - ÷ C A . The first equation, f1(y) = 0, is used
è RT ø
to express the concentration as a function of temperature. Substituting the value of Tj and
CA in the second equation, we get

kt UA
f 2 (T ) = ( -DH )
1 + kt
( FC A,in ) + F rc p (Tin - T ) -
1+ b
(T - Tj,in ) = 0 (9.19)

V UA
where t = , b= (9.20)
F Fj r j c j
 Section Wrap-Up   ◾    373

The derivation of the above equation is left as an exercise. Depending on the values of the
various parameters, the above equation can have one, two, or three solutions. These will be
investigated shortly.

MULTIPLE STEADY STATES IN CSTR: FROM UNDERGRADUATE

REACTION ENGINEERING TEXT
Multiple steady state behavior is also considered in an undergraduate reaction engineering
course. The conversion is defined as X = (CA , in − CA)/CA , in. With this definition, the mass bal-
ance equation (9.15) becomes
XA æ E ö
0= - k0 exp ç - ÷ (1 - X A ) (9.21)
t è RT ø
whereas the energy balance equation (9.16) becomes

0 = Frcp (Tin - T ) + ( -DH ) FC A,in X A - UA

(T - Tj ,in ) (9.22)
1+ b
The two equations can be rearranged to express XA as a function of T. In his book on reac-
tion engineering, Fogler denotes these two as XA , MB and XA , EB to represent mass and energy
balance equations, respectively. Thus
æ E ö
k0 exp ç - ÷t
X A,MB = è RT ø (9.23)
æ E ö
1 + k0 exp ç - ÷t
è RT ø

UA
(T - Tj ,in ) + Frc (T - T )
p in
1+ b (9.24)
X A,EB =
FC A,in ( -DH )

When XA is plotted against T, the former is an S-shaped curve, whereas the latter is a straight
line (see Figure 9.5). It is clear that the roots of the equations are the points of intersection of

0.8
Conversion, XA

0.6

0.4 MB
EB (350)
0.2 EB (298)
EB (398)
0
273 373 473 573 673 773
Temperature, T

FIGURE 9.5  Conversion vs. temperature from material balance (“MB” from Equation 9.23)
and energy balance (“EB” from Equation 9.24). The inlet temperature, Tin is shown in brackets.
374   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

TABLE 9.1  Model Parameters and Operating Conditions for a Jacketed CSTR
CSTR Inlet Cooling Jacket Other Parameters
F = 25 L/s Fj = 5 L/s CA , in = 4 mol/L
V = 250 L Vj = 40 L k0 = 800 s−1
ρ = 1000 kg/m3 ρj = 800 kg/m3 E/R = 4500 K
cp = 2500 J/kg · K cp = 5000 J/kg · K (−ΔH) = 250 kJ/mol
Tin = 350 K Tj , in = 25°C UA = 20 kW/K

the two curves. The parameters used in Chapter 3 are given in Table 9.1. The solid line and
solid S-shaped curve in Figure 9.5 represent the above two equations for the nominal values
of parameters shown in the table. The two curves intersect at three different points, which
are the three steady states of the system. When the inlet temperature is decreased to 298 K,
the material balance curve (denoted as MB) remains the same, while the energy balance
curve shifts to the left (dashed line, “EB (298)”). Now, there is only a single point of intersec-
tion of the two curves (and hence a single solution). Likewise, when the inlet temperature
is increased to 398 K (dash-dot line, “EB (398)”), again the MB and EB curves intersect at a
single point.
This analysis from standard textbooks is nothing but an analysis of multiple steady states
with the CSTR inlet temperature as a bifurcation parameter.

The discussion in the box is a popular approach to introduce multiple steady state
behavior in higher dimensions taken in standard undergraduate texts in reaction
engineering.
We will use another approach, similar to the one in the previous section, by plotting
f 2 (T ) vs. T. The points of intersection of this curve with the T-axis give the steady state
solutions of the original nonlinear system of equations. The curve f 2 (T ) vs. T is plotted
(see Table 9.1 for nominal values of parameters) in Figure 9.6. The curve intersects T-axis at
three points, {350, 478, 648 K}, which represents the three steady states. The corresponding
values of CA , Tj can be calculated from Equation 9.18.
Based on the approximate graphical method, the three steady state values are

é3918 ù é2420 ù é 459 ù

ê ú ê ú ê ú
y ss = ê 350 ú , y ss = ê 478 ú , y ss = ê648 ú (9.25)
ê 324 ú ê 388 ú ê 473 ú
ë û ë û ë û

The actual steady state values can be computed using fsolve with these as initial guesses.

9.2.2 Stability Analysis at Steady States

As before, two different approaches to analyzing the steady states will be discussed. First is
the qualitative graphical approach. Consider the f 2 (T ) vs. T curve in Figure 9.6. When the
 Section Wrap-Up   ◾    375

T (K)

373 473 573 673

f2(T)

FIGURE 9.6  Function f 2 (T ) from Equation 9.19 plotted against temperature. Steady state solutions
are indicated by roots of f 2 (T ). The arrows represent the direction of change in T for small variations
from steady state value.

CSTR state variables are moved slightly from their steady state values, the approximate
dynamics of the system is qualitatively governed by

f 2 (T )
T¢ =
V rc p

This is because assuming Equation 9.15 to be at steady state yielded CA(T) and assuming
Equation 9.17 at steady state yielded Tj(T). The function f 2 (T ) was obtained by substituting
these expressions in Equation 9.16. Thus, if the value of f 2 (T ) is positive in the vicinity of
a steady state, the temperature is likely to increase, whereas if it is negative, then the tem-
perature will decrease. As can be seen in Figure 9.6, f 2 (T ) is positive for T < 350 and nega-
tive between 350 < T < 478. So, if the temperature is nudged away from the low-conversion
steady state in either direction, it will return back to the steady state. This qualitatively indi-
cates that the first steady state is stable. Similarly, f 2 (T ) is positive slightly below 648 K and
is negative slightly above 648 K. Again, this high-conversion steady state is stable because
nudging the system from this steady state in either direction will cause the system to return
to the steady state. Finally, the steady state at 478 K is unstable. This is because f 2 (T ) is neg-
ative between 350 < T < 478 and positive between 478 < T < 648, indicating that nudging the
system away from the steady state will make the system diverge away from the steady state.
This is the qualitative analysis of system stability. Since the 3D space is projected on a
single dimension, this analysis is only approximate. This needs to be corroborated with
stability analysis at each steady state.
The function cstrFun.m, discussed in Chapter 3, can be used with the fsolve
solver to find the actual steady state values. The approximate values in Equation 9.25 will
be used as initial guesses for fsolve solver. The reader can verify that the steady state
solutions are indeed very close to the values shown in Equation 9.25. Once these values are
known, the next task is computing the Jacobian at each of the three steady states. One may
376   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

either compute the Jacobian analytically or numerically. In case of the latter, the function
cstrFun.m itself can be used to compute the numerical Jacobian as

fi ( y ss + d j ) - fi ( y ss + d j )
J ( i ,j ) = (9.26)
2e

where δj is a 3 × 1 vector such that its jth element is ε and the other elements are zero. For
example

é0 ù
ê ú
d2 = ê e ú
ê0 ú
ë û

The actual steady state was computed using fsolve, followed by computing the Jacobian
numerically for each of the three steady states. The results are given below:

é -0.102 -0.299 0 ù
ê ú
Low J = ê 0.0002 -0.102 0.032 ú , l = {-0.099, - 0.081, - 0.273} (9.27)
ê 0 0.125 -0.25úû
ë

é -0.163 -3.072 0 ù
ê ú
Mid J = ê 0.006 0.175 0.032 ú , l = {0..117, - 0.099, - 0.256} (9.28)
ê 0 0.125 -0.25úû
ë

é -0.872 -3.794 0 ù
ê ú
High J = ê 0.077 0.247 0.032 ú , l = {-0.108, - 0.402, - 0.365} (9.29)
ê 0 0.125 -0.25úû
ë

The qualitative predictions based on Figure 9.6 are confirmed by the linear stability analysis
above. The low- and high-conversion steady states are stable, whereas the middle steady
state is unstable (in fact, a saddle node).

9.2.3 Phase-Plane Analysis
Phase-plane analysis is very useful to get a global picture of the system behavior. The con-
centration values are in the range 0 < CA < 4000, whereas temperature values are in the
range 300 < T < 700. Choosing several points in the state space as initial conditions, simula-
tions are performed. The dynamical trajectories are then plotted on a CA–T plane. Circles
represent initial starting points, and stars represent the three steady states. The phase por-
trait for the nonlinear CSTR is shown in Figure 9.7.
 Section Wrap-Up   ◾    377

750

Temperature, T (K)
600

450

300
0 1000 2000 3000 4000
Concentration, CA (mol/m3)

FIGURE 9.7  Phase portrait of a nonlinear CSTR with Tin = 350 K. The filled stars represent stable
steady state, open star represents unstable steady state, and circles represent initial conditions.

9.2.4 Turning-Point Bifurcation
Like in the bioreactor case, the bifurcation analysis of the nonisothermal CSTR with respect
to the inlet temperature, Tin, as the bifurcation parameter will be discussed in this section.
Inlet conditions, which can be varied easily in practice, become the natural choice as bifur-
cation parameters. The curve f 2 (T ) intersects the T-axis at three points, indicating that
three different steady states coexist at the value of parameter Tin = 350 K. Since the inlet
temperature appears in Equation 9.19 as

F rc p (Tin - T )

increasing this value will simply move the curve f 2 (T ) upward. As the temperature Tin is
increased, the curve keeps moving upward. As seen in Figure 9.8, when the inlet tempera-
ture is increased to about 380 K, the lower and middle steady states merge. At this bifurca-
tion point, there are only two steady states. The high-conversion steady state is qualitatively
the same as before.* When the inlet temperature is further increased, the high-conversion
steady state remains the only steady state. Thus, the characteristic of turning-point bifurca-
tion is that two steady states come to merge at the bifurcation point and eventually disap-
pear when the bifurcation parameter is varied further. The turning-point bifurcation occurs
between the low- and mid-conversion steady states; the high-conversion steady state does
not undergo bifurcation when Tin is increased from 350 K.
A similar turning-point bifurcation behavior is seen when the inlet temperature Tin is
decreased from 350 K. Specifically, when this parameter reaches ~313 K, the high-conver-
sion and mid-steady states merge; further reducing the inlet temperature eliminates these
two steady states and only the low-conversion steady state remains. Thus, this is a second
turning point, often called extinction point, where two steady states (mid and high) disap-
pear, leaving only the low-conversion steady state.

*  The high steady state remains stable as before. The characteristic of turning-point bifurcation in one dimension is that one
stable node (low steady state) and one unstable node (middle steady state) merge to give a saddle node, according to
Figure 9.7. For this reason, the turning-point bifurcation is also known as saddle node bifurcation. However, I think this is a
misnomer because in multiple dimensions, the middle steady state was not unstable; it was already a saddle node!
378   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Tin = 380 Tin = 398

f2(T)
500 700 500 700

500 700 500 700

f2(T)

Tin = 313 Tin = 298

FIGURE 9.8  Effect of varying Tin on the multiple steady state behavior of CSTR. The top panels
show increase in Tin, and the bottom panels show decrease in Tin from the nominal value of 350 K. At
the bifurcation point, two steady states merge (represented as star in left panels) and then disappear.

We are now equipped to make a bifurcation diagram, which is shown in Figure 9.9. The
actual numerics behind constructing a complete bifurcation diagram is beyond the scope
of this text. Nonetheless, we will use the tools studied so far to make this plot. Between
the two bifurcation points, 313 ≲ Tin ≲ 380, all the three steady states exist simultane-
ously; below the lower bifurcation point, only the low steady state exists, whereas above
the higher bifurcation point, only the high steady state exists. Starting with Tin = 298, Tin is
increased progressively, each time using fsolve to obtain the low steady state. The previ-
ous fsolve solution may be used as an initial guess. This continues until Tin ≈ 380, beyond
which the solution jumps to the higher branch (denoted by the upward arrow in Figure 9.9).
Increasing Tin further, the solution continues marching along the high-conversion branch.

700
Temperature, T (K)

600

500

400

300
300 320 340 360 380 400
Inlet temperature, Tin (K)

FIGURE 9.9  Bifurcation plot for a nonlinear CSTR with Tin as the bifurcation parameter. The two
turning points are marked as stars.
 Section Wrap-Up   ◾    379

After reaching 398 K, the temperature is decreased again. The procedure of incrementally
decreasing Tin, each time using fsolve to obtain the steady state value, may be repeated.
At this stage, a hysteresis is observed; the system does not jump to the low-conversion
steady state at 380 K. Instead, it continues along the high-conversion branch until the other
turning point is reached at Tin = 313 K.
The high- and low-conversion branches correspond to stable steady states and are there-
fore shown as solid lines. The bifurcation points are marked as stars in Figure 9.9. The mid-
dle steady state branch is denoted by dashed lines since the middle steady state is unstable.
Obtaining the middle steady state branch can be a little tricky. At the first bifurcation point
of 380 K, the steady state solution jumps from T = 402 K to T = 685 K. Thus, at Tin = 379,
fsolve can be used to obtain the middle steady state by assuming the initial guess of the
temperature to be T(0) = 450 K. Indeed, the solution at the middle branch is obtained as
T = 420.8 K. Thereafter, the inlet temperature Tin may be progressively decreased, each time
using fsolve to chart out the middle steady state branch.
This procedure to chart out the bifurcation plot is known as parametric continuation.
Recall that we were already introduced to natural parameter continuation in Chapter 3.
There, we increased the inlet temperature Tin in the same step-wise manner but used an
ODE solver instead. That procedure will allow us to trace the two stable branches; the alge-
braic solver with the procedure elaborated in this section is required to trace the unstable
branch.
This completes our introduction to steady state multiplicity. There are two other types of
local bifurcation—subcritical and supercritical pitchfork bifurcation. We will skip them in
this book. The next interesting example is that of systems exhibiting oscillations.

9.3 LIMIT CYCLE OSCILLATIONS

9.3.1 Oscillations in Linear Systems
The mass-spring-damper system, introduced in Chapter 3, as an example of second-order
ODE-IVP is modeled as

mx ¢¢ + cx ¢ + kx = 0 (9.30)

where
x″ is the acceleration
v = x′ is the velocity

The ODE models the motion of a body with mass m attached to a spring. The mass is dis-
placed initially to x = x0 and released. The second-order ODE is converted to the following
set of first-order ODE-IVP:

é v ù
y¢ = ê ú , y ( 0 ) = é x0 ù (9.31)
c k
ê- v - x ú ê ú
êë m m úû ë0û

380   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

This can be written in standard linear ODE form, y′ = Ay, where

é0 1ù
A=ê ú
ë -k - c û

The eigenvalues of the above matrix can be computed to be

- c ± c 2 - 4k
l=
2

Consider the case where the spring constant k = 1 and the damping coefficient is varied.
When the damping coefficient is large, that is, c > 2k , the system is overdamped. The ori-
gin is a center and trajectories are attracted to the center. When the damping coefficient
is decreased, the response becomes oscillatory. For example, with c = 0.5, the eigenvalues
are λ =  − 0.25 ± 0.968i. The system is a stable spiral. As the damping coefficient value is
decreased, system response becomes increasingly underdamped and oscillations increase.
This happens until the damping coefficient becomes zero, in which case, the system oscil-
lates without any damping. We had analyzed such linear dynamical systems in Section 5.2.
The time response and phase portrait for the system are shown in Figure 9.10.
v

x
v
x and v

x
v

(a) Time (b)

FIGURE 9.10  Response of mass-spring-damper system for various values of damping coefficient.
(a) Show location (solid line) and velocity varying with time and (b) phase-plane plots. The top,
middle, and bottom rows indicate c = 3, c = 0.5, and c = 0, respectively.
 Section Wrap-Up   ◾    381

The closed circles are a characteristic response of linear systems with purely imaginary
eigenvalues. The oscillating system charts out multiple concentric circles. Thus, with an ini-
tial displacement of 1, the system oscillates between −1 ≤ x ≤ 1 without any attenuation, and
the amplitude remains equal to 1 even after a long time. Likewise, if the initial displacement
were 0.5, the system would oscillate between −0.5 ≤ x ≤ 0.5, and so on.

9.3.2 Limit Cycles: van der Pol Oscillator

The documentation for MATLAB® ODE solvers describes a van der Pol oscillator. It is
a standard example of nonlinear oscillating systems. Unlike the linear system described
above, van der Pol oscillator has a more interesting behavior, known as the limit cycle.
Before describing the limit cycle, let us consider the simulation of the van der Pol system.
The model for the system is given by

( )
x ¢¢ + m x 2 - 1 x ¢ + x = 0

(9.32)

A Dutch electrical engineer, Balthasar van der Pol, proposed this model and showed that
the system exhibited stable oscillatory behavior. He called these dynamics “relaxation oscil-
lations,” as will be described after the following example. In this example, the transient and
phase-plane plots of a van der Pol oscillator will be obtained, followed by a discussion of
their dynamics.

Example 9.2  van der Pol Oscillator

Problem: Simulate the van der Pol oscillator of Equation 9.32.
Solution: The ODE-IVP is written as the following set of two ODEs:

x¢ = v
(9.33)
( )
v ¢ = -m x 2 - 1 v - x

This becomes a 2D ODE-IVP problem, with the function defined as

function dy=vanderPolFun(t,y,mu)
dy(1,1)=y(2);
dy(2,1)=-mu*(y(1)^2-1)*y(2)-y(1);
end

The resulting problem is solved using ode45 for two different values of μ, 1 and 10.
The initial condition is chosen as [x v]T = [0.1  0]T. Figure 9.11 shows the transient
response and phase-plane plot of the van der Pol oscillator for two different values
of μ, that is, μ = 1 and μ = 10. Periodic oscillations are observed for both the values of
parameter μ.
Note the difference between these oscillations and those in Figure 9.10: The van der
Pol oscillator has a single stable closed trajectory. This is shown in the top right panel,
where the response to three different initial conditions is plotted in the phase plane
382   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

2
2

x΄
0

x
–2 2

–2 x
–2

2 10

x΄
0
x

–2 2
–2 x
–10

0 25 50
(a) Time (b)

FIGURE 9.11  Transient response of x (a) and phase-plane plots (b) for van der Pol oscillator. The
top row represents μ = 1 and bottom row represents μ = 10.

(as solid, dashed, and dash-dot lines). Irrespective of the initial condition, the system
settles at the same closed trajectory. This is known as limit cycle behavior.
The top row represents μ = 1. Notice how the trajectory is nearly uniform. However,
when the parameter value is increased to μ = 10, the transient trajectory gets a peculiar
qualitative behavior. There are long stretches of slowly changing response followed by
a short period of rapid change. This observation is discussed in this section.

9.3.2.1 Relaxation vs. Harmonic Oscillations

van der Pol coined the term “relaxation oscillations” to describe the behavior of this
oscillator. This may be contrasted with harmonic oscillations of the mass-spring-
damper system. When μ = 0, the model becomes equivalent to a (undamped) mass-
spring system. When μ is positive, damping is introduced in the system. Unlike the
mass-spring-damper system, the damping is nonlinear. This has significant conse-
quence on the system response near the origin. When the van der Pol equation (9.33)
is linearized at the origin, we get

é0 1ù
J =ê ú
ë -1 m û

The characteristic equation of the Jacobian

l 2 - ml + 1 = 0 (9.34)
 Section Wrap-Up   ◾    383

2 2

–2 2

–2 µ = 0.2 –2 µ = 0.5

FIGURE 9.12  Phase portrait of a van der Pol oscillator for small values of μ = 0.2 and 0.5.

indicates that the origin is an unstable node. Starting from a point close to the origin, the
trajectory will diverge. However, the nonlinear damping coefficient, c ≡ μ(x2 − 1) grows as x
increases. Thus, the state variables are not allowed to grow in an unbounded manner. This
is the physical interpretation of the closed cyclic trajectories seen in Figure 9.11.
Figure 9.12 shows the phase portrait when the damping coefficient is small. When μ = 0.2,
the damping term is small. The eigenvalues from Equation 9.34 are 0.1 ± 0.995i. The origin
is now an unstable spiral. As seen in the left-hand panel of Figure 9.12, the trajectory spirals
out from the origin. As the value of x increases beyond 1, the damping, c ≡ μ(x2 − 1) increases.
The trajectory spirals multiple times around the origin and settles at the limit cycle. When
μ is increased to 0.5 (and then to 1), the system still grows slowly away from the origin and
settles at the limit cycle. When the coefficient is increased further, damping is increased and
the shape of the limit cycle becomes highly skewed (Figure 9.11, bottom-right panel).
Finally, let’s discuss what the term “relaxation oscillation” implies. Consider the case
when μ = 10, indicating that the damping is quite high. Around time t = 15, as seen in
the bottom-left panel of Figure 9.11, x ≈ 2. The damping term is large, making the sys-
tem response highly overdamped (see previous example) and hence very sluggish. As x
approaches 1, the damping term reduces and the speed of response increases. When x falls
below 1, the damping c ≡ μ(x2 − 1) becomes negative and the system tries to become unsta-
ble. Thus, there is a brief period when the value of x falls rapidly. Once it goes below –1, the
damping term becomes positive, the van der Pol system becomes stable, and the response
again becomes overdamped when x <  −2. Thus, the system is characterized by a very long
“relaxation time” (when the response is overdamped), followed by a short “impulsive
period” where the state variable changes rapidly. The relaxation time governs the period of
oscillations for the system.
The van der Pol system shows limit cycle behavior, where a unique stable closed tra-
jectory exists. This manifests as constant-amplitude oscillations, irrespective of the initial
condition.

9.3.3 Oscillating Chemical Reactions

Boris Belusov was a Russian chemist who is credited for discovering oscillatory chemical
reactions, which then led to the development of nonlinear analysis of chemical systems.
While working on citric acid cycle, Belusov discovered an oscillating chemical reaction.
His discovery was ahead of its time and was met with skepticism within the scientific
384   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

community. This work was picked up by Anatol Zhabotinsky, who further investigated the
reaction. Their work spawned a lot of activity in similar systems. Their oscillating reaction
between citric acid, bromate, and cerium as catalyst is now popular as Belusov-Zhabotinsky
(B-Z) reaction.
Since then, several other oscillating chemical reactions have been discovered. The
Briggs-Rauscher reaction is a popular reaction for demonstrating this phenomenon. It is
a reaction between malonic acid, potassium iodate, and hydrogen peroxide in presence of
Mn+2 catalyst. Bromate solution from the original B-Z system is replaced with an iodide
solution. With starch added as indicator, the demo reaction is visually striking because it
oscillates between dark-blue color in the presence of iodide ion and amber color when it
gets converted to iodine.*
The basic mechanism that reproduces oscillations observed in the B-Z reaction is

A ¾k¾
1
®X
2 X + Y ¾k¾
2
® 3X (9.35)
B + X ¾k¾
3
®Y + C

X ¾k¾
4
®D

This mechanism is called the Brusselator scheme. The second reaction in the above mecha-
nism is an autocatalytic reaction. The overall reaction scheme remains oscillatory so long
as A and B are in significant excess. When A and B are in excess, we can assume CA , CB to
be constant. Since C and D are products, they do not affect the material balance of X and Y.
The ODEs for the two species X and Y are

C ¢X = k1C A0 + k2C X2 CY - ( k3C B 0 + k4 ) C X

(9.36)
CY¢ = k3CB 0C X - k2C X2 CY

Dividing throughout by k1CA0 and defining x = CX/k1CA0 and y = CY/k1CA0, the two ODEs can
be written as

x ¢ = 1 + ax 2 y - ( b + k4 ) x
(9.37)
y ¢ = bx - ax 2 y

where

a = k2 ( k1C A0 ) ,
2
b = k3CB 0

The following example shows the code for the Brusselator system.

*  A nice demonstration of this and other oscillating reactions is available on YouTube. For example, see https://www.youtube.
com/watch?v=IggngxY3riU [Last accessed: January 10, 2017].
 Section Wrap-Up   ◾    385

Example 9.3  Simulations of the Brusselator System

Problem: Perform dynamic simulations of the Brusselator system, given by Equation
9.37 for α = 1 , β = 1 , k4 = 1.
Solution: The function file for the Brusselator system is straightforward and given
below:

function dY=brusselatorFun(t,Y,par)
% Function file for Brusselator system
a=par.alpha; b=par.beta;
k4=par.k4;
x=Y(1); y=Y(2);
%% Model equations
dx=1+a*x^2*y-(b+k4)*x;
dy=b*x-a*x^2*y;
dY=[dx;dy];

The above function can be passed on to an ode45 solver to obtain the tran-
sient dynamics. The transients of the system obtained for the initial conditions
x0 = 1 , y0 = 0.5 are shown in the top panel (Figure 9.13). The bottom panel shows
the phase portrait, which was obtained starting from various initial conditions in
the phase plane. The thick dashed line in the phase-plane plot corresponds to the
initial conditions [1  0.5]T of the top panel. The point, (1, 1) is a stable steady
state point. It is a spiral since the trajectories show some oscillations before settling
down to the steady state.

1.2
1
x and y

0.8
0.6
0.4
0 5 10 15 20
Time

1
y

0
0.5 1 1.5 2 2.5 3
x

FIGURE 9.13  Transients of the Brusselator reactor and the phase portrait for α = 1 , β = 1 , k4 = 1. In
the top panel, the initial conditions are x0 = 1 , y0 = 0.5.
386   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Let us analyze the Brusselator system. The steady state for the system can be obtained by
equating the two transient equations to zero and adding them up. For constant values of
α = 1, k4 = 1, the steady state is

xSS = 1, ySS = b (9.38)

Linearizing the Brusselator equation at this steady state, we get the Jacobian as

éb - 1 1ù
J =ê ú (9.39)
ë -b -1û

The characteristic equation of the above matrix is

l2 + l ( 2 - b ) + 1 = 0 (9.40)

When β = 1, as in Example 9.3, the steady state [1  1]T is a stable attractor. The eigenvalues
of the Jacobian are λ =  − 0.5 ± 0.866i, which confirms our observation that the steady state
is a stable spiral.
As in Section 9.1, we will analyze the effect of varying the inlet concentration CB0 on
the dynamics of the system. Changing CB0 affects the parameter β. When the bulk concen-
tration of B is increased threefold, the value of the parameter β is increased to 3. Under
these conditions, the system shows interesting dynamics. The steady state can be calculated
from Equation 9.38 as YSS = [1  3]T. From the characteristic equation (9.40), one can com-
pute the eigenvalues at the steady state to be λ = 0.5 ± 0.866i. This indicates the steady state
is an unstable spiral. Although this steady state is unstable, it is circumscribed by a limit
cycle, as shown in Figure 9.14. Any trajectory starting close to the steady state diverges

4
x and y

0
0 10 20 30 40 50
Time

4
y

0
0 1 2 3 4 5
x

FIGURE 9.14  Transient response of the Brusselator system and phase portrait for β = 3.
 Section Wrap-Up   ◾    387

outward. However, as we have seen in the van der Pol oscillator, the trajectory does not
grow unbounded. Instead, it settles as a single closed trajectory, the limit cycle.
Thus, from β = 1 to 3, the system goes from a stable spiral to an unstable spiral, with
the unstable spiral being enclosed by a stable limit cycle. At β = 2, the eigenvalues of the
Jacobian are λ =  ± i. When β < 2, the real part of the eigenvalue is negative and the steady
state is a stable spiral. When β > 2, the steady state becomes an unstable spiral. Thus, when
the eigenvalues of the Jacobian are plotted in a complex plane, they shift from the left-half
plane (stable) to the right-half plane (unstable), with the eigenvalues crossing over from
stable to unstable at the bifurcation point β = 2. Such a crossing-over of eigenvalues at the
imaginary axis (instead of origin) is indicative of the presence of limit cycle oscillations.
Specifically, the above qualitative behavior of a stable spiral transitioning to an unstable
spiral combined with the appearance of a stable limit cycle is an example of supercritical
Hopf bifurcation. When CB0 is increased across the Hopf bifurcation point, the stable system
suddenly transitions into limit cycle oscillations.
This ends our brief introduction to oscillations and limit cycles.

9.4 SIMULATION OF METHANOL SYNTHESIS IN TUBULAR REACTOR

Methanol synthesis is carried out in a catalytic reactor at high pressure and moderate tem-
perature. The synthesis gas is feedstock for this process. The primary reaction taking place
in the presence of a supported copper/zinc catalyst is

CO + 2H2 → CH3OH

Since there is carbon dioxide also present in the syn gas, the water-gas shift reaction

CO2 + H2 → CO + H2O

and direct reduction of CO2

CO2 + 3H2 → CH3OH + H2O

also take place on the catalyst. The three reactions above are not linearly independent. The
third reaction is the sum of the first two reactions. Various kinetic models for different cata-
lysts, operating conditions, and reactor types have been developed in the past. In this case
study, the kinetic model of van den Bussche and Froment (1996) will be used.
Their model considers the methanol synthesis process comprising direct CO2 reduction
and water-gas shift reactions. The kinetics of the two reactions are given by

k1 pCO2 pH2 æ 1 ö

r1 =
G3
ç1 -
ç K eq,1
è
Õp i
ni 1
i ÷
÷
ø
(9.41)

k2 pCO2 æ 1 ö

r2 = ç1 -
G ç K eq,2
è
Õp i
ni 2
i ÷
÷
ø
(9.42)
388   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

where pi are partial pressures in bar, the reaction rate is in mol/kgcat · s, and the rate c­ onstants
are given by

æ 36, 696 ö æ 94, 765 ö

k1 = 1.07 exp ç ÷ , k2 = 1.22 ´ 1010 exp ç - (9.43)
è RT ø è RT ÷ø

The equilibrium constants are obtained as

3066 2073
log10 ( K eq ,1 ) = - 10.592, log10 ( K eq ,2 ) = 2.029 - (9.44)
T T

The inhibition term in the above rate expressions is given by

pH2O
G = 1 + Ka + K b pH2 + K e pH2O
pH2
æ 17,197 ö
K a = 3453.4, K b = 0.499 exp ç ÷, (9.45)
è RT ø
æ 124,119 ö
K e = 6.62 ´ 10-11 exp ç ÷
è RT ø

In this section, we will consider two cases: a steady state and transient simulations of an
isothermal plug flow reactor (PFR). In the case of the former, pressure drop through the
packed bed is considered, whereas pressure drop will be neglected in the transient simula-
tions. We will adopt a modular approach, so that the codes developed in the first part can
be reused in the transient simulations.

9.4.1 Steady State PFR with Pressure Drop

The model equations for the steady state PFR will be discussed in Section 9.4.1.3. Before
that, the calculation of surface reaction rate and processing of input parameters will be dis-
cussed in Sections 9.4.1.1 and 9.4.1.2, respectively.

9.4.1.1 Reaction Kinetics
The first step is to write a function that calculates the rates of the two reactions. The reac-
tion rates depend on the temperature of the catalyst and partial pressures of various species.
These two form the input arguments for the function. The output argument could either be
rate of reactions, rj (as per Equations 9.41 and 9.42), or rates of formation/consumption,
Rk = ∑jνkjrj. We choose the latter in this example. The following function computes the rates
as per the model of vanden Bussche and Froment (1996).
The following function, which is common to both cases, calculates reaction rates:

function rConv=surfRxn(T,pPress,par)
% To calculate rate for methanol synthesis
% Ref: vanden Bussche and Froment (1996) J. Catal.
 Section Wrap-Up   ◾    389

R=par.R;
nu=par.stoich;
pPress=pPress/1e5; % Pressure in bar

% Rate constants
k1=1.07*exp(36696/(R*T));
k2=1.22e10*exp(-94765/R/T);
% Inhibition term
K1=3453.4;
K2=0.499 * exp(17197/R/T);
K5=6.62e-11 * exp(124119/R/T);
G=1 + K1*pPress(5)/pPress(2) + ...
K2*sqrt(pPress(2)) + K5*pPress(5);
% Forward rate
rate =zeros(2,1);
rate(1)=k1/G^3 *pPress(2)*pPress(3);
rate(2)=k2/G *pPress(3);

% Equilibrium
Keq(1)=10^(3066/T-10.592);
Keq(2)=10^(-2073/T+2.029);
for j=1:2
eqTerm=prod(pPress.^nu(:,j));
rate(j)=rate(j)*(1-eqTerm/Keq(j));
end
% Rate of conversion of each species
rConv=par.rhoCat * (nu*rate);
end

Note the third line of the function. The function accepts the inputs in SI units (Kelvin
and Pascal). Since the reaction rate requires partial pressure in bar, this conversion is done
within the surface reaction code itself. Different sources in the literature compute the reac-
tion rate expressions in different ways (e.g., based on concentration, partial pressures in
Pa, mole fraction, etc.). Hence, a good programming practice is that the main code must
consistently use SI units, whereas the unit conversion must be done in the surface reaction
code. In this case, Rk is in mol/m3 · s.

9.4.1.2 Input Parameters and Initial Processing

Modular and flexible codes are often scalable, more efficient, easier to understand, and eas-
ier to extend to different systems. In this example, I want to reuse as many parts of the code
as possible for steady state and transient solutions. With this in mind, a separate function is
written for defining and processing input parameters.

function param=methanolParam
% Computes parameters for methanol synthesis
390   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

%% Geometric Parameters
d=0.016;
Acs=pi/4*d^2; % Cross-sectional area
L=0.15; % Length
dp=0.0005; % Particle diameter
epsi=0.5; % Void fraction

%% Operating conditions
Tin=523;
Pin=5e6;
mFlow=2.8e-5;

% CO, H2, CO2, CH3OH, H2O, N2

Xin=[4; 82; 3; 0; 0; 11]/100;
nu =[0 -3 -1 1 1 0;
1 -1 -1 0 1 0]’;
MW=[28; 2; 44; 32; 18; 28]/1000;
% Calculating Inlet Parameters
Mavg=Xin’*MW;
Ftot=mFlow/Mavg;
Fin=Ftot*Xin;
rhou0=mFlow/Acs;
%% Ergun’s Equation Parameters
ergun1=150*visc/dp^2 * (1-epsi)^2/epsi^3;
ergun2=1.75*rhou0/dp * (1-epsi)/epsi^3;
param.ergun1=ergun1;
param.ergun2=ergun2;

%% Store parameters in a structure

param.L=L;
param.Acs=Acs;
% Species / Reactions
param.MW=MW;
param.stoich=nu;
param.visc==2e-5; % Viscosity (approx.)
param.R=8.314;
param.rhoCat=1775;
% Inlet conditions
param.rhouIn=rhou0;
param.Pin=Pin;
param.Tin=Tin;
param.Fin=Fin;
param.Xin=Xin;

Most of the parameters computed in this function are not dependent on the model assump-
tions, which will get incorporated in the model function file. The discussion on Ergun’s
equation for pressure drop will follow in the next section.
 Section Wrap-Up   ◾    391

9.4.1.3 Steady State PFR Model

The steady state model for a PFR is given by

1 dFk
Acs dz
= rcat ån r kj j (9.46)
j

The mole fractions and partial pressures are calculated as

Fk
Xk = , pk = P (9.47)
å Fi
i

In the examples so far, the total pressure was assumed to be constant. If the pressure drop
along the reactor is significant, it needs to be accounted for using the Ergun’s equation for
pressure drop:

m (1 - e ) rv (1 - e )
2
dP
- = 150 2 3
v s + 1.75 s vs (9.48)
dz dp e d p e3
   
Erg1 Erg 2

Ergun’s equation may be used for a packed bed. For the second constant above, we use the
fact that mass flowrate remains constant:

rv = ( rv )in = Gin (9.49)

which can therefore be precomputed.

If instead the reaction is carried out in a tubular reactor, the pressure drop will instead be

dP 2
= - rv 2 f f (9.50)
dz d

where the Blasius equation

0.079
f = (9.51)
Re0.25

can be used to compute the friction factor for turbulent flow.

The superficial velocity, vs, is computed from the molar flowrates as

n
1 RT

vs =
Acs P åF
i =1
i (9.52)
392   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Thus, the steady state model for a pseudohomogeneous model of tubular reactor consists of
Equation 9.46, the reaction kinetics are given by Equations 9.41 and 9.42, the pressure drop
by Equation 9.48, and the velocity by Equation 9.52.
The following example demonstrates the steady state simulation of gas-phase catalytic
methanol synthesis in a packed bed reactor.

Example 9.4  Steady State Model for Methanol Synthesis

Problem: Solve the steady state model for methanol synthesis.
Solution: As described above, we adopt a modular approach in developing this code.
The reaction rate is computed using the function surfRxn.m and the initial parameter
computation is also given above. The main driver script for steady state simulation is
given below:

% Steady-State PFR for methanol synthesis

%% Parameters and Setup
param=methanolParam;
opt=odeset('abstol',1e-10,'reltol',1e-10);
Y0=[param.Fin; param.Pin];

%% Solve the ODE

[zSol,YSol]=ode15s(@(z,Y) methanolFun(z,Y,param),...
[0 param.L], Y0, opt);

%% Output and Plot

figure(1)
XSol=YSol(:,1:6);
for i=1:length(XSol)
XSol(i,:)=XSol(i,:)/sum(XSol(i,:));
end
plot(zSol,100*XSol(:,[1:5]));

Note that the constants used in computing the pressure drop using Ergun’s equation
were already computed in the inlet parameter function in the previous section. Since
the flowrates are in the order of 10−4, the default tolerances are not sufficient. Hence,
the tolerance values are specified as ~10−10.
Function file for solving the PFR problem: The next task is to write the function
file for computing dYdz. Here, Y represents the flowrates for all species and the
pressure:

function dYdz=methanolRxtrFun(t,Y,par)
% Function to calculate dY/dx for methanol reactor
% Isothermal reactor with pressure drop
%% Parameters and variables
T=par.Tin; R=par.R;
F=Y(1:6);
 Section Wrap-Up   ◾    393

P=Y(7);
X=F/sum(F);
pPress=P*X;
Mavg=par.MW'*X;
rho=P*Mavg/(R*T);

%% Model
RConvRxn=surfRxn(T,pPress,par);
dF=par.Acs*RConvRxn;
% Pressure Drop
vs=par.rhouIn/rho;
dP=-(par.ergun1+par.ergun2)*vs;
% Final Model
dYdz=[dF;dP];
end

Figure 9.15 shows the steady state profile of various species in the reactor. The reactor
attains equilibrium mole fractions for all the reacting species. This can be verified by
comparing the final steady state values of mole fractions with the ones computed using
the equilibrium conditions. This forms one check on the overall model performance.
On the same lines, another sanity check is given by the flowrate of ­nitrogen,  FN2.
Since it is inert, the molar flowrate of nitrogen at the reactor exit should equal the
molar flowrate at the reactor entrance. The final check is by comparing the results of
Figure 9.15 with that of the original paper. The qualitative match indicates that the
steady state results are valid.
Figure 9.16 shows the effect of temperature and pressure on methanol mole frac-
tion along the length of the reactor. The inlet consists of 25% of CO, 50% H2, 10% CO2,
and the rest nitrogen, which represents one of the input conditions from Graaf and
coworkers (1989). Under both cases, the pressure drop in the reactor is about 100 Pa,
that is, 0.001 bar. The low pressure drop is due to the low velocity in the bed. Hence,
pressure drop may be neglected in the rest of the simulations.

3 CO
Mole (%)

MeOH
2
CO2

1
H2O

0
0 0.05 0.1 0.15
Axial location, z (m)

FIGURE 9.15  Steady state profiles of mole fractions of all species in a methanol synthesis reactor.
394   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

20

25 bar/473 K
15

Methanol mole (%)

50 bar/523 K
10
25 bar/500 K
25 bar/523 K
5

10 bar/523 K
0
0 0.05 0.1 0.15
Axial location, z (m)

FIGURE 9.16  The effect of temperature and pressure on methanol mole fraction.

The methanol synthesis reaction is a slightly exothermic reaction with a decrease in the
number of moles. Thus, lower temperature and higher pressures increase the equilibrium
conversion. The thin solid line in Figure 9.16 represents the base case with 523 K and 50
bar pressure. When the pressure is decreased to 25 bar and 10 bar (solid lines) at the same
temperature, the equilibrium methanol concentration decreases. Due to high enough tem-
perature, complete conversion is obtained within 2–3 cm of the reactor length. On the other
hand, when the temperature is decreased (dashed lines), equilibrium conversion increases.
At 500 K temperature, conversion is higher than the corresponding case with 523 K. When
the temperature is further decreased to 473 K, equilibrium conversion further increases.
However, due to low temperature, the reactor length is not sufficient to ensure that the reac-
tion approaches equilibrium conversion.
With this, the steady state analysis is complete. Next, we focus on the transient reactor model.

9.4.2 Transient Model
The transient model for the pseudohomogeneous reactor is given by

¶ 1 ¶
¶t
Ck +
Acs ¶z
Fk = rcat ån r kj j (9.53)
j

When we solved the steady state model, we related concentration Ck to the flowrate Fk as

Fk æ P ö
Ck = ç ÷ (9.54)
å i
Fi è RT ø

Thus, the steady state model was converted to a molar flowrate basis and solved in the previ-
ous section. However, this strategy gets complicated for a transient model because flowrates
Fi and pressure P are all changing with time. An alternative way is to solve the equations in
concentration terms. To do so, we write

Fk = ( Acs v ) Ck (9.55)
 Section Wrap-Up   ◾    395

where (Acsv) is the volumetric flowrate. This leads us to the familiar equation we encoun-
tered in Chapter 4:

¶ ¶
¶t
Ck + vCk = rcat
¶z ån r kj j (9.56)
j

When a liquid-phase system or a gas-phase system with no volume change was considered,
the velocity was constant and could be taken out of the spatial differential. However, since
this is not the case here, we need to compute vs. From the overall mass conservation

rv = ( rv )in = Gin (9.49)

we can compute

Gin æ RT ö
v= = Gin ç ÷ (9.57)
r è PM ø

In the above expression

M= åX M
i
i i

is the average molecular weight.

We will solve the model using method of lines. The species balance equation (9.56) can
be discretized using the backward difference (first-order upwind) approximation.
The various species include CO2, H2, CO, H2O, CH3OH, and N2 (diluent). These are
specified at each location. Discretizing the spatial domain into n intervals will result in 6n
solution vectors and 6n ODEs. To do so, we define

éCCO2 , p ù
ê ú
êCH2 , p ú
êCCO, p ú
Yp = ê ú
êCH2O, p ú
êCCH OH, p ú
ê 3
ú
êëCN2 , p úû

at each node.
With this knowledge, we are equipped to formulate and solve the methanol synthesis
problem.
396   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 9.5  Transient Model for Methanol Synthesis

Problem: Solve the steady state model for methanol synthesis.
Solution: The function to compute the reaction rate, surfRxn.m, and model
parameters, methanolParam.m, remains the same as before. The function file is
modified for the transient model as given below.
Function file for solving the PFR problem:

function dY=methanolTFun(t,Y,par)
% Transient model for methanol synthesis reactor
%% Variables and Parameters
n=par.n;
h=par.h;
R=par.R;
C=reshape(Y,6,n);
dC=zeros(6,n);

%% Model
P=par.Pin; % Neglect pressure drop
T=par.Tin; % Isothermal
for i=1:n
% Reaction term
X=C(:,i)/sum(C(:,i));
pPress=P*X;
rxnTerm=surfRxn(T,pPress,par);

% Convection term
Mavg=par.MW'*X;
rho=P*Mavg/(R*T);
if (i==1)
uC_In=par.Fin/par.Acs;
u=par.rhouIn/rho;
convTerm=(u*C(:,i)-uC_In)/h;
else
uPrev=u;
u=par.rhouIn/rho;
convTerm=(u*C(:,i)-uPrev*C(:,i-1))/h;
end
dC(:,i)=-convTerm+rxnTerm;
end
dY=reshape(dC,6*n,1);

Notice the first two lines in the model section are T=par.Tin and P=par.Pin,
for the isothermal PFR with negligible pressure drop. In case of pressure drop, the
appropriate balance equation would be used to compute the pressure at each location,
whereas energy balance will be included for a nonisothermal reactor.
 Section Wrap-Up   ◾    397

Since velocity is not constant, the convection term is given by

(u*C(:,i)-uPrev*C(:,i-1))/h

where uPrev is the velocity computed at the previous axial location, i-1.
Driver script for methanol synthesis: The driver script required for methanol synthe-
sis is given below:

% Simulation of catalytic synthesis of methanol

% in a transient isothermal reactor
param=methanolParam;
n=100;
h=param.L/n;
param.n=n;
param.h=h;
%% Initial Conditions and setup
opt=odeset('abstol',1e-10,'reltol',1e-10);
Ctot=param.Pin/(param.R*param.Tin);
Cin=Ctot*param.Xin;
param.Cin=Cin;
C0=Cin; % Initial condition
Y0=repmat(C0,n,1);

%% Solving the ODE

[tSol,YSol]=ode15s(@(t,Y) methanolTFun(t,Y,param), ...
[0 100], Y0, opt);
figure(1)
CSS=reshape(YSol(end,:),6,n);
XSS=zeros(size(CSS));
for i=1:n
XSS(:,i)=CSS(:,i)/sum(CSS(:,i)) * 100;
end
XSS=[param.Xin,XSS];
plot(0:h:param.L, XSS, '--');

Figure 9.17 shows a comparison between steady state and transient simulations for the
same operating conditions. The thin solid lines represent the profiles from the steady
state model. The transient model is simulated for a long enough time (100 s, in this
example) for the system to attain steady state. The results from the transient model at
this end time are plotted as thick dashed lines. The two overlap, indicating that the tran-
sient model is likely to provide a reasonable prediction of methanol synthesis trends.
Figure 9.18 plots the axial profiles of methanol at various times from the start.
Initially, there is no methanol in the reactor (thick dashed line). As time progresses,
the amount of methanol along the reactor length increases and eventually reaches the
steady state value. The steady state profile is represented with thick lines.
398   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Solid: Steady state

4 Dashed: Transient

Mole (%)
2

0
0 0.05 0.1 0.15
Axial location, z (m)

FIGURE 9.17  Comparison between the steady state solution computed using Example 9.4 and the
same solution from the transient model.

3
Methanol mole (%)

1
Increasing time

0
0 0.05 0.1 0.15
Axial location, z (m)

FIGURE 9.18  Axial profiles of methanol mole fraction at various times from the start obtained
using the transient solver.

9.5 TRAJECTORY OF A CRICKET BALL

A ball is hit with an initial velocity and at an angle with the ground. The aim is to find the
horizontal location from the starting point where the ball lands on the ground. This is a
standard numerical problem in several texts. The numerical methods book by Chapra and
Canale uses this example for solving a nonlinear equation for the trajectory of a projectile,
with gravity as the only force acting on the projectile. In some problems, the air drag is
explicitly included in calculations. For example, in the book on numerical methods using
MATLAB, Fausett includes air drag into the formulation to determine where a golf ball
lands. In their numerical problem solving book, Cutlip and Shacham formulate a problem
of computing the trajectory of a baseball in Denver, Colorado, and New York. The problem
described in this section is closest to the latter example.
This problem statement originated as a class project in an undergraduate class on sim-
ulation that I taught at IIT-Madras several years back. The Indian Premier League is a
popular cricket league. After winning a must-win cricket match, the Indian cricket team
 Section Wrap-Up   ◾    399

captain Mahendra Singh Dhoni remarked that it was easier to “hit sixers” in Dharamsala
cricket ground than at Mohali. Dharamsala is at an elevation of approximately 2000 m
above mean sea level. The students modified a homework problem to a project problem
to find out how gravitational acceleration and air drag influence where the ball lands. We
will consider the first part of the problem: to obtain the trajectory of a cricket ball hit with
a certain velocity and at an angle and, hence, to find the location where the ball hits the
ground.

9.5.1 Solving the ODE for Trajectory

The model equations for computing the ball trajectory comprise force balance in x- and
y-directions. At any point, the velocity of the ball has two components:

v = ui + vj

Since the initial speed and angle are given, the two components u0 and v0 are known at
t = 0. Air drag acts against the direction of motion of the ball, and gravity acts downward.
Thus

mu¢ = - k v u
(9.58)
mv ¢ = - g - k v v

form the overall balance equations for the ball. The net air drag is given by κ|v|v, which acts
against the direction of motion of the ball. Here, |v| is the magnitude of the velocity. The two
components of the air drag are, therefore, −κ|v|u and −κ|v|v (the negative sign indicating
the direction is opposite to the corresponding velocity component) in x- and y-directions,
respectively. Thus, the overall ODE-IVP is given by

éx ù é u ù
ê ú ê ú
d êyú ê v ú
= (9.59)
dt ê u ú ê - k v u ú
ê ú ê ú
ëê v úû êë - g - k v v ûú

with the initial conditions

é 0 ù
ê ú
0
Y (0) = ê ú (9.60)
êV0 cos ( q ) ú
ê ú
êë V0 sin ( q ) úû

The following example shows the basic code for solving the ODE-IVP.
400   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Example 9.6  Trajectory of a Cricket Ball

Problem: Given an initial velocity and initial angle, compute the trajectory of a cricket
ball by solving the ODE (9.59).
Solution: This is a rather straightforward problem as posed. The function
ballFun.m is given below:

function dY = ballFun(t,Y,param)
% Function used with ODE solver to calculate trajectory
% of a cricket ball hit with a particular velocity
% Y(1) x (Horizontal displacement)
% Y(2) y (Vertical displacement)
% Y(3) u (Horizontal velocity component)
% Y(4) v (Vertical velocity component)
u=Y(3); % X-velocity
v=Y(4); % Y-velocity
vel=sqrt(u^2+v^2); % Velocity magnitude
% Model Parameters
g=param.g;
c=param.kappa;
%% Model equations
dY =zeros(4,1);
dY(1)=u;
dY(2)=v;
dY(3)=-c*vel*u;
dY(4)=-c*vel*v - g;

The driver code for this problem is straightforward and will be skipped in this section.
The next section provides a modified driver script.
The problem is solved with the initial velocity of 35 m/s and angle of π/4. Figure
9.19 shows the variation in x and y locations with time.

The next aim will be to find the location and time where the ball hits the ground.

9.5.2 Location Where the Ball Hits the Ground

The approximate time and location where the ball hits the ground can be obtained from
Figure 9.19. The ball hits the ground when y = 0. Under these conditions, the time is approx-
imately 4.5 s and the horizontal location where the ball lands is approximately 80 m. Let us
now modify the code above for obtaining these results numerically, by stopping the ODE
solver when the algebraic equation

y ( t ) = 0 (9.61)

is satisfied.
 Section Wrap-Up   ◾    401

80

60
x

Location (m)
40
y
20

0
1 2 3 4

–20 Time (s)

FIGURE 9.19  x and y locations of the ball with time.

An analytical case: To understand how the above equation works, consider the case where
the air drag is neglected. In such a case, the ODE (9.59) can be solved analytically to get

u ( t ) = u0 , v ( t ) = v0 - gt
1 (9.62)
x ( t ) = u0t , y ( t ) = v0t - gt 2
2

Solving Equation 9.61 implies finding the value of t that forms the root of the equation. In
the case of no air drag

2v0 2V0 cos ( q0 )

t landing = = = 5.05 s
g g

In the case of the nonlinear problem, Equation 9.59 along with (9.61) forms a higher-order
differential algebraic equation (DAE). This cannot be converted into an index-1 DAE.
Thankfully, MATLAB provides Events Options in ODE solvers, which allows us to specify
the events. This can be activated using the option
opt=odeset('events',@eventFun);

where eventFun(t,y) is a function that returns three output arguments: (i) event func-
tion of the type (9.61), (ii) a flag to indicate whether the ODE solver should be halted, and
(iii) a flag to indicate the direction of change of the event function. The use of the events
option to obtain the location of ball landing is shown in the example below.

Example 9.6  (Continued) Location of Ball Landing

Problem: M.S. Dhoni hits a cricket ball with an initial velocity of 35 m/s and angle
of 45° with the horizontal. The boundary line is at 75 m from the batsman. Find the
location from the batsman where the ball lands on the ground, and hence determine
whether Dhoni scores a six. (A sixer is scored if the x-location exceeds 75 m.)
402   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Solution: We will use the event function in MATLAB to obtain the location where
the ball lands. The ODE function, ballFun.m, remains the same as in the previous
example. We will first write an event function, as given below:
function [pos,isTerminal,dir]=ballLanding(t,Y)
pos=Y(2); % Check if Y-location is zero
isTerminal=1; % Stop simulation on true
dir=0; % Ignore direction

The first value determines the condition to be checked. This is nothing but the left-
hand side of Equation 9.61. The second line indicates that the simulation should be
stopped when the event condition y(t) = 0 is met.
The overall driver function for solving this problem is given below:

%% Define Parameters and Initial Conditions

param.g=9.81; % gravitational acceleration
param.kappa=0; % air drag coefficient
initialVel=35; % initial speed
initialAngle=pi/4; % initial angle
u0 = initialVel*cos(initialAngle);
v0 = initialVel*sin(initialAngle);

%% Setting up and Solving the problem

X0 = [0; 0; % starting position: origin
u0; v0]; % starting velocity
tSpan = [0 20];
opt=odeset('events',@ballLanding);
[tOut,XOut]=ode45(@(t,X) ballFun(t,X,param),...
tSpan,X0,opt);

%% Displaying the results

figure(1);
plot(tOut,XOut(:,1),'-b',tOut,XOut(:,2),'--r');
xlabel('Time (s)'); ylabel('Location (m)');
figure(2);
plot(XOut(:,1),XOut(:,2),'bo');
xlabel('x (m)'); ylabel('y (m)');
%% Animating results
exitCode = ballAnimation(tOut,XOut);

The result of running the code is similar to that in the earlier part of this problem. The
main difference is that the code stops when the event is reached. The time and location
at which the ball lands can be obtained as

>> disp(tOut(end))
4.4430
>> disp(XOut(end,1))
81.3707
 Section Wrap-Up   ◾    403

25

20

15

y (m)
10

0
0 20 40 60 80
x (m)

FIGURE 9.20  Trajectory of the ball hit in the X–Y plane of the cricket field.

Clearly, since the ball lands beyond 75 m, Dhoni has scored a six. The trajectory of the
ball is plotted in Figure 9.20. The origin is where Dhoni hit the ball. Locations in the
X–Y plane that the ball traverses are shown as circles.

Let us consider a slightly different problem: Find the height of the ball from the ground
when the ball reaches the boundary. In other words, we need to obtain the height y when
the horizontal location is 75 m.
The event function can be written as

x ( t ) - 75 = 0 (9.63)

Thus, we change the function ballLanding.m as below:

function [pos,isTerminal,dir]=ballLanding(t,Y)
pos=Y(1)-75; % Check if X-location is 75
isTerminal=1; % Stop simulation on true
dir=0; % Ignore direction

With this change, the ODE code is executed again. The time required for the ball to reach
the boundary is found to be approximately 4 s. The height of the ball at that time is 8.16 m.
Thus, if there was a 6 ft tall fielder at the boundary, he would not be able to catch the ball
and Dhoni would still score a six!

9.5.3 Animation
Finally, let’s get to the fun stuff: animation. The way we will animate motion of the ball is to
obtain the location of the ball at every 0.1 s. This is already done in Figure 9.20. However,
all the symbols are plotted at the same time. In animation, what we need instead is to plot
the first circle at time 0, then replace that circle with the second circle at time 0.1, replace
that with a third circle at time 0.2, and so on. If we use the plot command at each time,
404   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

the previous plot will get overwritten and the animation will show a flicker. Hence, we are
not going to plot a separate circle; instead, we will only change its X- and Y-coordinates. We
do so using

set(gca, 'xData',XOut(i,1),'yData',XOut(i,2));
pause(0.1);

The last line ensures MATLAB will pause for 0.1 s before changing the location of the ball
for the animation.
There is, however, one more issue. As the location changes, MATLAB changes the limits
of the two axes automatically. To avoid this, we need to fix the X- and Y-limits using
set(gca,'xLim',[0 85], 'yLim',[0 25]);

This will ensure that the two axes will always remain fixed to the range of 0–85 and 0–25 m,
respectively.
Finally, you may notice the animation to still be a bit jerky. To make it smooth, we will
animate it every 0.02 s. The MATLAB code ballAnimation.m that does this is given
below:
function exitCode = ballAnimation(tOut,XOut)
% To animate trajectory of a ball
% Interpolate data every 0.02 s
tAnim = 0:0.02:tOut(end);
Xanim = spline(tOut,XOut(:,1),tAnim);
Yanim = spline(tOut,XOut(:,2),tAnim);

% Plot a blue ball at the origin and

% fix the limits of X- and Y-axes
figure(4);
oHnd=plot(Xanim(1),Yanim(1),'bo');
set(gca,'xLim',[0 85], 'yLim',[0 25]);
xlabel('x (m)','fontsize',18);
ylabel('y (m)','fontsize',18);
set(oHnd,'markerFaceColor','blue');
pause(1); % Pause 1 second before start

for i = 2:length(tAnim)
set(oHnd,'xData',Xanim(i),'yData',Yanim(i));
pause(0.02);
end
exitCode = 1;

The steps explained the following:

We first set up the data for plotting using interpolation, if required.

Next, we plot the ball at the origin and fix the X- and Y-axes limits.
Finally, we animate the ball by changing its X- and Y-locations in a loop.
 Section Wrap-Up   ◾    405

9.6 WRAP-UP
This chapter wraps up Part II of this book by bringing in various tools to analyze and simu-
late complex processes. The first three sections of this chapter presented nonlinear analysis
using several examples. The first tool in nonlinear analysis is used to obtain various steady
state solutions (Sections 9.1.1 and 9.2.1), also known as fixed points. The model can be
linearized, and the linear stability analysis (Section 5.2) around the fixed point is used to
study the local stability behavior of the system. Phase-plane analysis is a useful tool to study
the overall dynamic behavior. Such an analysis is also useful in studying oscillating sys-
tems (Section 9.3), both harmonic oscillations and limit cycle behavior. Indeed, nonlinear
dynamics (which also includes study of chaos, logistical maps, etc.) is a rich field itself; this
chapter barely scratches the surface.
This was followed by the simulation of tubular reactor in Section 9.4. A steady state PFR
is an ODE system, whereas a transient PFR is a hyperbolic PDE. As the velocity changes due
to reaction, careful attention needs to be paid to the overall problem formulation. Finally,
Section 9.5 simulates the trajectory of a projectile (cricket ball, in this case), where the event-
tracking feature of MATLAB ODE solvers was also introduced. This section concluded with
a fun example of animation in MATLAB to visualize the trajectory of the cricket ball.

EXERCISES
Problem 9.1 Perform the bifurcation analysis for a chemostat, as shown in Section 9.1 for
a larger value of saturation constant, K = 1.0. All other parameters are kept
the same as in Section 9.1.
Problem 9.2 Transcritical bifurcation: Perform bifurcation analysis for the following
systems:

æ x ö
x ¢ = (1 - x ) ç a -
è 1 - x ÷ø

x ¢ = x - ax (1 - x )

Problem 9.3 Derive Equation 9.19:

kt UA
f 2 (T ) = ( -DH )
1 + kt
( FC A,in ) + F rc p (Tin - T ) -
1+ b
(T - Tj,in ) = 0

Problem 9.4 (c.f., Strogatz’s book) Perform bifurcation analysis for the following autocata-
lytic series reactions:

A + X  2 X , X + B ® Products
406   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Assume concentrations of A and B are kept constant at a and b, respectively.

Let k1 , k−1, and k2 be the rate constants of the three reactions. Show that the
concentration of X can be given by X′ = c1X − c2X2. What are the conditions
for stability of the various steady states of the system?
Problem 9.5 Repeat the ball animation problem to find the time required to reach the
highest height, after which the ball starts falling.
 III
Modeling of Data

407
 CHAPTER 10

Regression and
Parameter Estimation

10.1 GENERAL SETUP
Several models of various types were discussed in the preceding two parts of this book.
These included differential equations, algebraic equations, expressions for certain proper-
ties, and differential algebraic equations. The aim of these models is to represent a relation-
ship between independent and dependent quantities and/or to predict the behavior of a
system. These models had several parameters, for example, rate constants to express reac-
tion rate, thermal conductivity in heat transfer problem, drag coefficient, etc. The param-
eter values were assumed to be known, which allowed us to set up and solve the problems
of interest.
The aim of this chapter is to focus on the process of obtaining the model parameters that
“best represent” the observed data. This is known by various terms: regression or param-
eter estimation. We will use these terms to mean the same process: Given a finite number
of observations, how do we fit the parameters of a chosen model that best represent the
observed data?
Such a model may be phenomenological. For example, the Arrhenius rate law for tem-
perature dependence on reaction rate

æ E ö
k (T ) = k0 exp ç - ÷ (10.1)
è RT ø

has a basis in statistical mechanics. Some others may represent a convenient form of rep-
resenting correlation observed in the data. For example, dependence of specific heat on
temperature

c p = a + bT + cT 2 + dT 3 (10.2)

409
410   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

is a convenient polynomial form that represents the observed trends for a wide range of
temperatures. Then there are other examples, such as Antoine’s relationship between satu-
ration pressure of a pure liquid and its temperature. Antoine’s equation

B

( )
ln psat = A -
T +C
(10.3)

is a semiempirical relationship, since it is derived from Clausius-Clapeyron relation and

modified to represent a majority of pure species. Irrespective of the theoretical, semiempiri-
cal, or empirical nature of the relationship, regression aims to compute parameters that best
represent the observed data.
The earliest example of regression that we encounter, perhaps in high school or earlier, is
fitting of a straight line. In our undergraduate laboratory, we have often plotted experimen-
tal observations on a graph in an appropriate way and tried to fit a straight line. In all these
cases, we attempted to fit a straight line of the form

y = mx + c

The abscissa x may be considered an “independent variable,” whereas the ordinate y may
be considered a “dependent variable.” The two may either be directly measured variables or
may be derived quantities. For example, you may recall taking a logarithm of reaction rate

æ E öæ 1 ö
ln ( r ) = ln ( k0 ) + ç - ÷ ç ÷ (10.4)
è R ø è T ø

and plotting ln(r) vs. 1/T.

We may also recall that the data did not lie exactly on the straight line. There was some
amount of error in the experimental data. If the error is only in the measurements (called
measurement noise), the data will lie neatly spread around the straight line. However, there
are other sources of errors, including systematic errors, and the fact that the model does not
truly represent the data. The topic of regression is intended to not only determine the model
parameters that best fit the data but also to determine whether the model is adequate or
appropriate to represent the observed data. The latter is often termed as hypothesis testing.

10.1.1 Orientation
A set of observations—either from an experiment, any other measurement, or from a more
complex simulation—are available at certain discrete points. Let us consider that the data is
available at N different points, x represents the independent variable, and y represents the
dependent variable. In the three examples, (10.1) through (10.3), the choice of x and y were
clear. Let the data be represented as

( x1 , y1 ) , ( x2 , y2 ) ,¼, ( xN , yN ) (10.5)

pairs at these N data points.

 Regression and Parameter Estimation   ◾    411

Let us represent the model that we try to fit as

y = f ( x; F ) (10.6)

where ΦT = [a1  a2  ⋯   am] is the m-dimensional vector of model parameters.

Let us represent model predictions as y . Given a value of parameters F,

y i = f ( xi ; F ) (10.7)

represents the model prediction of the ith data point when the corresponding observed
value of the independent variable xi is substituted in the model (10.6). The difference

ei = yi - y i (10.8)

is the model error or residual at the ith data point.

Model fit, regression, or parameter estimation are the terms used to imply the proce-
dure of finding the values of Φ that will minimize, in some way, the errors ei across all the
observed data.
We now review some of the basic statistics that will be useful in this chapter.

10.1.2 Some Statistics
Let us recap some definitions. The arithmetic mean of the data is

å
N
xi
x= i =1
(10.9)
N

Let us represent the numerator as Σx. Then, the mean is written as

Sx
x= (10.9)
N

The sum of square deviation from the mean is represented as Sx, variance is represented as
var(x), and the standard deviation in the data as sx:
N

å(x - x )
2
Sx = i (10.10)
i =1

Sx
var ( x ) =
N -1

å (x - x )
2
Sx i
sx = = i
(10.11)
N -1 N -1
412   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The denominator is var(x) and sx is the degrees of freedom, (N − 1). For example, if there is
a single data point, the variance of that data around its mean does not have any meaning!
Next, we come to an important definition: the sum of squares of the residuals:

å ( y - y )
2
Se = i i (10.12)
i

( )
Since the modeling error ei = yi - y i , the above expression forms a convenient merit func-
tion or objective function for parameter fitting process.
Finally, let us use the example of specific heat data for methane (given in Table 10.3) to
further understand some of these concepts. Since this data is obtained at various tempera-
tures, there is an underlying trend in the data, as seen in Panel (a) of Figure 10.1. The aim of
regression is to find that trend. Let us next consider the case where the specific heat is cal-
culated five times at the temperature of 400 K. The two cases are shown in Figure 10.1, with
the data plotted against the observation index in the abscissa. While there is a clear trend in
Panel (a), the data in Panel (b) is well spread around the value of 40.6 J/mol · K.
The data in Panel (a) was obtained from NIST WebBook of thermochemical data,
whereas that in Panel (b) is “synthetic” data that I generated randomly. The latter was
generated from an underlying normal or Gaussian distribution (also popularly known as
“the bell-shaped” curve of probability distribution) with a mean of μ = 40.6 and a standard
deviation of σ = 1.
The data is given as: c  = [40.00 41.09 41.14 42.31 40.31]T. The underlying mean
and standard deviation (which are often unknown) are μ and σ. We distinguish them from
the sample mean y = 40.97 and the sample standard deviation sy = 0.897. Notice that since
we have a small number of data points, the sample mean and standard deviation is differ-
ent from the inherent statistics behind the data. The data shown here is just one realization
of the stochastic process. After the measurements are taken, this realization is fixed. If we
were to take the measurements again, we will get a different set of values, even though the
underlying process is the same.

45 45

40 40

35 35
1 2 3 4 5 6 7 1 2 3 4 5 6 7
(a) (b)

FIGURE 10.1  Specific heat of methane (a) at various temperatures and (b) at 400 K obtained with
five different experiments.
 Regression and Parameter Estimation   ◾    413

10.1.3 Some Other Considerations in Regression

Unlike the previous chapters in this book, the data for x and y are available; the parameters
F are unknown. The model may either be linear or nonlinear in parameter space. In this
chapter, we are not concerned whether the model is linear or nonlinear in x and y; we are
concerned about linearity in parameters, a1 ,¼, am.
Models may have more than one input, where the model may be written as

y = a1 + a2 x + a3w + a4 u (10.13)

The aim is to find parameters for the above linear model, for which we use multilinear
regression. As we shall show soon, multilinear regression is a straightforward extension of
linear regression in multiple variables.
The model for specific heat

c p = a + bT + cT 2 + dT 3 (10.2)

although nonlinear in T, is linear in parameters a , b , c , d. Since T, T2, and T3 are linearly
independent, this has the same form as Equation 10.13, with x ≡ T , w ≡ T2 , u ≡ T3. The
regression for polynomial data as in Equation 10.2 is called polynomial regression.
Likewise, if we define a1 = ln(k0) and a2 =  − E/R, model (10.4) is linear in parameters a1
and a2. Recall that Equations 10.1 and 10.4 represent the same equation. However, Equation 10.1
is nonlinear in parameter space. Obtaining the values of k0 and E, with the model expressed
in the original form of Equation 10.1, requires nonlinear regression. It may sometimes not
be easy to convert a nonlinear regression into a linear regression. Equation 10.3 provides an
example where a nonlinear regression is recommended.
All these examples and analyses will be covered in the remainder of this chapter. The
problem of fitting a straight line to observed data will be discussed in Sections 10.2.1 and
10.2.2, and statistical properties related to goodness of fit will be discussed in Section 10.2.3.
The linear regression problem will be extended to multiple variables in Section 10.3. Section
10.4 will discuss nonlinear regression, including conversion of a nonlinear regression prob-
lem to linear regression (as we indicated in reaction rate Equation 10.2 being converted to
linearize form (10.4)). Finally, Section 10.5 will present several case studies.

10.2 LINEAR LEAST SQUARES REGRESSION

This section will be dedicated to problems involving regression in single variable. We will
start with fitting a straight line, reinterpret the results in a matrix least squares form, and dis-
cuss some statistics to determine goodness of fit. It is not sufficient to just compute the best-
fit parameters for a model; we would also like to estimate some error bounds around these
parameters, as well as get some information about how well the model fits the observed data.

10.2.1 Fitting a Straight Line

The problem of fitting a straight line of the form

y = a1 + a2 x (10.14)
414   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

is manageable to understand, while still having all the key features of regression and obtain-
ing goodness of fit estimates. It also covers a rather broad spectrum of regression problems.
Given the data at N discrete points, the model predictions are

y i = a1 + a2 xi (10.15)

Since the error is defined as

ei = yi - y i
= yi - ( a1 + a2 xi ) (10.16)

the sum of squared errors is written as

N

Se = åe
i =1
2
i

å ( y - (a + a x ))
2
= i 1 2 i (10.17)
i =1

Least squares solution: The aim of least squares solution is to find the values of a1 and a2 for
which Sε is minimum, that is

( a1 , a2 ) = min
a ,a
Se
1 2
(10.18)

This is said to be a least squares problem because we minimize the sum of squared errors.
For the linear mode, the least squares parameter values can be obtained by differentiating
Equation 10.17 with respect to a1 and a2 and equating them to zero. Differentiating with
respect to a1
N
¶Se ¶
å ¶a ( y - (a + a x ))
2
= i 1 2 i =0 (10.19)
¶a1
i =1
1

yields

å2 ( y - (a + a x )) = 0
i =1
i 1 2 i (10.20)

Thus, we get the first equation in parameters a1 and a2:

N N

a1N + a2 å åy
i =1
xi =
i =1
i (10.21)
 Regression and Parameter Estimation   ◾    415

The other equation may be derived in a similar manner, with

N
¶Se ¶
å ¶a ( y - (a + a x ))
2
= i 1 2 i =0 (10.22)
¶a2
i =1
2

yielding

å - 2x ( y - (a + a x )) = 0
i
i i 1 2 i (10.23)

Thus, we get the second equation in the two unknowns:

N N N

a1 å
i =1
xi + a2 å åx y
i =1
xi2 =
i =1
i i (10.24)

Using the shorthand notation, Equations 10.21 and 10.24 are written as

éN Sx ù é Sy ù
ê úF = ê ú (10.25)
ëS x S xx û ëS xy û

to form two linear equations. The above equation can be solved simultaneously to obtain
least squares estimates of the parameters, a1 and a2.

10.2.2 General Matrix Approach

Before moving to statistical analysis of the estimation error, we will rewrite the above prob-
lem in matrix operations form, in line with the discussion in Chapter 2. It is easy to see that
the error at the ith point is

é a1 ù
ei = yi - éë1 xi ùû ê ú (10.26)
a2 û
ë
F

Let us enumerate the above for all N data points:

e1 = y1 - ëé1 x1 ùû F
e2 = y2 - éë1 x2 ùû F
(10.27)

eN = y N - ëé1 x N ùû F

416   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Writing the above in a matrix form

é e1 ù é y1 ù é1 x1 ù
ê ú ê ú ê ú
ê e2 ú = ê y2 ú - ê1 x2 ú é a1 ù
ê  ú ê  ú ê ê ú (10.28)
 ú ëa2 û
ê ú ê ú ê ú
êëeN úû êë

y N úû êë1 x N úû F
 
E Y X

allows us to define errors in a compact form, E = Y − XΦ. Recall that the model equation

Y = X F (10.29)

is in the familiar form encountered in Chapter 2. In this example, the matrices X and Y
consist of N rows, corresponding to the N data points. Singular value decomposition (SVD)
on X matrix

X = U SV T (10.30)

gives two nonzero singular values. When there are two equations in two unknowns, a
unique solution is found by inverting the matrix X. However, in this case with N rows, since
the matrix X has two nonzero singular values, its left inverse, given by (XTX)−1XT, exists and
will provide a least squares solution.
Let us derive this result using a procedure similar to the one used earlier. The sum of
squared errors is given by

Se = ET E
= (Y - X F ) (Y - X F )
T
(10.31)

Recall that if we have a quadratic function, f(x) = hx2 − 2gx, with h > 0, then the value x = g/h
is minima. Analogously, the vector x that minimizes

argmin x T H x - 2g T x
x

is x = H -1g. This can be easily derived using rules of matrix differentiation.

The least squares solution Φ can be obtained by expanding Equation 10.31

{ (
F = argmin FT X T X F - 2Y T X F
F
) } (10.32)

where the constant term YTY does not affect the value of Φ. By comparison, H ≡ XTX is a
positive definite matrix. Thus, the least squares solution that minimizes the sum of squared
errors, Sε, is

( )
-1
F = XT X XTY (10.33)

 Regression and Parameter Estimation   ◾    417

The following example demonstrates linear regression using Equations 10.25 and 10.33.

Example 10.1  Fitting Specific Heat Data to a Straight Line

Problem: The specific heat data for methane is given in Table 10.3 as a function of
temperature. Fit a straight line to the data at the lower range of temperatures, from
298 to 500 K.
Solution: The following code computes the linear least squares solution for specific
heat.
% Linear regression for specific heat of methane
T=[298; 325; 350; 375; 400; 425; 450; 475; 500];
cp=[35.64; 36.69; 37.85; 39.13; ...
40.63; 41.93; 43.39; 44.87; 46.63];

%% Method-1
N=length(T);
Sx=sum(T); Sy=sum(cp);
Sxx=sum(T.*T); Sxy=sum(T.*cp);
A=[N Sx; Sx Sxx];
b=[Sy; Sxy];
Phi1=inv(A)*b;

%% Method-2: Matrix Method

Y=cp;
X=[ones(N,1), T];
Phi2=inv(X'*X)*X'*Y;
Phi3=X\Y;

Using the above code, the specific heat of methane (in J/mol · K) is obtained as the fol-
lowing linear function of temperature (in Kelvin):

c p = 18.92 + 0.0546T (10.34)

Figure 10.2 shows a comparison between the data and the straight-line model fit
obtained above. One can visually see from this figure that the model does a reasonable
job of predicting the experimental data.
One can also verify that Phi1, Phi2, and Phi3 values are exactly the same.
Furthermore, both A and X'*X give the same value:

9 3598
3598 1476304

The example above was a recap of fitting a straight line to data. This also showed numeri-
cally the equivalence between Equations 10.25 and 10.33. In Problem 10.1, you are asked to
prove this equivalence for general N-dimensional X and Y matrices.
Next, we will calculate some statistics and analyze how well the model fits the data.
418   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

46

Specific heat, cp (J/mol · K)

42

38

34
300 350 400 450 500
Temperature (K)

FIGURE 10.2  Comparison of specific heat data (symbols) and a straight-line model fit (lines).

10.2.3 Goodness of Fit
10.2.3.1 Maximum Likelihood Solution*
Linear least squares described above implicitly assumes that the measurement errors draw
from a normal distribution. The discussion here simply follows the one in the Numerical
Recipes book by Press et al. The reader is referred to that book for more details. Let us
assume that there exist some true models:

y true ( x ; F ) , F = ëéa1
T
 am ùû (10.35)

from which the experimental data yi are derived. The data has a certain measurement error
associated with it. These measurement errors are independent, that is, the measurement error in
the ith data point does not influence the measurement error in the jth data point. Furthermore,
let us assume the measurement errors to draw from a normal (Gaussian) distribution.
Consider the problem of finding the parameters, Φ, that are most likely to produce the
experimental data ((x1, y1), (x2, y2), … , (xN, yN)). If σ is the actual standard deviation of the
measurement errors, then

æ æ yi - y true ( xi ;F ) ö ö
2
1
Pi µ exp ç - ç ÷ ÷ (10.36)
çç 2 ç s ÷ ÷÷
è è ø ø

is the probability at each data point. Since the measurement errors are independent, the
probability of all the data is a product of the individual probabilities. The most likely set of
parameters F are the ones that maximize this probability:
æ ö
1 æ yi - y true ( xi ; F ) ö ÷
N 2

F mle
= max
F Õ ç
a exp - ç
çç 2 ç
è s
÷
÷ ÷÷
ø ø
(10.37)
i =1
è

*  This portion may be skipped without loss of continuity.

 Regression and Parameter Estimation   ◾    419

where “mle” represents that Φmle is the maximum likelihood estimate. Taking a logarithm

ìï 1
N
ï ü
å ( y - y ( x ; F )) ý
2
F mle = max íN ln ( a ) - 2 i true i (10.38)
F 2s
îï i =1 þï

Since N, σ, α are constants, the maximum likelihood estimator is given by

F mle = max {-Se } (10.39)

F

which is exactly the least squares estimation (10.18).

In summary, if the residuals, ei = yi - y i, are independent and draw from a normal
(Gaussian) distribution, the least squares solution is also the maximum likelihood estimate.
It should be mentioned that the assumption of residuals being normally distributed is
rather stringent. Measurements may have gross errors or outliers, systematic errors, or
process drifts, or they may be correlated. Furthermore, measurements may not draw from
normal distribution, for example, due to physical constraints (e.g., mole fractions lie between
0 and 1). Finally, the model may not adequately represent the data. Note that the model
ytrue(x) is often unknown. However, if the residuals are independent and Gaussian, the least
squares solution is indeed the maximum likelihood estimate, even for a nonlinear model.

10.2.3.2 Error and Coefficient of Determination

It is not sufficient to obtain the parameters. We also need to know how well the model pre-
dicts the data. The sum of squared errors, Sε is an important parameter to determine the
modeling errors. However, a specific value of Sε does not itself give an indication of how
good a fit is.
The sample standard deviation in the residual is computed as

Se
se = (10.40)
N -m

Since the data has been used to compute m fitting parameters, the degrees of freedom
remaining are (N − m). For example, a unique line will pass exactly through two data points.
So, if N = 2 and m = 2, the variance is not defined.
The coefficient of determination is a popular way of quantifying how well the model fits
data. It is more popularly known as r2 value. It is commonly calculated as

S y - Se
r2 = (10.41)
Sy

where
Sy represents the variance in the data
Sε represents the variance not captured by the model
420   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

If the latter is low, r2 → 1 and the model is said to have a good fit. The coefficient of determi-
nation is a convenient way to quantify the performance of a model.
Another approach to qualitatively determine the goodness of fit is to plot the original
data and model fit on the same figure. Usually, the model is shown as a curve, whereas the
data are shown as points. Alternatively, a parity plot between the data yi as the abscissa and
the model prediction y i as the ordinate is obtained. If the data lies along the 45° line, we
have a good fit. Finally, the errors ei may be plotted against the data yi. Any trends in the
errors may become clear with such a plot. However, problems with “overfitting” the data (by
using many more parameters than necessary) are difficult to ascertain using this approach.
Likewise, it fails to compare two putative models to select the better one.
Quantitative information about the goodness of fit is provided by determining the vari-
ance in the estimates of the parameters ai . The diagonal elements of M = (XTX)−1 give the
variance of the corresponding parameters. Thus

sai = Mi ,i se (10.42)

However, since the actual value of σε is not available, it needs to be computed from the data.
Thus, the standard deviation can only be estimated from the data.
If the actual standard deviation σε is known, the standard results for normal distribution
may be used. For example, the range of parameter values with 95% confidence interval is
given by (ai ± 2σai). However, since we have a limited amount of data, Student’s t-distribution

dciai = Mi ,i set N -m (10.43)

may be used to calculate the confidence interval for the parameters. Thus, the 95% confi-
dence interval for the parameters is

ai ± dciai (10.44)

The following example demonstrates these calculations.

Example 10.2  Calculating Statistics for Specific Heat Problem

Problem: Compute the various statistical information for Example 10.1 to verify the
fitted linear model.
Solution: The MATLAB® code of Example 10.1 can be expanded to calculate some
statistics.
Error Variance: Sum of squared errors and the estimate of error variance are
­calculated as

err=cp-cpHat;
sse=err'*err;
var_e=sse/(N-2);
stdErr=sqrt(var_e);
 Regression and Parameter Estimation   ◾    421

From the above

Se = 0.5382, var ( e ) = 0.0769, se = 0.2773

Coefficient of determination (“R-squared”): From the variance in the cp data, the term
Sy is calculated as

S y = ( N - 1) var ( c p ) = 113.555

The two can be combined to give the coefficient of determination (R-squared):

Se
r2 = 1- = 0.9953
Sy

Visualizing the model fit: The term r2 indicates that 99.5% of the variance in the original
data can be explained by the linear model. This can be visually seen from Figure 10.2.
Parity plot and error plots are two other ways of visualizing how well the model repre-
sents the data (Figure 10.3). The top panel is the parity plot of cp (data) vs. c p (model).
The closeness of the data points to the 45° line indicates a good model fit. Another
way of visualizing the same data is to plot the residuals (errors), ei = c p,i - c p,i as the
ordinate vs. cp , i as the abscissa. The errors are spread around the X-axis.
Although the errors are small, they form a convex curve, which may indicate the
existence of a higher-order polynomial term.
Confidence interval on least squares parameter values, Φ: The final task is to obtain confi-
dence intervals on the least squares parameters Φ. This will contain two parts: Estimate the

45
cp,model

40

35
35 40 45
cp

0.5
Error

0
40 45

cp
–0.5

FIGURE 10.3  Parity plot and error ei vs. cp , i for analyzing model fit.
422   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

standard deviation (σai) of the parameters and use it to compute the confidence interval. We
will use Equation 10.42 to compute σai, whereas Student’s two-sided t-­distribution will use
σai to provide the 95% confidence intervals on Φ.
The diagonal elements of (XTX)−1 are

>> sqrt(diag(inv(X'*X)))
ans =
2.0803
0.0051

The two elements are indicators of the standard deviations, σai, of the two parameters,
as given by Equation 10.42. However, in the absence of information about the mea-
surement errors, we replace the standard deviation of measurement error, σyi, with the
value sε computed from the data. Thus, the estimated value

sest
ai ~ M ii se

If we had a very large number of data points, sε → σε (i.e., sε approaches the true stan-
dard deviation of measurement noise sequence). Under this assumption that sε is the
true value, the 95% confidence interval is given by “mean ±2 × standard deviation.”
However, since we have a limited amount of data, the Student’s t-distribution is
appropriate. The multiplier for 95% confidence interval with a degree of freedom
(N − m) = 7 is 2.365. The t-distribution tables are easily available. For example, please
see Wikipedia link https://en.wikipedia.org/wiki/Student’s_t-distribution for this
information. If you have the Statistics toolbox in MATLAB, the value tN − m for 95%
confidence interval can be calculated as*

>> tVal=tinv(0.975,7);

Once the tVal is obtained, the confidence intervals can be computed using (10.43):

>> stdPhi=sqrt(diag(inv(X'*X)))*stdErr;
>> confValue=stdPhi*tVal;
>> confInterval=[Phi-confValue, Phi+confValue]
confInterval =
17.5573 20.2852
0.0512 0.0580

Thus, based on the above information, the 95% confidence interval for the two param-
eters is 17.56 £ daci1 £ 20.29 and 0.0512 £ daci2 £ 0.058.

*  The above form is because MATLAB uses one-sided t-distribution. Please see the table in the above link for more informa-
tion. Thus, tinv(p,N-m) will compute the probability.
 Regression and Parameter Estimation   ◾    423

Since the variance in both the parameters is rather small, the confidence interval computed
above is narrow. This indicates a good model fit to the data.

10.3 REGRESSION IN MULTIPLE VARIABLES

Let us now focus on regression in multiple variables.

10.3.1 General Multilinear Regression

Recall that we used the following matrix form:
é e1 ù é y1 ù é1 x1 ù
ê ú ê ú ê ú
ê e2 ú = ê y2 ú - ê1 x2 ú é a1 ù
ê  ú ê  ú ê ê ú (10.28)
 ú ëa2 û
ê ú ê ú ê ú
êëeN úû êë

y N úû êë1 x N úû F
 
E Y X
for linear regression in two variables. The sum of squared errors was obtained as

Se = ET E (10.31)

In the derivation of least squares solution, we made no assumption about the number of
parameters, m. The derivation is more general and is applicable for a larger dimensional Φ
as well. In general, if Φ is an m × 1 vector, then X will be a N × m matrix. The objective func-
tion can be expanded to give the following expression for the least squares solution for Φ:

{ (
F = argmin FT X T X F - 2Y T X F
F
) } (10.32)

Thus, the expression for least squares solution

( )
-1
F = XT X XTY (10.33)

which minimizes the sum of squared errors, is the same as before.

This result can be expanded to linear regression in multiple linearly independent input
variables. Specifically, we are interested in parameter estimation for a linear model:

y = a1 + a2 x + a3w +  + amu (10.45)

with m parameters. The N data points are in the form (xi, wi,  … , ui; yi). The prediction using
the above linear model is

é a1 ù
ê ú
ê a2 ú
yi = éë1 xi wi  ui ùû ê a3 ú (10.46)
ê ú
ê ú
êam ú
ë û
424   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Following the same procedure as above, the model predictions for all the data points can be
obtained, and the error equation written as
é e1 ù é y1 ù é1 x1  u1 ù é a1 ù
ê ú ê ú ê úê ú
ê e2 ú = ê y2 ú - ê1 x2  u2 ú ê a2 ú
ê  ú ê  ú ê    úê  ú (10.47)
ê ú ê ú ê úê ú
ëeN úû êë
ê y N úû êë1 x N  uN úû êëam úû
 
E Y X F
With this definition, the same solution

( )
-1
F = XT X XTY (10.33)

gives the linear least squares solution for an m-dimensional parameter vector Φ.

10.3.2 Polynomial Regression
Consider the example of fitting the specific heat to a wider range of temperatures.
A straight-line fit does not work.
Polynomial of the form

c p = a1 + a2T + a3T 2 +  + amT m-1 (10.48)

is often fitted to the cp vs. T data.

This is still linear regression, because the expression (10.48) is linear in the unknown
parameters that are to be estimated.
Above equation could be written in the familiar form:
é a1 ù
ê ú
a2
c p = éë1 T  T m-1 ùû ê ú (10.49)
ê ú
ê ú
êëam úû

F
With the above definition

( )
-1
F = XT X XTY
é1 T1 T12  T1m-1 ù éc p1 ù
ê ú ê ú (10.50)
ê1 T2 T22  m -1
T2 ú c p2
where X = ê ú , Y =ê ú
     ê ú
ê ú ê ú
êë1 TN TN2  TN úû
m -1
êëc pN úû

The next example aims to fit a higher-order polynomial to the data ranging from low to high
temperature in steps of ~100 K.
 Regression and Parameter Estimation   ◾    425

Example 10.3  Specific Heat of Methane for Full Range of Temperature

Problem: Fit a polynomial of the form (10.48) to the specific heat data in Table 10.3 for
the full range of temperatures from 298 to 1300 K in steps of ~100 K.
Solution: We will use Equation 10.50 to compute the parameters, as shown in the
code below:

% Linear regression for specific heat of methane

%% Data
T=[298; 400; 500; 600; 700; 800; ...
900; 1000; 1100; 1200; 1273; 1300];
cp=[35.64; 40.63; 46.63; ...
52.74; 58.60; 64.08; 69.14; ...
73.75; 77.92; 81.68; 84.1; 85.07];
N=length(T);

%% Matrix Method
Y=cp;
X=[ones(N,1), T, T.^2];
m=size(X,2);
M=inv(X'*X);
Phi=M*X'*Y;

%% Plotting and comparing

cpHat=Phi (1)+Phi(2)*T+Phi(3)*T.^2;
err=cp-cpHat;
plot(T,cp,'o'); hold on;
plot(T,cpHat);
xlabel('Temperature (K)'); ylabel('c_p (J/mol.K)');

plot(cp,err,'o');
xlabel('c_p (J/mol.K)'); ylabel('error');

plot(cp,cpHat,'o'); % Parity Plot

plot([0 100],[0 100]); % 45-deg line

%% Error analysis
sse=err'*err;
Yvar=Y-mean(Y);
sst=Yvar'*Yvar;
Rsquare=1-sse/sst;

% Parameter std.dev. and confidence interval

stdPhi=sqrt(diag(M))*stdErr;
tVal=tinv(0.975,N-m);
ciRange= stdPhi*tVal;
CI=[Phi+ciRange, Phi-ciRange];
426   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

80

65

50

35

Specific heat, cp (J/mol · K)

80

65

50

35

80

65

50

35
300 700 1100
Temperature (K)

FIGURE 10.4  Polynomial fit to cp vs. T data for first-, second-, and third-order polynomials.

Figure 10.4 shows the fit for polynomials of first-, second-, and third-order to the cp
data. The corresponding R-squared values are 0.9923, 0.9992, 0.9998, respectively. All
the three R-squared values are excellent.
Figure 10.5 shows the parity and error plots for the three polynomial fits. Although
the straight line fit gives an excellent R-squared value, a higher-order polynomial gives
a better qualitative fit with regard to the spread of the errors across the X-axis.
Based on “eyeballing the errors” from the graphs, a second-order polynomial seems
a reasonable fit for the data.

The above procedure of eyeballing the errors is not very reliable. We need some quantitative
measure to determine the goodness of fit. If the variance of measurement error is known,
the Chi-squared value

å ( y - y )
N 2
N 2
æ yi - y ö
å
i i
c2 = ç i
÷ = i =1
(10.51)
ç si ÷ s2
i =1 è ø
provides a good estimate of goodness of fit. However, in the example above, we have no idea
of the estimate of measurement error. In such a case, the standard deviation of the param-
eters becomes a useful criterion for analyzing the model fit. For the straight line
é 22.27 ù é 1.254 ù
F=ê ú , s F = ê ú
ë0.0499 û ë0.0014 û
 Regression and Parameter Estimation   ◾    427

80
0.2

65
0

50
–0.2

35
1
80
cp,estimated

65
0

50

35 –1

80
2

65
0
40 60 80
50
–2
35
35 50 65 80
(a) cp,data (b)

FIGURE 10.5  Parity plots (a) and error plots (b) for first-, second-, and third-order polynomials for
fitting cp vs. T data.

The parameters for the second-order curve are

é 13.70 ù é 1.036 ù
ê ú ê ú
F = ê 0.0749 ú , s F = ê 0.0028 ú
ê -1.52 ´ 10-5 ú ê1.68 ´ 10-6 ú
ë û ë û

In both these cases, the standard deviation of parameters is an order of magnitude lower
than the parameter values. However, when a third-order polynomial is considered

é 20.004 ù é 1.436 ù
ê ú ê ú
ê 0.0452 ú ê 0.0064 ú
F=ê , s F = ê
2.542 ´ 10-5 ú 8.57 ´ 10-6 ú
ê ú ê ú
êë -1.680 ´ 10-8 úû êë3.52 ´ 10-9 úû
428   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The variance in third-order polynomial is about one-third to one-fourth of the parameter

value for the parameter a3. Consequently, we could either choose second-order (preferred)
or third-order polynomial fit. Any higher-order would probably lead to overfitting the data.
When the code in Example 10.3 is modified for a third-order polynomial (with four
parameters), the matrix X becomes ill-conditioned. MATLAB gives the following warning:

Warning: Matrix is close to singular or badly scaled. Results may

be inaccurate. RCOND = 2.492404e-21.

Methods to handle this are discussed next.

10.3.3 Singularity and SVD

The equations of the form Equation 10.50 are known as normal equations.
A practical difficulty in solving the linear least squares problem is that as the number
of parameters increase, a larger amount of data is needed, and the matrix X becomes ill-
conditioned. Inverting an ill-conditioned matrix must be avoided, because such an opera-
tion is prone to large round-off errors and small measurement errors in the data manifest
as large errors in computation of the parameter Φ. SVD, discussed in Chapter 2, provides a
way around this. The SVD on matrix X can be written as

X = U SV T (10.52)

where . We have used to represent singular values

because σ has already been used to represent standard deviation in this chapter. The matrix
X T X = V S T SV T
(10.53)
( X X ) = V (S S ) V
-1 -1
T T T

Since S is an N × m matrix, ( S S ) is an m × m matrix and
T

Thus, the least squares parameter estimates may be written as

( ) ( S )U Y
-1
F = V ST S T T
(10.54)

( ) ( S ) is given by
-1
The term S T S T

 Regression and Parameter Estimation   ◾    429

Thus, according to Press et al., the least squares parameter estimate is given by

(10.55)

where vi and ui are the ith column vectors of V and U, respectively. Furthermore, Press et al.
suggest that if certain singular values are too small, they may be dropped. Let us say that
only first r singular values of X are considered to be important; then

(10.56)

gives the desired estimate.

10.4 NONLINEAR ESTIMATION
10.4.1 Functional Regression by Linearization
A classic example is that of temperature-dependent Arrhenius rate law:

æ E ö n
r = k0 exp ç - ÷C (10.57)
è RT ø

Taking logarithm on both sides

æ E öæ 1 ö
ln ( r ) = ln ( k0 ) + ç - ÷ ç ÷ + n ln ( C ) (10.58)
è R øè T ø

Defining y = ln(r), x = 1/T and w = ln(C), we get

y = a1 + a2 x + a3w (10.59)

with k0 = exp(a1) ,   E =  − Ra2 ,   n = a3.

The above strategy is useful for both exponential models

y = ae bx (10.60)

as well as power-law models

y = ax b (10.61)

Another classic example is that of Michaelis-Menten kinetics for enzyme-catalyzed reac-

tions. The reaction rate is given by

VCS
r= (10.62)
K m + CS
430   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

This expression is nonlinear in parameters, as written. The so-called Lineweaver-Burke

plot is a “double reciprocal” plot, where the plot of y = 1/r vs. x = 1/CS gives a straight line.
Inverting the above equation yields

1 Km 1 1
= +
r V CS V (10.63)
a1 a2

Since this equation is written in a slightly different form

y = a1 x + a2

the matrix X also must reflect this appropriately. The parameters can be obtained by linear
least squares regression:

( )
-1
F = XT X XTY
é 1/CS1 1ù é 1/r1 ù
ê ú ê ú (10.64)
1/CS 2 1ú 1/r2 ú
where X = ê , Y= ê
ê  ú ê  ú
ê ú ê ú
êë1/CSN 1úû êë1/rN ûú

Monod kinetics in the presence of substrate inhibition is given by

m max CS
r= (10.65)
K + CS + aCS2

Taking the reciprocal yields us

1 K æ 1 ö 1 a
= max ç ÷ + max + max CS (10.66)
r m è CS ø m m

which is of the form required for linear regression.

Example 10.4  Linear Regression for Monod Kinetics

Problem: The data for the rate of microbial reaction (r) was obtained at different values
of substrate concentration and at a constant biomass concentration. For this data shown
in Table 10.1, use linear regression and hence compute the parameters K and μmax.
Solution: We can invert the above equation to obtain

1 K æ 1 ö 1
= max ç ÷ + max
r m è CS ø m
 Regression and Parameter Estimation   ◾    431

TABLE 10.1  Reaction Rate vs. Substrate Concentration Data for Monod Kinetics
[S] 0.24 0.32 0.70 1.37 1.58 2.04 2.26 2.28 2.39 2.41
r 0.3839 0.3935 0.911 1.4975 1.5735 1.849 1.9355 1.893 1.970 1.924

which is of the same form as Equation 10.63. Thereafter, the procedure is as described
in Equation 10.64. Specifically, we define y = 1/r and x = 1/Cs and perform the regression.
Once the least squares values are obtained, the original parameters are calculated as

1
m max = , K = m max a1
a2

The values of parameters and their expected variance are obtained in a manner similar
to Example 10.1 as

é0.6210 ù é0.0376 ù
F=ê ú , sF = ê ú
ë0.2530 û ë0.0662 û

The coefficient of determination, R-squared, equals 0.9716.

The original parameter values computed are

m max = 3.95, K = 2.45

Caution!
One must, however, exercise caution in using a nonlinear model, either directly or linearized.
For example, consider the model

y = a × exp ( bx + c ) (10.67)

The parameters a and c cannot be obtained independently. This is because the above equa-
tion may be written as

y = ae c
 ×e
bx
(10.68)
a1

The parameters a1 and b can be obtained using linear or nonlinear regression. However, the
parameters a and c are not independently obtainable from x vs. y data. A practical example
of this will be discussed in Section 10.5.3.
Another example: Antoine’s equation

B

( )
log P sat = A +
T +C
(10.69)
432   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

Multiplying by (T + C) and rearranging, we get

( )
T log P sat = AT + ( AC + B ) - C log P sat( ) (10.70)

There is nothing wrong with the above formulation, and the resulting X matrix is also
nonsingular. However, an important assumption made in our analysis of parameter
estimation was that of uncorrelated and independent Gaussian noise sequence. In the
above equation, y = T log(P sat) does not satisfy that condition of Gaussian noise; more
importantly, the term w = log(P sat) and y are now correlated. Thus, one should avoid a
formulation where any experimentally measured quantity appears in both definition of
dependent variable y and independent variable(s) x/w.

10.4.2 MATLAB® Solver: Linear Regression

MATLAB has several solvers for linear and nonlinear regression. However, most solvers
require a toolbox to be installed. The Statistics and Machine Learning Toolbox in MATLAB
gives a broad spectrum of tools for data analysis, regression, and hypothesis testing. The
command tinv used in Example 10.2 is a part of the Statistics toolbox.
The linear regression and related statistics provided in Example 10.2 can be handily
calculated using the Statistics toolbox command regress. The specific syntax for using
regress is

[Phi,confInterval,err,~,STATS]=regress(Y,X);
Rsquare=STATS(1);
stdErr=sqrt(STATS(4));

The above command can replace the calculations in Example 10.2. The various outputs are
explained below:

Phi Estimated parameter vector, Φ = [a1  ⋯  am]T

confInterval Confidence interval for each parameter, Equation 10.44
err Model error (residual) at each data point, ei = yi - y i
Rsquare Coefficient of determination (or R-squared value), Equation 10.41
stdErr Standard deviation of residuals, Equation 10.40

The advantage of using regress is that it can handle ill-conditioned X matrix better
than the direct matrix method of Example 10.3. For example, the matrix X in Example 10.3
for a third-order polynomial fit was ill-conditioned. The round-off error problem is avoided
by regress since it uses QR factorization for solving the problem. The other SVD-based
approach was presented in Section 10.3.3.
 Regression and Parameter Estimation   ◾    433

PERSONAL EXPERIENCE: DON’T TAKE SHORTCUTS!

It is often the tendency of beginners to directly use a tool such as regress and skip the
harder steps of stepwise solving a problem. This is especially true when there is any mention
of statistics in an engineering course. I have tried to keep statistics in this chapter to a mini-
mum. However, model fitting is not an easy task. Getting the parameters Φ is easy; figuring
out whether the model obtained is a good model is not easy.
Example 10.2 is not intended to be a complete word in linear regression and analysis. We
barely scratched the surface! However, this chapter is intended to equip the reader to get
started with reading advanced material on regression and model fitting.

The Optimization Toolbox provides another set of tools for linear and nonlinear regres-
sion. These are optimization-based solvers. The solver useful for linear regression
is lsqlin. If the parameter estimation problem is unconstrained, then the method
described in Example 10.3 or Example 10.4 gives good results. However, if there are physi-
cal constraints on the parameter values, lsqlin provides a good option, since it solves
constrained optimization of the form*

1
min XF - Y 2
F 2 (10.71)
F min £ F £ F max

The syntax is as follows:

[Phi,sse,err]=lsqlin(C,d,[],[],[],[],PhiMin,PhiMax);

Phi Estimated parameter vector, Φ = [a1  ⋯  am]T

sse Sum of squared errors, Sε
err Model error (residual) at each data point, ei = yi - y i

Example 10.5  MATLAB® Solvers

The reader may verify the results of using regress and lsqlin and compare them
with those from Examples 10.1 and 10.2.
Using regress:

[Phi1,confInterval1,err1,~,STATS]=regress(Y,X);
Rsquare1=STATS(1);
stdErr1=sqrt(STATS(4));

*  In addition to bounds on Φ, lsqlin also handles linear inequality and equality constraints. I favor this approach to keep
things simple and pertinent. Advanced readers may refer to MATLAB help or documentation of Optimization toolbox
for more information.
434   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The reader can verify that the values of Phi1, confInterval1, err1, and Rsquare1
obtained here are the same as those obtained in Examples 10.1 and 10.2.
Using lsqlin:

[Phi2,sse2,err2]=lsqlin(C,d,[],[],[],[],PhiMin,PhiMax);

The readers can verify that Phi2 and sse2 are same as those in previous exam-
ples, and the residual error, err2, is just negative of that in previous examples (since
­lsqlin computes (XΦ − Y)).

10.4.3 Nonlinear Regression Using Optimization Toolbox

The task of obtaining a model that fits the given data is an involved one. First, we choose
candidate models based on domain information that could represent the underlying physics
of the system or process that generated the data. The next task is to estimate the parameters,
including some statistical information regarding the same. The final task is to use goodness
of fit measured to determine how well the model represents the data. This task gets quite
complex if we do not have a clear idea of what underlying physics dictated the observa-
tions, as it often happens in real-world examples. We use hypothesis testing to determine
whether there is statistical evidence that the observed data is represented by the model and
its parameters. This is a cyclic process.
Throughout this chapter, we took examples where the first part was known. We know
with a reasonable confidence that a polynomial can capture temperature effects on spe-
cific heat data, that the Michaelis-Menten or Monod kinetics are reasonable for simple
enzymatic or microbial reactions, that Antoine’s equation represents pure component VLE
(vapor-liquid equilibrium), and so on. Later, in Sections 10.5.3 and 10.5.4, we will visit
an example where the data generated from the same system is used to fit the Langmuir-
Hinshelwood model and power-law kinetics, respectively. Nonetheless, the first part of
choosing the model structure that represents data reasonably was assumed to be known in
this chapter. We gave a brief glimpse of the third aspect: to use goodness of fit measures to
determine how well the model represents the data. This chapter, by no means, is a definitive
introductory text on this rather complex issue. The primary focus of this chapter, however,
was on tools to obtain the model parameters.
While we focused a fair deal on error bounds and confidence intervals for linear models,
this section on nonlinear parameter estimation will focus only on the process of obtaining
least squares fit for nonlinear models.
The optimization-based solvers (from Optimization toolbox in MATLAB) include
lsqnonlin and lsqcurvefit. These solve a nonlinear least squares problem. A generic
optimization solver, fmincon, is also available to use from the toolbox. The three methods
use similar sets of optimization algorithms but go about the task of finding the least squares
parameter fit in a slightly different manner.
Recall that we are interested in finding the parameters, Φ, for a general nonlinear model

y = f ( x ; F ) (10.6)
 Regression and Parameter Estimation   ◾    435

where x and y are measured at N different data points. The aim of the least squares fitting is
to find the parameters that minimize the least squares objective function:

ì N 2ü
argmin ï
F í å( yi - f ( xi ; F ) ï
ý ) (10.72)
ïi =1  ï
î Se þ

Recall that we define our model prediction for a nonlinear model as

y i = f ( xi ; F ) (10.73)

The three MATLAB solvers, lsqnonlin, lsqcurvefit, and fmincon require differ-
ent functions to be defined. The first solver, lsqnonlin, requires us to supply the residual
error as a vector:

é e1 ù é y1 - f ( x1 ; F ) ù
ê ú ê ú
e2 ê y2 - f ( x2 ; F ) ú
E=ê ú=ê ú (10.74)
ê ú 
ê ú ê ú
êëeN úû ëê y N - f ( x N ; F ) úû

with Φ being the adjustable parameter that lsqnonlin needs to determine. The syntax
for this code is

Phi = lsqnonlin(@(X) fittingFun(X), Phi0);

where Phi0 is the initial guess. The function, fittingFun.m, takes in the parameter
( )
vector as input argument and computes the residuals ei = yi - y i . The N × 1 vector of
residual errors must be returned by the function. Since fittinFun will also require the
data to calculate the residuals, the more appropriate syntax aligned with our way of using
MATLAB is

Phi=lsqnonlin(@(X) fittingFun(X,xData,yData), Phi0);

The second solver, lsqcurvefit, requires us to provide yi and y i, with the latter being
calculated in a function that is supplied to the solver. In other words, we will write a func-
tion modelFun.m that will calculate y i = f ( xi ; F ) and return a vector

é f ( x1 ; F ) ù
ê ú
=
Y
ê f ( x 2 ; F ) ú
ê  ú
ê ú
ê f ( x N ; F )ú
ë û
436   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

The syntax for using lsqcurvefit is

Phi=lsqcurvefit(@(X,xData) modelFun(X,xData),Phi0,xData,yData);

Personally, I find not much to choose between the two solvers. Since lsqnonlin has a
more general structure, I prefer it over lsqcurvefit.
The final option is to use any generic optimization solver to solve the least squares prob-
lem. If a solver, such as fmincon or fminunc is used, the objective function should pro-
vide the least squares objective, that is, Sε from Equation 10.72. The syntax for using them is

Phi=fmincon(@(X) estimObj(X,xData,yData), Phi0);

and the function estimObj.m should return the sum of squared errors.
The next example demonstrates the three methods for solving nonlinear regression
problem.

Example 10.6  Solve Example 10.4 Using Nonlinear Regression

Problem: To solve Example 10.4 using nonlinear regression.
Solution: The nonlinear model for Monod kinetics is

m max CS
r=
K s + CS

lsqcurvefit: An external function modelFun.m is written to compute r(Csi)

 . The function is given as
and return the result as a vector Y

function Rate=modelFun(Phi,CsData)
mu=Phi(1); K=Phi(2);
Rate=mu*CsData./(K+CsData);

lsqnonlin: An external function fittingFun.m is written to compute

ei = ( ri - r i ) and return the result as a vector E. The function is given as

function err=fittingFun(Phi,CsData,rData)
mu=Phi(1); K=Phi(2);
Rate=mu*CsData./(K+CsData);
err=rData-Rate;

fmincon / fminunc: An external function estimObj.m is written to compute

the scalar objective function, which is the sum of squared errors:

function sse=estimObj(Phi,CsData,rData)
mu=Phi(1); K=Phi(2);
Rate=mu*CsData./(K+CsData);
err=rData-Rate;
sse=err'*err;
 Regression and Parameter Estimation   ◾    437

Now that these functions are written, the following driver script is used to compute
the estimates Φ using these three methods:

% Nonlinear regression for Monod Kinetics

%% Data
CsData=[0.24; 0.32; 0.70; 1.37; 1.58; ...
2.04; 2.26; 2.28; 2.39; 2.41];
rData=[0.3839; 0.3935; 0.911; 1.4975; 1.5735; ...
1.849; 1.9355; 1.893; 1.970; 1.924];
N=length(rData);

%% Nonlinear curve fit

Phi0=[1;1];
Phi1=lsqcurvefit(@(X,xData) modelFun(X,xData),...
Phi0,CsData,rData);
% Verify the fit
mu=Phi1(1); K=Phi1(2);
rHat=mu*CsData./(K+CsData);
plot(CsData,rData,'o', CsData,rHat,'-');
xlabel('Concentration, C_s'); ylabel('Rate');

%% Nonlinear least squares

Phi2=lsqnonlin(@(X) fittingFun(X,CsData,rData), Phi0);

%% Generic Minimization
Phi3=fminunc(@(X) estimObj(X,CsData,rData), Phi0);

T
The parameters estimated using all these three methods are F = éë3.80 2.23ùû .
Compare these with the parameter values found in Example 10.4 using linear
regression:

μmax = 3.95 ,   K = 2.45

Figure 10.6 compares the model predictions from nonlinear regression (top) and linear
regression (bottom) for this example. The coefficient of determination, R-square, was
0.996 for nonlinear regression. Thus, both the models provide reasonable performance.

10.5 CASE STUDIES AND EXAMPLES

A few examples are discussed in this section to highlight the procedure of parameter
­estimation followed in this chapter.

10.5.1 Specific Heat: Revisited

The example of fitting the specific heat of methane as a function of temperature was used
to demonstrate various concepts in this chapter. First, a straight line was fitted to low-
temperature specific heat data (Example 10.1) in the temperature range of 298–500 K, and
438   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

2
Isqnonlin

Rate
1

0
(a)

2
Linear regression
Rate

0
0 1 2
(b) Concentration, Cs

FIGURE 10.6  Model fit (lines) for Monod kinetics data (symbols). (a) Shows results for lsqnonlin
and (b) for linear regression from Example 10.4.

goodness of fit based on R-squared values and 95% confidence intervals was calculated
(Example 10.2). In Example 10.3, polynomials of various orders were fitted to the specific
heat data for the full range of temperature from 298 to 1300 K. A quadratic or cubic poly-
nomial was found to give a good fit to the data. Interested readers will find it useful to
review these three examples to understand linear regression and goodness of fit estimates.
Finally, Example 10.5 showed that the same results are obtained from in-built MATLAB
functions from statistics and optimization toolboxes.

10.5.2 Antoine’s Equation for Vapor Pressure

Antoine’s equation

B

( )
ln psat = A -
T +C
(10.3)

is a semiempirical correlation between pure component vapor pressure and temperature. In

the above equation, psat is in bars and temperature is in °C. The pure component vapor pressure
data for benzene and ethylbenzene is given in Section 10.6.2 (see Table 10.4).
 Regression and Parameter Estimation   ◾    439

10.5.2.1 Linear Regression for Benzene

In case of Benzene, we will assume that the constant C is known and equal to C = 250. With
this, the problem becomes a linear regression problem between y = ln(psat) and x = 1/(T + C).
This can be easily solved with the tools from Section 10.2.

Example 10.7  Fitting Antoine’s Equation Coefficients: Benzene

Problem: Given C = 250, use the vapor pressure data for benzene to estimate the values
of parameters A and B for Antoine’s equation.
Solution: By now, the linear regression problem should be familiar to the readers.
The following is the code for solving this problem:

%% Observed data
T=[50:10:140];
pSatB=[0.3751, 0.5027, 0.7112, 0.9883, 1.2529,...
1.8758, 2.3648, 2.9474, 3.9049, 4.5455];
%% Obtain Antoine's coefficients
C=250; % Coefficient C is given
Y=log(pSatB');
X=[ones(10,1), -1./(T'+C)];
PHI=inv(X'*X)*X'*Y;
A=PHI(1);
B=PHI(2);
pSatModel=exp(A-B./(T+C));
%% Plot results
plot(T,pSatB,'bo',T,pSatModel,'-r');
xlabel('Temperature (^oC)'); ylabel('p^{sat} (bar)');
figure(2);
plot(T,(pSatB-pSatModel),'bo');
xlabel('Temperature (^oC)'); ylabel('Residual, e_i');

The values of the parameters are A = 10.12 and B = 3343.0. The coefficient of deter-
mination is r2 = 0.998. Figure 10.7 shows the comparison between the model fit and
observed data (top panel) as well as how the model errors are spread.

Let us also look at 95% confidence intervals for the two parameters, which can be computed
as discussed in Section 10.2.3 to yield A = 10.12 ± 0.358 and B = 3343 ± 122.
Note how narrow the 95% confidence intervals are for the parameters A and B. Very nar-
row confidence intervals means that the model is very likely to capture the actual variance
underlying the observed data. This could either be due to overfitting, or if the measurement
errors are low and all the measurements nicely line up as we expect from the model. If these
values sound too good to be true, they really are! The vapor pressure data in Table 10.4 is
not actual observed data; it is synthetic data that I generated using the same model.
Thus, the statistical analysis of model parameters can reveal additional information
about the model fit and the data, which is not revealed by merely looking at Figure 10.7 or
440   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

4 Benzene

psat (bar)
2

0.2
Residual, ei

–0.2
50 80 110 140
Temperature (°C)

FIGURE 10.7  Observed data (symbols) and model fit (lines) for the saturation pressure of benzene
and the residual errors at various temperatures.

the R-squared value. This is merely a brief introduction to this field. Interested readers are
referred to advanced texts on regression and data analysis for more information.

10.5.2.2 Nonlinear Regression for Ethylbenzene

We now use nonlinear regression to fit the model parameters for ethylbenzene.

Example 10.7  (Continued) Antoine’s Coefficients: Ethylbenzene

Problem: Use the vapor pressure data for ethylbenzene to estimate the values of param-
eters A, B, and C for Antoine’s equation.
Solution: The following code is used to estimate coefficients using nonlinear regres-
sion. We will use lsqnonlin in this example. The following function computes the
residual error vector required by the solver:

function errVal=antoineFun(Phi,xData,yData)
T=xData';
lnPsat=log(yData');
% Model calculation
A=Phi(1); B=Phi(2); C=Phi(3);
 Regression and Parameter Estimation   ◾    441

modelVal=A-B./(T+C);
errVal=lnPsat-modelVal;
end

The following script uses lsqnonlin to obtain model parameters:

%% Observed data
T=[50:10:140];
pSatEB=[0.0489, 0.0703, 0.1082, 0.1626, 0.2182, ...
0.3595, 0.4786, 0.6281, 0.8885, 1.0714];

%% Regression
PhiGuess=[10; 2500; 200];
PHI=lsqnonlin(@(X) antoineFun(X,T,pSatEB),PhiGuess);
A=PHI(1); B=PHI(2); C=PHI(3);

%% Verify model fit

pSatModel=exp(A-B./(T+C));
figure(3)
plot(T,pSatEB,'bo',T,pSatModel,'-r');
xlabel('Temperature (^oC)'); ylabel('p^{sat} (bar)');
figure(4)
plot(T,pSatEB-pSatModel);
xlabel('Temperature (^oC)'); ylabel('Residual, e_i');

The values of the three parameters are A = 11.3604, B = 4583.9, C = 267.9, whereas
Figure 10.8 shows the model fit for ethylbenzene.

10.5.3 Complex Langmuir-Hinshelwood Kinetic Model

A Langmuir-Hinshelwood-Hougen-Watson (LHHW) model for catalytic reaction

A ® B

is given by the following rate expression:

kC A
r= (10.75)
(1 + K ACA + K BCB )
2

A series of experiments were run and the reaction rate vs. concentration data was obtained.*
We will do this problem in two parts. In the first case, the reactor was operated with only
A in the feed at an initial concentration of CA0 = 1. With only this data available, we would
be unable to fit all the three parameters to the data. Next, we will use experimental data at
various initial concentrations of A and B to obtain all the rate constants.

*  This is also synthetic data used for demonstration purpose. It was generated with the same underlying model to highlight
the issues discussed in this example.
442   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

1.2

0.9 Ethylbenzene

psat (bar)
0.6

0.3

0
0.05

0
Residual, ei

–0.05

–0.1
50 80 110 140
Temperature (°C)

FIGURE 10.8  Observed data (symbols) and model fit (lines) for saturation pressure of ethylbenzene
and the residual errors at various temperatures.

10.5.3.1 Case 1: Experiments Performed at Single Concentration of B

The following table shows experimental data obtained from kinetic experiments:

CA 1 0.9 0.8 0.7 0.6 0.5 0.4

CB 0 0.1 0.2 0.3 0.4 0.5 0.6
r 5.55e−3 5.58e−3 5.45e−3 5.31e−3 5.14e−3 4.96e−3 4.52e−3

Since the only reaction taking place is A → B, the concentration of B is obtained from over-
all mass balance, noting that CA + CB = CA0 holds for the duration of the experiment. As a
first try, let us naïvely use the above data for performing linear regression of the LHHW
model. The nonlinear expression (10.75) can be converted to a linear form by inverting and
taking a square root:

1 æ 1 ö KA K B æ CB ö
1
=
r 
ç ÷+
k çè C A ÷ø k
( )
CA + ç
k çè C A
÷÷ (10.76)
 ø
f1 f2 f3

The next example demonstrates this attempt.

 Regression and Parameter Estimation   ◾    443

Example 10.8  Fitting an LHHW Model—Part 1

Problem: For the experimental data given above, use linear regression to fit an LHHW
kinetic model (10.75).
Solution: Given the data, we construct the required matrices and solve as below:
rateData=[5.55e-3, 5.58e-3, 5.45e-3, 5.31e-3, ...
5.14e-3, 4.96e-3, 4.52e-3];
CaData=1:-0.1:0.4;
CbData=1-CaData;
%% Linear least squares
Y=sqrt(1./rateData');
rootCa=sqrt(CaData');
X=[1./rootCa, rootCa, CbData'./rootCa];
phi=X\Y;
k=1/phi(1)^2;
Ka=phi(2)*sqrt(k);
Kb=phi(3)*sqrt(k);

When the above code is executed, MATLAB shows the following warning message:

Warning: Rank deficient, rank = 2, tol = 5.144832e-15.

This message should not be ignored. Since we have used the left division operator “\”
to compute Φ, MATLAB will give a solution. The software does not know whether the
rank deficient condition was intended. Some students would look at the result vector:

>> phi
phi =
6.7348
6.6996
0

and accept it as answer without further scrutiny.

If the importance of the above example is not yet clear, let me write it again in bold font:
Do not ignore warnings in MATLAB.
Let’s see why this happens—due to the material balance, CB = 1 − CA. Substituting this in
Equation 10.75, we get
kC A
r=
(1 + K )
2
A C A + K B (1 - C A )
kC A (10.77)
= 2
æ ö
ç (1 + K ) + ( K - K ) C ÷
B A B A
çç 
    ÷÷
è a1 a2 ø
444   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

As seen in the above expression, only a1 and a2 can be identified independently with the
data used in this example. When we write the rate expression in this form, the problem per-
haps becomes obvious. But what about the modified expression, Equation 10.76:

1 æ 1 ö KA K B æ 1 - CA ö
1
= ç ÷+
k çè C A ÷ø 
( )
CA + çç ÷÷ (10.78)
r  k  è CA
k ø
f1 f2 f3

Consider the three modified independent variables:

1 æ 1 ö
x= , u = CA , w = ç - CA ÷
CA ç ÷
è CA ø

When written this way, we can immediately observe that x, u, and w are linearly dependent.
While this problem is fairly clear when we use linear regression, naïve use of nonlinear
regression will mask these problems. Recall our statement in Section 10.4.1: One must exer-
cise caution when using regression.

10.5.3.2 Case 2: Experiments Performed at Different Initial Concentrations of B

The three kinetic parameters can be independently determined if the data in CA and CB is
not linearly dependent. In fact, this is something that is done in our CRE (chemical reac-
tion engineering) books in the “Determining kinetic constants” chapter without us realiz-
ing it. The experiments are repeated with different initial conditions, introducing different
amounts of B each time. Such a data set is shown in Section 10.6.2 in Table 10.5. Three
different sets of experiments were run, with concentration of A kept constant at CA0 = 1. In
the first set, only A was introduced; in the second set, CB0 = 0.1 was also introduced; and in
the third set, CB0 = 0.25 was introduced. The data collected during these experiments are
tabulated in Table 10.5.
We randomly split this data into two parts: training set and testing set. Four of the eighteen
data points (highlighted cells in the table) were selected as test set; the model parameters were
fit to the remaining fourteen data points. Thereafter, linear regression was used as before.

Example 10.8  (Continued) Fitting an LHHW Model—Part 2

%% Linear estimation of LHHW kinetics
load LHdata
Y=sqrt(1./rateData');
rootCa=sqrt(CaData');
X=[1./rootCa, rootCa, CbData'./rootCa];
phi=X\Y;
k=1/phi(1)^2;
Ka=phi(2)*sqrt(k);
Kb=phi(3)*sqrt(k);
 Regression and Parameter Estimation   ◾    445

× 10–3
5.6

5.2

Rate (estimated)
4.8

4.4
4.4 4.8 5.2 5.6
Rate (observed) × 10–3

FIGURE 10.9  Parity plot for the test data, with estimated values plotted vs. observed values.

%% Testing results
NTest=length(rateTest);
rHatTest=(k*CaTest)./(1+Ka*CaTest+Kb*CbTest).^2;
err=rateTest-rHatTest;
sse=err*err';
ssy=var(rateTest)*(NTest-1);
Rsquare=1-sse/ssy;
plot(rateTest,rHatTest,'bo','markersize',3);

The rate parameters obtained are k = 0.051, KA = 2.03, and KB = 0.49. Figure 10.9 shows
a comparison between observed data and model predictions. The symbols lie close
to the 45° line, indicating a reasonable fit. The R-squared value of r2 = 0.97 with test-
ing data indicates a good fit. Statistical information about confidence intervals also
indicates a good fit for the kinetic model. Thus, including additional data at different
initial CB0 concentrations improves the model performance.

10.5.4 Reaction Rate: Differential Approach

Contrary to the examples of estimating reaction rate constants in this chapter, the reac-
tion rate r is not directly measured. Instead, it is the concentration and temperature that
are directly measured and the reaction rate is computed from these measurements. It is in
this context that “differential approach” and “integral approach” are introduced in reac-
tion engineering texts. In this example, we will apply a differential approach for catalytic
reactions taking place in a batch reactor. The reactor contains the reactant at a concen-
tration of CA0 = 1 mol/L at initial time. The change in concentration with time is tracked.
The observations are shown in Table 10.2. The objective is to find a power-law model of
the type

r = kC An (10.79)

to fit the observed data.

446   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

TABLE 10.2  Concentration vs. Time Data for Determining Kinetic Rate Constants
t 5 30 60 90 120 150 180 210 240
CA 0.988 0.828 0.651 0.525 0.379 0.253 0.160 0.086 0.063

There are two different approaches that chemical engineers are familiar with. The first
one is the differential approach. Here, we use the definition of the reaction rate in constant
volume batch reactor as
1 dN A dC
r= = A (10.80)
V dt dt
Given the above data, we may be tempted to use numerical differentiation to compute the
reaction rate defined above. However, this approach is discouraged for two reasons. First,
the experimental data is available at sparse intervals, making the rate computations highly
approximate. However, much more importantly, there are measurement errors in the data.
High frequency errors (such as measurement errors) get highly accentuated in numerical
differentiation. For example, at time t = 120, numerical derivative gives
0.253 - 0.525
r120 = = -4.48 ´ 10-3 mol/L × s
60

However, if there was up to 2.5% error in the experimental data (which is actually on the
lower side of what one can expect in experiments)
0.246 - 0.535
r120 = = -4.82 ´ 10-3 mol/L × s
60

may have 7% or higher error.

Hence, an alternative is to fit a polynomial to the reaction rate data and hence compute
the rate of reaction. As will be shown in the next example, we find that second-order poly-
nomial is adequate to represent the data.

Example 10.9  Differential Method of Kinetic Analysis

Problem: Use the differential method of kinetic analysis to obtain rate parameters for
the power-law model (10.79) and fit it to the observed data in Table 10.2.
Solution: We will use the differential approach, where we will first calculate the rate
of reaction. We will do so by fitting polynomials of order 1 through 4. After doing this,
we choose polynomial of order 2:

rApoly ( t ) = a1 + a2t + a3t 2

to fit the observed data. The following part of the code does that:

%% 1. Fit a polynomial to original data

load batchData
Y=CaData;
 Regression and Parameter Estimation   ◾    447

n=length(CaData);
X=[ones(n,1), tData, tData.^2];
p=X\Y;
% Plot and verify the fit
Y=p(1)+p(2)*tData+p(3)*tData.^2;
plot(tData,CaData,'bo',tData,Y,'-r');

Figure 10.10 shows that the quadratic polynomial represents the data quite well. We
are not done yet. This is just a correlation that we fitted for convenience. We want to
use it for obtaining reaction rate parameters. It is easy to see that for the fitted polyno-
mial, the reaction rate is

r = - ( a2 + 2a3 )

where the negative sign is because A is a reactant. The following part computes the
corresponding reaction rate:

%% 2. Calculate reaction rate

rData=-(p(2)+2*p(3)*tData);
disp([tData, CaData, rData*1000]');

Let us now update Table 10.2 as below:

0 30.0 60.00 90.00 120.0 150.0 180.0 210.0 240.0

0.988 0.828 0.651 0.525 0.379 0.253 0.160 0.086 0.063
6.459 5.841 5.224 4.607 3.990 3.372 2.755 2.138 1.521

The last row is multiplied by 1000 to display. Now that we have reaction rate and con-
centration data for each, we can proceed with parameter estimation.

0.75 Quadratic fit

Concentration, CA

0.5

0.25

0
0 50 100 150 200 250
Time (s)

FIGURE 10.10  Observed data (symbols) and quadratic polynomial fit (line) to the data.
448   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

0.75 Model prediction

Concentration, CA
0.5

0.25

0
0 50 100 150 200 250
Time (s)

FIGURE 10.11  Observed data (symbols) and the fit for kinetic rate expression (dashed line).

%% 3. Compute parameters using linear regression

Y=log(rData);
X=[ones(n,1), log(CaData)];
par=X\Y;
k0=exp(par(1));
mu=par(2);
% Model comparison
tSol=tData;
ySol=(1-k0*(1-mu)*tSol).^(1/(1-mu));
plot(tSol,ySol);

The overall code for using differential method for rate analysis consists of the above
three parts, solved together in the same script file. Figure 10.11 shows that the model fits
the overall data very well. The kinetic rate expression obtained through this approach is

r = 6.46 ´ 10-3 C A0.487

10.6 EPILOGUE
10.6.1 Summary
In this chapter, we covered methods for obtaining model parameters that fit a set of obser-
vations. We also provided a basic introduction to analyzing statistical properties to ver-
ify goodness of fit. I would like to impress upon the reader that obtaining least squares
parameters is the easy part of the regression process. These parameters are not useful unless
accompanied by some goodness of fit measures. Three different ways were introduced: (i)
qualitative method by plotting experiments and model fits together, (ii) simple statistics
such as coefficient of determination (“R-squared”) and sum of squared errors, and (iii) sta-
tistical bounds on parameters and confidence intervals.
I close this chapter by mentioning matrix-based and singular value decomposition–
based approaches as my recommended approaches for linear least squares. If the parameter
estimation problem is not linearizable, then the nonlinear estimator may be used. I would
recommend lsqnonlin as a preferred algorithm (Optimization toolbox).
 Regression and Parameter Estimation   ◾    449

If you have access to the Statistics toolbox, using the full power of the toolbox is highly
recommended. The treatment in this chapter will help you build the foundation for under-
standing more advanced material in statistical analysis.

10.6.2 Data Tables
Table 10.3 shows the data for specific heat of methane at two different temperature ranges
(298–500 K and 600–1300 K). The data for pure component vapor pressures of benzene and
ethylbenzene are shown in Table 10.4, whereas reaction rate data is shown in Table 10.5.

TABLE 10.3  Specific Heat of Methane at 1 bar Pressure

Normal Temperature Range High Temperature Range
T (K) cp (J/mol · K) T (K) cp (J/mol · K)

298 35.64 600 52.74

325 36.69 700 58.6
350 37.85 800 64.08
375 39.13 900 69.14
400 40.63 1000 73.75
425 41.93 1100 77.92
450 43.39 1200 81.68
475 44.87 1273 84.1
500 46.63 1300 85.07
Sources: Data obtained from NIST WebBook, http://webbook.
nist.gov/cgi/cbook.cgi?ID=C74828&Mask=1; Gurvich,
L.V. and Alcock, C.B., Thermodynamic Properties of
Individual Substances, Hemisphere, New York, 1989.

TABLE 10.4  Pure Component Vapor Pressure Data

for Benzene and Ethylbenzene
Vapor Pressure (Bar)
Temperature (°C) Benzene EB

50 0.3751 0.0489
60 0.5027 0.0703
70 0.7112 0.1082
80 0.9883 0.1626
90 1.2529 0.2182
100 1.8758 0.3595
110 2.3648 0.4786
120 2.9474 0.6281
130 3.9049 0.8885
140 4.5455 1.0714
Sources: Benzene: NIST WebBook, http://webbook.nist.gov/cgi/
cbook.cgi?ID=C71432&Mask=4#Thermo-Phase; Ethyl
benzene: NIST WebBook, http://webbook.nist.gov/cgi/
cbook.cgi?ID=C100414&Mask=4#Thermo-Phase.
450   ◾    Computational Techniques for Process Simulation and Analysis Using MATLAB®

TABLE 10.5  Reaction Rate Data for Langmuir-Hinshelwood

Kinetics for Section 10.5.3
CA CB r CA CB r

0.9 0.1 5.58e−3 1 0.25 5.08e−3

0.8 0.2 5.45e−3 0.8 0.45 5.05e−3
0.7 0.3 5.31e−3 0.7 0.55 4.88e−3
0.5 0.5 4.96e−3 0.6 0.65 4.72e−3
1.0 0.1 5.37e−3 1.0 0 5.55e−3
0.9 0.2 5.34e−3 0.6 0.4 5.14e−3
0.7 0.4 5.19e−3 0.8 0.3 5.36e−3
0.6 0.5 5.01e−3 0.9 0.35 5.12e−3
0.5 0.6 4.81e−3 0.5 0.75 4.37e−3
The model parameters are fitted to the testing data (unshaded rows
in the table), whereas the shaded rows indicate the test data to test
the model performance.

EXERCISES
Problem 10.1 Show that Equations 10.25 and 10.33 are equivalent. In other words, show
that

éN Sx ù é Sy ù
XT X = ê T
ú, X Y = ê ú
ëS x S xx û ëS xy û

Problem 10.2 Write your code for Example 10.4 and derive the parameter values and the
standard deviations of these parameters.
For the data in Example 10.4, fit substrate inhibited rate law:

m max CS
r=
K + CS + aCS2
Appendix A: MATLAB® Primer

MATLAB® is a portmanteau of matrix laboratory. It is a high-level computing language,

widely used in computational analysis, control, signal processing, communication, and
related fields. This appendix provides a nonexhaustive primer for the reader to get started
with MATLAB. The treatment here will be necessarily succinct. This appendix may also be
used by people who have used MATLAB in the past but would like to orient their way of
using MATLAB to the one followed in this book.
There are several resources available to get started with MATLAB. The MathWorks web-
site has video tutorial on Getting Started with MATLAB.* I have a video course on NPTEL†
that focuses on MATLAB.
Each individual set of concepts are discussed in sections below. Each section starts with
a set of problems that a user can solve, followed by the solution. Users of MATLAB are
encouraged to try solving these problems on their own before checking the solutions pro-
vided in the same section.

A.1 SOME SPECIAL VARIABLES

The following constants and special variables are used in MATLAB:

ans Captures the last evaluated value that was not

assigned to a variable
pi The value of π
i or j The imaginary unit -1 ( )
eps Machine precision (see Chapter 1)
inf Infinity ∞
0
nan Not a number (e.g., evaluates as nan)
0

If your code replaces any of the above variables, then that new assigned value stays with
that variable and it loses its original (default) value. Thus,

>> i = 2
i =
2

*  http://in.mathworks.com/videos/getting-started-with-matlab-68985.html (August 1, 2016).

†  National Programme for Technology Enhanced Learning (NPTEL) is a Government of India initiative, which provides

online web and video courses free. Video lectures on MATLAB and related material can be accessed at: http://nptel.ac.in/
courses/103106118/ (August 1, 2016).

451
452   ◾    Appendix A: MATLAB® Primer

From this point onward, i will not represent the imaginary unit but instead shall represent
the value assigned to it.
Note that the value of i above is echoed (i.e., displayed) on the screen. The echo can be
suppressed by ending the statement with a semicolon:

>> i=2; % This will suppress echo on the screen

The variable ans is a special variable. When an expression is executed but the value is not
assigned to any variable, the value is captured in the variable ans. For example

>> 3*i
ans =
6

Since the expression 3*i is not assigned to any variable, the latest such value is captured in
ans and the value is echoed on the screen (since there is no semicolon to end the statement).

A.2 MATRIX OPERATIONS AND VECTOR FUNCTIONS

Users who are new to MATLAB may wish to review video lectures on NPTEL and
MathWorks.*

A.2.1 Creating and Accessing Vectors and Matrices

A set of problems that I will use to introduce students to matrix and vector operations is listed
below. The readers can try to solve these problems before proceeding to the discussions.

1. Create the following 3 × 4 matrix A:

é -4 2 3 4ù
ê ú
A=ê 3 1 4 7ú
ê 8 úû
ë4 0 5

2. Create a vector p = [1  2  ⋯   n]. Choose n = 3.

In other words, I want you to use “ : ” command instead of typing p=[1,2,3];
3. Create a 3 × 3 identity matrix and assign it to B.
4. Type help diag to understand the diag command.
If you type diag(A), what do you get? Try and check.
5. What will you get if you type diag(diag(A)). Check. Does it make sense?
6. If you type A(2,p), what will you get?

*  http://in.mathworks.com/videos/working-with-arrays-in-matlab-69022.html (August 1, 2016).

 Appendix A: MATLAB® Primer   ◾    453

7. Obtain the second row of A and assign it to vector d.

8. Obtain E as a 2 × 2 subarray of A starting from row 1–column 2. In other words

é2 3ù
E=ê ú
ë1 4û

However, E should be obtained from array A, and not by entering a new matrix.

A.2.1.1 Building Up Matrices
Let us now look at MATLAB commands that achieve the above. Matrix A can be assigned as

>> A = [-4, 2, 3, 4; 3, 1, 4, 7; 4, 0, 5, 8];

The semicolons separate multiple rows. Individual cells on each row can be separated by
comma (or spaces). It is important to know a couple of things: First, like math operations fol-
low brackets–exponent–multiplication–addition, MATLAB parses row–columns. For example

>> A = [4; 3; 4, 2; 1; 0, 3; 4; 5, 4; 7; 8];

Dimensions of matrices being concatenated are not consistent.

Note that MATLAB gives an error because it parses the command as

A = [4;
3;
4, 2 etc.

The error signifies that I am trying to concatenate the first two rows with one element each
and the third row with two elements, hence the error. However, one may use brackets to
create the matrix:
>> A = [[4; 3; 4], [2; 1; 0], [3; 4; 5], [4; 7; 8]]
A =
4 2 3 4
3 1 4 7
4 0 5 8

Here, each bracket creates a 3 × 1 vector; four such vectors are concatenated to give a
3 × 4 matrix. Note that square brackets enclose a vector/matrix/array. On the other hand,
­parentheses are used to query a location in the array. Thus, the command
>> A(3,2)
ans =
0

returns the element in the third row and second column of A.

The next problem brings us to colon notation. In MATLAB, a:b is read as “from a to b
in steps of 1,” whereas a:h:b is read as “from a to b in steps of h.” Thus, 1:3 (or 1:1:3)
454   ◾    Appendix A: MATLAB® Primer

will result in a row vector [1 2 3]. You may try the following commands in MATLAB,
thinking about what the result would be before you execute the command in MATLAB
(and hence check your understanding):

>> p=1:3
>> q1=1:3:5
>> q2=1:1.5:5
>> q3=5:-1:1
>> q4=5:1

Perhaps the last command needs explanation. It says “5 to 1 in steps of 1.” However, the first
value, 5, is greater than the final value. Hence, no value can be assigned and q4 becomes
an empty matrix. Note that this does not give an error; instead an empty matrix is returned.

A.2.1.2 Some Special Matrices

The commands for creating identity matrix, matrix of zeros, and matrix of ones are
eye(m,n), zeros(m,n), and ones(m,n), respectively. The command eye(m) is
equivalent to eye(m,m). Clearly then, B = eye(3); returns a 3 × 3 identity matrix.
There are some further commands to create matrices:

magic(3); Creates a 3 × 3 magic matrix

rand(m,n); Creates an m × n matrix of random numbers from uniform distribution
randn(m,n); Creates an m × n matrix of random numbers from normal distribution
diag(A); Extracts diagonal elements from A and stores them as a vector
diag(vec); Creates a diagonal matrix with elements of vec forming the diagonal
tril(A); Extracts lower triangular matrix from A
triu(A); Extracts upper triangular matrix from A

The next command I will use is diag, as follows:

>> diag(A)
ans =
4
1
5

The above result is fairly straightforward—the vector returned contains diagonal elements of A:

>> diag(diag(A))
ans =
4 0 0
0 1 0
0 0 5

From the above description of the diag command, does your understanding of diag
match MATLAB results?
 Appendix A: MATLAB® Primer   ◾    455

A.2.1.3 Querying Elements of a Matrix

Elements of a matrix, as described earlier, can be queried as A(k,l). If k and l are scalars,
this returns the element in the kth row and lth column. If k and/or l are vectors, all ele-
ments corresponding to all the row-column pairs are returned:

>> A(2,p)
ans =
3 1 4

The above command returns from the second row of A, the elements corresponding to
column numbers indicated by p vector, [1 2 3]. In other words, it returns the first three
elements of the second row of A.
The command to extract the entire second row of A is

>> d=A(2,:)
d =
3 1 4 7

Note that simply using colon implies “all.” Thus, the above command implies elements in A
at row 2—and all elements in that row.
It should be fairly clear how to get matrix E that contains entries from first two rows and
columns 2 and 3 of matrix A:

>> E = A(1:2,2:3)
E =
2 3
1 4

Finally, here is a command for the reader to try. It is perhaps a good idea for you to think of
what result you would expect and then execute the command in MATLAB:

>> F = A([3,2],[1,3])

Does the result match your reasoning? If still confused, think what the commands below
will give:

>> A(3,[1,3])

Next, consider

>> A(2,[1,3])

The result F above is nothing but the result of the above two commands placed in the first
and second rows of F, respectively.
456   ◾    Appendix A: MATLAB® Primer

Finally, there is a special keyword, end, to represent the last element of a vector/matrix:

>> d(end)
ans =
7

Since d represents the second-last row of matrix A, it can also be obtained as

>> A(end-1,:)
ans =
3 1 4 7

A.2.2 Basic Mathematical Operations on Arrays

In this section, we focus on basic math operations on arrays, using the following questions
to expound the concepts:

1. Perform scalar addition, multiplication, and division of A and verify.

2. Get transpose of matrix A. Assign it to Atrans.
3. Compute Cr = AAT and Cl = ATA.
4. We computed d in Item #7 above. What will the following commands yield:
sum(d) cumsum(d) prod(d) cumprod(d) diff(d)?

5. Calculate inverse of Matrix E (see Item #8 above) and assign it to F.

6. Compute 1/E. What do you get? Why? Now compute G=1./ E
7. Compute H=E^(-1) and I=E.^(-1). Compare with F and G.
Do you understand the meaning of .^ , ./ , and .* ?

>> 2*A;
>> A/2;
>> A+2;

In the commands above, each element of A is doubled and halved, and 2 is added to each
element of A, respectively. Note that in MATLAB, (A + 2) is not equivalent to (A + 2I).*
Transpose in MATLAB is obtained using single quotation (apostrophe) key. Thus, the
reader can verify the following commands:

>> Atrans=A';
>> Cr=A*A';
>> Cl=A'*A;

*  The origin of this misunderstanding among my students is not clear to me. In matrix algebra, one does not add a scalar
to a matrix. In this book, however, we will understand (A+2) in the context of the MATLAB definition: 2 added to each
element of A.
 Appendix A: MATLAB® Primer   ◾    457

Since A is a 3 × 4 matrix, the above three matrices have size 4 × 3, 3 × 3, and 4 × 4, respec-
tively. The variable Cr is

Cr =
45 54 63
54 75 88
63 88 105

The commands sum(d) and prod(d) compute the sum and product of all elements of
the vector, d, respectively.* Since the vector d=[3 1 4 7], the two values are 15 and 84,
respectively. The cumulative sum is computed using cumsum(d), the result being a vector
of the same dimension as d itself. The first element of the resulting vector is the first element
of d, the second element is the sum of the first two elements, the third element is the sum of
the first three elements, and so on:

>> cumsum(d)
ans =
3 4 8 15

The command cumprod works in a similar way and gives the cumulative product.
The command to compute the inverse is inv. The following two commands are equivalent:

>> F=inv(E)
F =
0.8000 -0.6000
-0.2000 0.4000
>> H=E^(-1)
H =
0.8000 -0.6000
-0.2000 0.4000

The latter is just the matrix E to the power -1.

At this stage, I end this section by describing element-wise operations in MATLAB. The
element-wise operator† has a dot preceding the regular operator, for example, .*, ./ , and
.^, and here is what they give:

>> E.*E
ans =
4 9
1 16

*  The sum (or prod) command operates on arrays as well, where the sum (or product) of all elements in each of the columns
of the array is computed.
†  MATLAB calls element-wise operator as array operator to distinguish it from matrix operator. Thus, E*E is “matrix multi-

plication,” whereas E.*E is “array multiplication” of individual elements of the first array with the corresponding elements
of the second array.
458   ◾    Appendix A: MATLAB® Primer

Note that the product operates on each element of E individually. Since E = [2 3; 1 4],
the result of the above operation is a matrix of the same dimension, with each individual
element squared. Contrast that with the regular matrix product:

>> E*E
ans =
7 18
6 19

In the same context:

>> G=1./E
G =
0.5000 0.3333
1.0000 0.2500
>> I=E.^(-1)
I =
0.5000 0.3333
1.0000 0.2500

The element-by-element power operation (array operation) not only works to get scalar
power of a vector, it can also be employed as follows:

>> 2.^d
ans =
8 2 16 128

Note that each element of the resulting ans is the scalar 2 raised to the power of the cor-
responding element of the vector d.

A.2.3 Matrix Divisions and the Slash Operators

I left Item #14 for last. It deserves its own subsection since matrix division is a more involved
concept. Let us try the command below:

>> 1/E
Error using /
Matrix dimensions must agree.

The forward slash operator is the so-called right division. Roughly speaking, A/B evaluates
as A*inv(B) if B is a square matrix.* Likewise, the backward slash operator is the left divi-
sion, with A\B roughly evaluating as inv(A)*B.

*  A right division is a least-squares solution of a linear equation xB = A, whereas a left division is a least-squares solution of a
linear equation Ax = B. Please refer to Chapter 10 for more information on least-squares solutions.
 Appendix A: MATLAB® Primer   ◾    459

A.2.4 Test Yourself

Example A.1  Test Yourself with Array Operations

Test yourself with the following questions:

1. Generate a vector v = [1,   3,   5,   7,  … ,   n] (where n is an odd number).

2. Given a scalar x, calculate f = [x1,   x3,   x5,  … , xn] using vector v.
3. Calculate g such that each element is the inverse of the corresponding element of f.
1 1 1
4. Compute the value of + 3 +  + n . Save all the steps as a single script file.
x x x

Here is the MATLAB code to compute the above:

% MATLAB Array Operations

n=11; x=2; % Assign values to variables
v=1:2:n;
f=x.^v;
g=1./f;
res=sum(g);

The percentage sign (%) signifies that all text following it is a comment, which is
ignored by MATLAB. The vector v is defined using the colon notation described in
Section A.2.1. The array operations described in Section A.2.2 give the vectors f and g,
and the final result is calculated using the command sum. The result is

>> res
res =
0.6665

The above code can be saved in a MATLAB file. As discussed in Section A.5, such a file is
known as “MATLAB Script.”

A.3 MATHEMATICAL FUNCTIONS
I have already covered a few vector functions (sum, cumsum, etc.) and a couple of matrix
functions (inv and slash). Let us now cover a few more functions.

A.3.1 Common Matrix and Array Functions

One of the important things to query in a vector or array is its size:

>> l=length(d);
>> [m,n]=size(A);
460   ◾    Appendix A: MATLAB® Primer

The first command returns the length of the vector d, whereas the second command returns
the number of rows (in variable m) and columns (in variable n). Thus, l=4, m=3, and n=4.
Applying the length command to an array returns the larger between m and n:

>> length(A)
ans =
4

Power, logarithm, and exponent are other important functions in MATLAB, which have
both matrix and array versions. In the previous section, I explained matrix multiplication,
division, and power and contrasted them with array (i.e., element-wise) versions of the
same. An alternate command for power include mpower (matrix power, E^n) and power
(array power, E.^n):

>> power(E,2)
ans =
4 9
1 16

This is same as E.^2. The next command is equivalent to E^2:

>> mpower(E,2)
ans =
7 18
6 19

In the same manner, the sqrtm and sqrt functions are used to find the matrix square root
and element-wise square root of an array. The commands E^0.5, mpower(E,0.5),
and sqrtm(E) all give the same results.
The functions for finding element-wise exponent or natural logarithm of an array are:

exp(A) Array exponent of any array A

log(A) Array logarithm of any array A
expm(E) Matrix exponent of a square matrix E
logm(E) Matrix logarithm of a square matrix E

Self-Test Question: What do you expect if you use sqrtm(A)?

>> sqrtm(A)
Error using sqrtm
Expected input to be a square matrix.

The matrix functions mpower, expm, logm, and sqrtm can be applied to square
matrices only.
 Appendix A: MATLAB® Primer   ◾    461

A.3.2 Trigonometric and Other Array Functions

The trigonometric functions sin(theta), cos(theta), tan(theta) and their
inverses asin(x) (stands for sin−1(x)), acos(x), and atan(x) are all array functions,
in that they operate on individual elements of an array. It needs to be emphasized that the
argument, θ in trigonometric functions, and the result of inverse trigonometric functions
are in radians. Hyperbolic functions are similarly defined as sinh, cosh, and tanh and
inverse hyperbolic functions as asinh, acosh, and atanh.
1
It bears emphasizing that sin(theta)^-1 implies and sin^−1(theta) will
sin ( q )
return an error.
Some other important array functions include

min(d) or max(d) Minimum or maximum value in vector d.

mean(d); Average of all values in vector d.
std(d); Standard deviation of vector d.
round(d,2); Round off each element of d to two decimal places.
ceil(d); Round up each element of d to the next higher integer.
floor(d); Round down each element of d to the previous integer.

A.4 OUTPUT DISPLAY AND PLOTTING

A.4.1 Text Display on Command Window
After a MATLAB script completes execution, we would want to display some of the key
results on the command window. This was shown in Example A.1: Typing the variable of
interest (“res” in this example) without the trailing semicolon made MATLAB echo the
variable value on the screen. Echoing MATLAB variables without the trailing semicolon is
one way to display the results, which can be used to display any variable or expression from
a MATLAB file. Another equivalent way* of doing this is to use the command display:

>> display(res)
res =
0.6665

Either echoing a variable or using display causes MATLAB to display the name of the
variable as well. Moreover, the entire display takes three lines.† Alternatively, the disp
command is a more succinct method since the variable name is suppressed:

>> disp(res)
0.6665

*  In reality, when one does not use a trailing semicolon, MATLAB internally calls the display command itself. This is hid-
den to the user but is the reason why one sees the same result.
†  The example shown above is exactly how MATLAB echoes a variable or uses display. A blank line is left before the dis-

played information and another blank line between the variable name and values. In all of this text, these superfluous blank
lines are not shown for brevity.
462   ◾    Appendix A: MATLAB® Primer

Since the above method does not print any other information than the variable value,
MATLAB string operations are used instead. For example

>> str = ['first string', 'second string'];

will yield a string str = 'first stringsecond string'. Note the lack of space
between the two strings that are concatenated. The above string can be displayed using
disp(str). Let us now add a space at the end of the first string and replace the second
string with a numeric string:

>> disp(['first string ', '0.6665']);

first string 0.6665

Here are two important points to note: (i) the use of square brackets to define a concatenated
string and (ii) the use of single quotes enclosing '0.6665'. The command is disp(s1),
where s1 and s2 are string variables. If the square brackets are eliminated, MATLAB reads
this as disp(s1,s2). Since disp takes only one input argument, this will result in an
error: Too many input arguments. Since the two strings need to be printed side by
side, horizontal catenation is used (exactly in a similar way as that with numeric variables).
Thus, the command used is disp([s1,s2]). The second point is regarding the differ-
ence between 0.6665 and '0.6665': The former is a number, whereas the latter is a
string. Numbers cannot be concatenated with strings.
So, what do we do if we have the result in numerical variable, res? This number is con-
verted to a string using the num2str command. Thus, a better way of displaying the result is

>> disp(['The result is ',num2str(res)]);

The result is 0.6665

A recap of the various things just discussed: (i) using num2str to convert numeric
variable res to a string; (ii) concatenation of this to a string 'The result is ';
(iii) enclosing the strings to be concatenated within square brackets; and (iv) inclusion
of a space within the prefix-string to ensure there is a space between the string and
displayed value.
Next, consider the command:

>> disp(['Matrix E is: ',num2str(E)])

Error using horzcat
Dimensions of matrices being concatenated are not consistent.

The reason for this error is that num2str(E) results in a string array with two rows; this
cannot be concatenated with a string ('Matrix E is: ') having a single row.
An alternative way of displaying results is to use the command sprintf. Since this
command is not used much in this book, it will be skipped for brevity.
 Appendix A: MATLAB® Primer   ◾    463

A.4.2 Plotting Results
Try the following problems yourself:

1. We want to plot y = 2x2 + 0.5 for the values of 0 ≤ x ≤ 1 in steps of 0.01. Generate x
using colon “:” notations. This line should be dashed-red line.
2. Please use help plot to learn how to plot in MATLAB, and to find out how to plot
with a dashed-red line instead of solid blue.
3. Label the two axes as “x” and “quadratic,” respectively, using xlabel and ylabel
commands in MATLAB.
4. On the same figure, plot z = x2 + 2x as a default line

The following video on the MathWorks site gives an introduction to basic plotting functions:
http://in.mathworks.com/videos/using-basic-plotting-functions-69018.html
The following example solves the above problem.

Example A.2  Basic Plotting Functions

The MATLAB code below plots the above requirements:

% Define variables and plot

x=0:0.01:1;
y=2*x.^2+0.5;
plot(x,y,'--r');
xlabel('x'); ylabel('quadratic');
% Define and plot the second line
z=x.^2+2*x;
hold on; % To keep the previous line
plot(x,z)

The first plot command tells MATLAB the format for the line to be plotted: '--r'
implies dashed line (--) with red color (r). The resulting plot is shown in Figure A.1.
Note the use of the command hold on. Without the use of this command, the
current plot will be overwritten. Since I wanted to plot the second line on the same
plot as the first one, I used this command to hold the previous plot. The hold on
command needs to be used only once for each figure. To toggle back* to the default
mode of overwriting a previous plot, use hold off.

Note that symbols may be displayed by using the appropriate plot formatting string. The last
item in the format string signifies the symbol. Thus, '-b.' indicates solid line, blue color,
with dot symbols, whereas 'ko' implies no line, black color with circle symbols.

*  Simply using hold will toggle between on and off states. I personally discourage such use in favor of using hold on
and hold off explicitly.
464   ◾    Appendix A: MATLAB® Primer

Quadratic
1

0
0 0.5 1
x

FIGURE A.1  Demo on using plot command to plot two lines.

In addition to plot, xlabel, and ylabel, other useful commands include

loglog Make a log-log plot.

semilogx Semilog plot, logarithmic scale for X-axis.
semilogy Semilog plot, logarithmic scale for Y-axis.
mesh, surf 3D mesh or surface plots.
figure Opens a new figure (or selects existing figure).
subplot Make multiple axes on same figure in tiled position.
title Insert a title for the plot.
legend Insert a plot legend.

A.5 WORKING WITH MATLAB® FILES

MATLAB files are of two types: scripts and functions. A good video tutorial on using files
is provided on MATLAB website.* Lecture 1–4 of my NPTEL course† discusses MATLAB
scripts and functions, and when to use them. All MATLAB files are in plain text and have
extension “.m.” MATLAB comes with a powerful editor. Although MATLAB m-files can be
read by any text editor, the MATLAB editor has very powerful and useful features, and is
used almost exclusively to program using MATLAB files.
A MATLAB script is a sequence of commands written sequentially. MATLAB treats
these commands in the script file as if it were executed sequentially at the command prompt
(or within a calling function that calls this script file). The variables in a script file share the
workspace from where they were called. When the script files are called from the command
prompt, as will be the case in most of this book, they will use the MATLAB’s command
workspace. Consider the program in Example A.1. As mentioned in the example, the entire

*  Please see: http://in.mathworks.com/videos/writing-a-matlab-program-69023.html.

†  Please visit: http://nptel.ac.in/courses/103106118/ and click on Lecture 1–4. In this section, I summarize the details dis-

cussed in this online video lecture.

 Appendix A: MATLAB® Primer   ◾    465

code can be written in a MATLAB file (say “arrayOperations1.m”). The code can be
executed by typing
>> arrayOperations1

at the command prompt. All the variables declared and used in the script file are available
in the MATLAB workspace after the script completes its execution.
MATLAB function, on the other hand, is a file that takes certain sets of inputs, executes
a sequence of steps defined in that file, and returns the outputs to the calling entity. The
set of inputs and outputs are known as input / output arguments. A MATLAB function file
(usually) has the same name as the name of the function itself. The first line of a function
(myFirstFun.m) will be
function [out1,out2,...] = myFirstFun(in1,in2,...)

There can be zero or more input arguments. These input arguments (in1, in2, etc.) are
written after the function name, and are comma-separated and enclosed within parenthe-
ses. Likewise, there can be zero or more output arguments (out1, out2, etc.), which are
comma-separated and enclosed within square-brackets and written before the function
name. Each MATLAB function has its own workspace and exchanges information through
these input and output arguments. Any other variables defined or changed within the func-
tion have a local scope, meaning that they are not accessible outside the function and are
“lost” once the function finished execution.*,†

A THOUGHT EXERCISE
Consider a thought exercise: You and your friend have a set of instructions on how to solve
a problem. Your friend will assist you in solving the problem. You have a notepad where you
have written down several values that are required for solving the problem. You have access
to your own set of instructions, but not to those of the other person. After executing some of
your instructions, you are told to seek your friend’s help.
Scenario 1: Consider the first scenario, where you and your friend use the same shared note-
pad. At this stage, you pass on this notepad to your friend, who then executes their instructions
and does all the computations on this notepad. On completion, your friend returns the notepad
to you. Since you shared the notepad, you have access to not only the result but also to all the
number-crunching work done by your friend. In this case, your friend is a MATLAB Script.
Scenario 2: Consider another scenario, where your friend has their own notepad that is not
accessible to you. For helping you, they only need a couple of pieces of information from you.
You write them on a yellow post-it note and give the post-it to your friend. Your friend then
implements instructions and does all the computation on their own notepad. On completion,
the information you seek is returned to you written on another green post-it note. In this case,
your friend is a MATLAB function, their notepad is the function’s own workspace, the yellow
post-it note is a set of input arguments and the green post-it note is a set of output arguments.

*  Exception to this rule is global variables, which have to be declared as global in the function. They are accessible to any
function or script using global declaration.
†  Additionally, MATLAB also allows defining persistent variables, which are not lost once the function finishes execu-

tion. They are mentioned here for the sake of completeness, but will not be discussed in this book.
466   ◾    Appendix A: MATLAB® Primer

Let us now consider an example where we will use MATLAB files. In Chapter 10, the spe-
cific heat of methane gas at various temperatures is obtained in the form of the following
quadratic function:

cp = 13.7 + 0.075T - 1.52 ´ 10-5 T 2 (A.1)

where
cp is the specific heat in J/mol · K
T is the temperature in Kelvin

Let us consider two cases: (i) where we want to compute the specific heat for a given tem-
perature and (ii) where this computation of cp(T) needs to be used as a part of a larger code.
The next example distinguishes the two cases.

Example A.3  Specific Heat of Methane: Use of MATLAB® Files

Problem: Write a MATLAB file to compute the specific heat of methane using Equation
A.1 at a given temperature in Kelvin.
Solution: The following MATLAB script computes the specific heat of methane:

% Compute specific heat of methane

T=input('Please enter temperature (K): ');
% Specific heat parameters and computation
a1=13.7; a2=0.075; a3=-1.52e-5;
cp=a1+a2*T+a3*T^2;
disp(['At T = ', num2str(T),...
' K, c_p = ', num2str(cp), ' J/mol.K']);

The above lines are typed in MATLAB editor, and the file is saved as spHeat.m. This
file is MATLAB script. It can be executed by typing the file name on the command
prompt (or in any other file). This gives

>> spHeat
Please enter temperature (K): 450
At T = 450 K, c_p = 44.372 J/mol.K

Note that the value of 450 (underlined for highlighting) was entered by the user.
Specific heat was computed at that temperature and assigned to the variable cp.

A script is a perfect way to write a sequence of MATLAB statements that one needs to
execute for a particular job. In examples in Chapters 4 and 7, the specific heat will be used
for other computations. In such a case, a MATLAB function will be more appropriate.
 Appendix A: MATLAB® Primer   ◾    467

Example A.3  (Continued) Specific Heat of Methane: Use of MATLAB® Files

Solution: Here, we will write a MATLAB function that takes temperature as an input
and returns specific heat as the output. The MATLAB code written above is modified
as below and used as a MATLAB function:

function cp=spHeat(T)
%% Compute specific heat at a given temperature
a1=13.7;
a2=0.075;
a3=-1.52e-5;
cp=a1+a2*T+a3*T.^2;
end

The computation of cp is vectorized by using array operand “.^” so that the specific
heat can be computed at multiple temperature values if T is a vector. The above com-
mands were saved as a function. The function needs to be invoked from the command
line by providing input arguments and capturing the results as output arguments:

>> clear all

>> T_gas=450;
>> cp=spHeat(T_gas)
cp =
44.3720

The first command clears all the workspace variables, whereas the final command
calls the function to compute specific heat. The input argument may either be a vari-
able or just a value (scalar, vector, or array, as required in the function).
The first difference between the script and function is based on scope of the variables.
Variables of a function are local to that function itself. So, after executing the function,
if we were to check variables in our workspace, we will find that there are only two
variables in the workspace, T_gas and cp, because the parameters a1, a2, and a3
are local to the function spHeat and hence unavailable in the MATLAB workspace.
Another difference is the way the two are invoked. If the function is simply called
by the file name (without providing the adequate number and type of input argu-
ments), MATLAB will return an error:
>> spHeat
Not enough input arguments.
Error in spHeat (line 7)
cp=a1+a2*T+a3*T^2;

The final thing to note is that the file name should be the same as the name of the
function.

This completes our discussion on MATLAB scripts and functions. Before I close this sec-
tion, I would like to draw the attention of the user to the variables used. Note that the
468   ◾    Appendix A: MATLAB® Primer

temperature was named in the MATLAB workspace as T_gas. This value was passed on to
the function. As described in the pullout text box, this is equivalent to the “workspace”
writing the value of T_gas on a post-it note and handing it to “spHeat.” The function
“spHeat” refers to this value as variable T, does its computations using its own copy of the
variable (equivalent to doing this “on its own notepad”), and has no access to any variable
from the MATLAB workspace.

A.6 LOOPS AND EXECUTION CONTROL

A.6.1 The for and while Loops
MATLAB provides two constructs for executing a set of tasks repeatedly in a loop. The
first, and more commonly used, is the for loop. The command for indicates start of
the loop, whereas the end statement indicates termination of the loop. The structure of
the for loop is

for index=<list of values>

<commands that are repeated>
end

The most common use is when a block of commands need to be repeated a certain number
of times. For example, if the block is to be repeated five times, the first line written as

for i=1:5

so that the loop is repeated five times, and the index i is incremented every time the termi-
nal end statement is encountered. The increment of the index need not be in steps of 1; any
other increment is also possible, such as

for j=1:2:10

In this case, the index j takes the values 1, 3, 5, 7, and 9 in each iteration; clearly, the loop is
executed five times. Note that the value of the index is available within the loop, but it may
not be modified when the loop is being executed. When the loop completes execution, the
index variable takes the last value used in the loop. This value is accessible outside the loop.
Thus, after the two loops mentioned above finish execution, the variables i and j have the
values of 5 and 9, respectively.
With this background and the discussion in previous sections, the reader may try answer-
ing the following questions. For the several for statements below, what are the values that
the index will take each time the loop executes?

for p=0:0.2:1
for q=5:1
for r=5:-1:1
for s=[1 -2 0 2]
 Appendix A: MATLAB® Primer   ◾    469

In each of the above example, the following lines of code may be executed:

for p=0:0.2:1
disp(p);
end

with the first and second line replaced appropriately.

1. The first case should be fairly clear based on the preceding discussions. Here, the loop
will execute six times; the variable p takes the values of 0, 0.2, 0.4, 0.6, 0.8, and
1 each time the statements in the loop get executed.
2. Since the command [5:1] returns a blank matrix, the loop will not get executed. In
other words, the commands in the for block, before the corresponding end state-
ment, will be skipped, and variable q will become an empty variable (i.e., q=[ ]).
3. The loop will get executed five times, with the value of r starting at 5 and decrement-
ing with each iteration. In other words, in each of the five iterations of the for loop,
r will consecutively take the values of 5, 4, 3, 2, and 1.
4. The final example is a uniquely MATLAB-specific implementation of the for loop. In
each iteration, the index variable s consecutively takes the values from each column
of the argument. In other words, the loop will get executed four times. During the first
iteration, s takes the value of the first element, i.e., s=1; in the second iteration, it
takes the value of s=-2; in the third iteration, s=0; and in the fourth iteration, s=2.

While the last example shows the versatility of the for loop in MATLAB, it can make the
code somewhat confusing to debug. Instead, I suggest using the following, rather tradi-
tional, approach:

A=[1 -2 0 2];
for i=1:length(A)
s=A(i);
disp(s);
end

Although the variable s takes the same values in each iteration as in the previous case, the
latter code is more readable. The readers can compare the two codes and verify that they
give the same results.
What do you expect when the following code is used?

for s=A
disp(s);
end

The reader may verify that the above code also gives the same results.
470   ◾    Appendix A: MATLAB® Primer

Next, we will write a small code that uses the for loop for computing the terms of a
Fibonacci series. A Fibonacci series is a series comprising [1 1 2 3 5 8 13 21 ...],
where each element is the sum of the preceding two elements.

Example A.4  Fibonacci Series Using for Loop

Problem: Write a code that computes the first n terms of a Fibonacci series.
Solution: The following script computes the Fibonacci series:

% Compute n terms of a Fibonacci series

n=10;
fSeries=ones(n,1); % Initialize the series
for i=3:n
fSeries(i)=fSeries(i-1)+fSeries(i-2);
end
disp(fSeries')

The result of executing the above code is the first ten terms of the series:

>> fibo
1 1 2 3 5 8 13 21 34 55

Astute readers will notice that the for loop starts with an initial value of 3. This is
done because the first two terms of the series are given to be 1, and the calculation of
the series starts from the third term.
The other construct that can be used for iteratively executing a block of code is the
while loop:

while <condition>
<block of commands that are repeated>
end

The while loop keeps executing as long as the abovementioned <condition> is true.
If the condition becomes false at any time, MATLAB finishes executing the block of the
code, reaches the end line, and exits the loop. If the <condition> evaluates as false
­during the first instance, the block of commands within the while construct are not exe-
cuted. If the condition never becomes false, we get an infinite loop (which needs to be
interrupted using Ctrl-C).
The reader is encouraged to use the next example as a test example to check their under-
standing of the while loop.
 Appendix A: MATLAB® Primer   ◾    471

Example A.5  The while Loop

Problem: For each of the three cases below, identify the response from MATLAB to
test your understanding of the while loop.
Case 1: How many times is the while loop expected to run?
i=1;
while i<5
disp(i);
i=i+1;
end

Case 2: How many times is the while loop expected to run?

i=10;
while i<5
disp(i);
i=i+1;
end

Case 3: How many times is the while loop expected to run?

i=1;
while i<5
disp(i);
i=i-1;
end

Solutions:

1. The loop will run four times. In the fourth iteration, the value of i is incre-
mented to 5; the condition i<5 computes as false, and the loop does not execute
the fifth time.
2. The commands within the loop will not execute at all because, at the first instance,
the condition i<5 is false.

Here, it will run in an infinite loop because the condition i<5 always evaluates as true
since i is decremented.
This completes our discussion of iterative loops.

A.6.2 Conditional if Block
The syntax for the if-then-else block is
if <condition>
<statements-1 evaluated for true>
else
<statements-2 evaluated for false>
end
472   ◾    Appendix A: MATLAB® Primer

Here, <condition> refers to any comparison (including Boolean expression) that evaluates
as either true or false. If the condition is true, the first block, statements-1, is executed;
otherwise, the second block, statements-2, is executed. Nesting of multiple if-blocks is
permitted. Let us write a code for printing all prime numbers between 1 and n.

Example A.6  Using if Statement

Problem: Write a code to display prime numbers between 1 and n.
Solution:

n=20;
for i=1:n
if isprime(i)
disp([num2str(i), ' is a prime number']);
end

end

The command to display is only executed when isprime(i) evaluates as true

(i.e., when i is a prime number), giving the following result:

2 is a prime number
3 is a prime number
5 is a prime number
7 is a prime number
11 is a prime number
13 is a prime number
17 is a prime number
19 is a prime number

This concludes our introduction to a conditional if statement. If there are multiple cases
to be analyzed, the switch-case statements are more efficient and readable. Interested
readers may look up MATLAB help for the switch statement, if required.

A.7 FUNCTION HANDLES
MATLAB functions were discussed in Section A.5. A function to calculate specific heat was
written in Example A.3. The function was used to calculate the specific heat at any desired
temperature as

>> cp=spHeat(T_gas);

There are several occasions, as we will see throughout this book, where a function needs
to be provided to another function for performing numerical computations. Function
handle is MATLAB’s way to provide or pass on a function to another function. As per
MATLAB help documentation, a function handle is a “data type that stores an association
 Appendix A: MATLAB® Primer   ◾    473

to a function.” The function handle for the spHeat function may be written in one of the
following two ways:

1. More convenient form: @spHeat

2. More efficient form (which I use in this book): @(T) spHeat(T)

Let us deconstruct the second approach, which is called the anonymous function method
and was introduced in MATLAB quite recently.* The symbol @ indicates function handle
and is immediately followed by comma-separated input arguments in round brackets and
then the function name (note that in the spHeat example, the function name is the same
as the file name). This function handle can then be passed to another function for further
computations.
For example, the enthalpy at a temperature, say 450 K, is computed as

450

ò
+ c p (T ) d T
0
H 450 = H 298 (A.2)
298

The integral in the above equation can be computed using the MATLAB command
integral (see Appendix D). This command requires one to pass the function handle
to the function cp(T). This can be done as follows:

>> IntCp = integral(@(T) spHeat(T), 298,450);

The anonymous function handle passed on to the MATLAB solver integral is under-
lined above.
This brings us to the end of this primer on MATLAB.

*  For this reason, students and practitioners still prefer the @spHeat form of function handle. However, the anonymous
function method is more modern and versatile and will be followed in this book. Readers are however free to follow the
method of their choice.
Appendix B: Numerical
Differentiation

B.1 GENERAL SETUP
Differentiation is one of the essential tools in engineering on which the foundation of cal-
culus rests. For a function y = f(t), it is defined as

dy f ( t + Dt ) - f ( t )
= lim (B.1)
dt t ®0 Dt

The shorthand representation of the first derivative is f  ′(t). The value of the derivative eval-
uated at a certain point, t = ti, is represented as f  ′(ti). The following notations will be used
throughout:

d
f ¢ (ti ) º f (t )
dt ti

whereas

d
f (ti ) = 0
dt

The former indicates the value of the derivative of f(t) at t = ti, whereas the latter indicates
derivative of the (constant) value that the function achieves at t1.
The second derivative is defined as

d 2 y d æ dy ö
f ¢¢ ( t ) º = (B.2)
dt 2 dt çè dt ÷ø

Likewise, higher-order derivatives are also defined.

Geometrically, the first derivative is the slope of tangent of the curve f(t) vs . t at the point
t = ti. It represents the rate at which the function f(t) is changing at ti. The second derivative
is the rate at which the slope of f(t) changes.
475
476   ◾    Appendix B: Numerical Differentiation

(a) (b)

FIGURE B.1  Schematic of the first derivative, f  ′(t) and numerical approximation using (a) forward
and (b) central difference formulae.

Numerical differentiation involves approximating the derivative with an appropriate

finite difference formula. The simplest one seems evident from Equation B.1—choose a
step-size, Δt or h, small enough and apply the difference formula:

f (ti + h ) - f (ti )
f ¢ (ti ) »
h

This is the forward difference formula for finding the first derivative of a function. A formal
derivation, error analysis, and trade-off between round-off and truncation errors (also see
Chapter 1) will be presented in the rest of this chapter.
Figure B.1 shows a schematic representation of derivative as a (slope of) tangent to the
curve in the Y–T plane. The slope of the line connecting the points a and (a + h) is the
approximation using forward difference formula. The approximation can be improved by
reducing h. Alternatively, a different method (called central difference formula) may be used,
where the derivative is approximated as the slope of the line connecting (a − h) and (a + h).
As indicated in the schematic in Figure B.1, the central difference formula better approxi-
mates the true derivative.
Numerical differentiation finds several applications. A large number of numerical
techniques for solving nonlinear algebraic equations (Chapter 6), implicit ODEs and dif-
ferential algebraic equations (Chapter 8), and regression (Chapter 10) requires deriva-
tives (or Jacobian) to be calculated. For example, in the Newton-Raphson method of
Chapter 6

x (i +1)
=x (i )
-
( )
f x( )
i

(B.3)
f ¢( x( ) )
i

if the derivative f ′(x) is not available, numerical differentiation may be used instead.
Solutions to partial differential equations (Chapters 4 and 10) using finite difference
approximation discussed in this chapter is popular for generic engineering problems.
 Appendix B: Numerical Differentiation   ◾    477

Another application is in the calculation of heat or mass flux. If the walls of a heat
exchanger are at a higher temperature than the fluid in the channel, a temperature gradient
exists. For even slightly complex geometries, the net heat flux into the fluid

dT
J = -l f (B.4)
dz

often needs to be calculated numerically. Other applications include finding the rate-
determining step in a complex network of reactions, analyzing sensitivity of system perfor-
mance to various parameters, as well as in data analytics where gradient (first derivative)
and curvature (second derivative) can reveal critical information about the qualitative
nature of systems.

B.2 NUMERICAL DIFFERENCE FORMULAE

Numerical differentiation rules are computed from Taylor’s series approximation, which
provides both differentiation formulae as well as error estimates. As discussed in Chapter 1,
these refer to truncation errors since they result from truncating an infinite series to a finite
number of terms. Usually, retaining a larger number of terms in the series expansion results
in a more accurate approximation of numerical derivatives. Derivation and error analysis
of first and higher derivatives will be presented in this section.

B.2.1 First Derivatives
Consider the Taylor’s series expansion of f(a + h):

h2 h3
f ( a + h ) = f ( a ) + hf ¢ ( a ) + f ¢¢ ( a ) + f ¢¢¢ ( a ) +  (B.5)
2 3!

Retaining the term in f  ′(a) and moving the other terms to the left-hand side, we get

f (a + h ) - f (a ) é h h2 ù
f ¢ (a ) = - ê f ¢¢ ( a ) + f ¢¢¢ ( a ) + ú (B.6)
h ë2 6 û

The first term on the right-hand side is the forward difference approximation of f  ′(a),
h
whereas the terms in square brackets represent the error. Here, f ¢¢ ( a ) is the leading error
2
( )
term. Hence, the forward difference formula is O h1 accurate. Using the mean value theo-
rem, the above equation may be written as

f (a + h ) - f (a ) h
f ¢ (a ) = - f ¢¢ ( x ) (B.7)
 h   2  
Fwd . diff Error

There exists a point ξ ∈ [a, (a + h)] such that the terms in the brackets of Equation B.6 may
be equivalently written in the above form.
478   ◾    Appendix B: Numerical Differentiation

Additional nodal points are required to derive a more accurate formula for the first
derivative. The central difference formula uses f(a − h), in addition to f(a) and f(a + h), to
approximate the derivative f  ′(a) (hence the name). Again, Taylor’s series expansion is

h2 h3
f ( a - h ) = f ( a ) - hf ¢ ( a ) + f ¢¢ ( a ) - f ¢¢¢ ( a ) +  (B.8)
2 3!

Subtracting from Equation B.5

h3
f ( a + h ) - f ( a - h ) = 2hf ¢ ( a ) + f ¢¢¢ ( a ) +  (B.9)
3

This leads to the following central difference formula:

f ( a + h ) - f ( a - h ) h2
f ¢ (a ) = - f ¢¢¢ ( x ) (B.10)
 2h   6 
Central diff Error

Comparing the forward and central difference formulae in Equations B.7 and B.10 demon-
strates what I argued in the schematic of Figure B.1. Since the forward difference formula
( )
scales as O ( h ), whereas the central difference formula scales as O h2 , the latter is more
accurate for the same choice of step-size h. This has already been observed in Chapter 1 and
will be demonstrated later in this section.
Similar to the forward difference formula, it is easy to observe that the backward differ-
ence formula for the first derivative is

f (a ) - f (a - h )
h
f ¢ (a ) = f ¢¢ ( x )
+ (B.11)
 h   2  
Bkd difference Error

The backward difference formula has the same accuracy as the forward difference formula.
In certain situations, a forward (or backward) difference formula with a higher accuracy
is needed, for example, to calculate the heat flux at the boundary with higher accuracy or in
solving PDEs (see Chapter 4). A three-point forward difference formula would be used in
such a case. Here, the values f(a) , f(a + h) and f(a + 2h) are used to calculate the derivative
f′(a). This is in contrast to f(a − h) , f(a) and f(a + h) used in the central difference formula.
Taylor’s series expansion of f(a + 2h) is

4h 2 8h3
f ( a + 2h ) = f ( a ) + 2hf ¢ ( a ) + f ¢¢ ( a ) + f ¢¢¢ ( a ) +  (B.12)
2! 3!

Note that subtracting 4f(a + h) from the above equation eliminates the term in f ″(a), and
the third-order term becomes the leading term. This can indeed be done by observation.
 Appendix B: Numerical Differentiation   ◾    479

However, as the functions become more complex, or if higher-order formulae are required,
a more versatile method called method of undetermined coefficients may be used to compute
the approximation. For example, the three-point forward difference formula is written as a
weighted sum:

f ¢ ( a ) = w1 f ( a ) + w2 f ( a + h ) + w3 f ( a + 2h ) (B.13)

Using the Taylor’s series expansion, the above may be written as

é h2 h3 ù
f ¢ ( a ) = w1 f ( a ) + w2 ê f ( a ) + hf ¢ ( a ) + f ¢¢ ( a ) + f ¢¢¢ ( a ) + ú
ë 2 3! û
é 4h2 8h3 ù
+ w3 ê f ( a ) + 2hf ¢ ( a ) + f ¢¢ ( a ) + f ¢¢¢ ( a ) + ú (B.14)
ë 2 3! û

Collecting terms in f(a), f  ′(a), etc., together

h2
f ¢ ( a ) = ( w1 + w2 + w3 ) f ( a ) + ( w2 + 2w3 ) hf ¢ ( a ) + ( w2 + 4w3 ) f ¢¢ ( a )
2
h3
+ ( w2 + 8w
w3 ) f ¢¢¢ ( a ) +  (B.15)
3!

Comparing with the left-hand side, the coefficient of the second term on the right-hand
side should equal 1, whereas the others should be zero. Thus, we obtain three equations in
three unknowns:

w1 + w2 + w3 = 0
w2 + 2w3 = 1 / h (B.16)
w 2 + 4w 3 = 0

The above equations can be solved to obtain

-3 2 -1
w1 = , w2 = , w3 = (B.17)
2h h 2h

The coefficient of the leading error term is

2
w2 + 8w3 = -
h
480   ◾    Appendix B: Numerical Differentiation

Thus, one can derive that the error term is given by

h2
E=- f ¢¢¢ ( x ) (B.18)
3

The three-point forward difference formula is thus given by

-3 f ( a ) + 4 f ( a + h ) - f ( a + 2h ) h2
f ¢ (a ) = - f ¢¢¢ ( x ) (B.19)
2h 3

This is more accurate than the standard forward difference formula.

A three-point backward difference formula may be derived in a similar manner. One can
verify that substituting h ← (−h) in Equation B.19 will yield a three-point backward differ-
ence formula.

B.2.2 Second Derivative
Having derived the formula for f  ′(a), let us now determine higher-order differentiation
formulae. Unlike first derivatives, at least three nodes are required for computing the sec-
ond derivative. The central difference formula for f  ″(a) can be derived by inspection from
Equations B.5 and B.8. Note that adding the two eliminates the term in f  ′(a):

é h2 h4 ù
f (a + h ) + f (a - h ) = 2 ê f (a ) + f ¢¢ ( a ) + f ¢¢¢¢ ( a ) + ú (B.20)
ë 2 4! û

The odd-powered terms of the Taylor’s series vanish. The fourth-order term becomes
the leading error term. Thus, the formula and error estimate for the central difference is
given by

f ( a + h ) - 2 f ( a ) + f ( a - h ) h2
f ¢¢ ( a ) = 2
- f ¢¢¢¢ ( x ) (B.21)
 h
  12
  
Formula Error

( )
Thus, the central difference formula for f  ″(a) is O h2 accurate. This formula can also be
derived using method of undetermined coefficients, discussed earlier, by writing

f ¢¢ ( a ) = w1 f ( a - h ) + w2 f ( a ) + w3 f ( a + h )

An interested reader can verify that this method yields the same formula and error infor-
mation as derived in Equation B.21.
In a similar manner, higher-order derivatives can also be derived. Since these formulae
are not required in this book, I will not discuss them further. Still, the method of undeter-
mined coefficients forms a useful template to derive these formulae, including cases with
unequal grid size.
 Appendix B: Numerical Differentiation   ◾    481

Example B.1  Numerical Differentiation

Problem: Find f  ′(x) for the function f(x) = tan−1(x) at x = 1. Also compute the error.
Solution: The following code is used for numerical differentiation:

% Problem Setup
a=1; h=0.01;
trueVal=1/(1+a^2);
%% Compute numerical derivatives and errors
% Forward difference for f’(x)
d1_fwd=(atan(a+h)-atan(a))/h;
err1_fwd=abs(d1_fwd-trueVal);
% Central difference for f’(x)
d1_ctr=(atan(a+h)-atan(a-h))/(2*h);
err1_ctr=abs(d1_ctr-trueVal);
% 3-point forward difference for f’(x)
d1_3pt=(-3*atan(a)+4*atan(a+h)-atan(a+2*h))/(2*h);
err1_3pt=abs(d1_3pt-trueVal);
% Display Results
disp([d1_fwd, d1_ctr, d1_3pt]);
disp([err1_fwd, err1_ctr, err1_3pt]);

With the step-size h = 0.01, the forward difference formula gave the numerical deriva-
tive value as 0.4975. For all other cases, the displayed value was 0.5000. Hence,
it is more instructive to see the errors. The results below show the errors for forward,
central, and 3-point forward difference formulae for various values of h:

h err1_fwd err1_ctr err1_3pt

0.01 0.0025 8.333e-6 1.666e-5
0.001 2.499e-4 8.333e-8 1.667e-7
1e-4 2.500e-5 8.33e-10 1.666e-9
1e-5 2.500e-6 8.83e-12 2.276e-12
1e-6 2.501e-7 4.11e-11 1.522e-10

Clearly, the central and three-point forward difference formulae are more accurate
than the standard forward difference formula.
Moreover, when step-size is reduced by one order of magnitude, the error in for-
ward difference formula decreases by one order of magnitude, whereas the errors in
central and three-point forward difference formulae decrease by two orders of magni-
( )
tude. This is a consequence of the fact that the latter two are O h2 accurate, whereas
the standard forward difference formula is O ( h ) accurate.
For the initial few step-sizes, the error in the central difference formula is approxi-
mately half of that in three-point forward difference formula. This approximate
relationship is expected, comparing the error terms for the two formulae from
Equations B.10 and B.19.
482   ◾    Appendix B: Numerical Differentiation

Finally, notice that the error in central and three-point forward difference formulae is
greater at h = 10−6 than it is at h = 10−5. This will be the topic of discussion in the next
section.

B.2.3 Effect of Round-Off Error

The trade-off between truncation and round-off errors is apparent from Example B.1. It is
also demonstrated in Chapter 1. In the previous section, we observed that the trunca-
tion error decreased as the step-size was reduced. The round-off error, on the other hand,
increases as the step-size is reduced. Calculation of the numerical derivatives requires sub-
traction between two (or more) numbers that are very close to each other. The smaller the
step-size, h, for accuracy of the numerical scheme, the closer are the two numbers and,
hence, the greater is the effect of round-off errors. There is an optimal value of h for which
the total error is minimized. It is apparent from Example B.1 that this optimum lies some-
where in the vicinity of h ~ 10−5.
Consider the forward difference formula from Equation B.7:

f (a + h ) - f (a ) h
f ¢ (a ) = - f ¢¢ ( x ) (B.7)
h 2

The computer representation of a value differs from its true value due to machine precision.
So, the true value of f(a) differs from the value represented in the computer, f ( a ).
Consider the example of tan−1(1). The true value is 0.785398… (additional digits are
ignored for this example). Presuming that there is a computer using the decimal number
system (as discussed in Chapter 1), which uses a four-digit representation of the mantissa,
this number is represented in the “decimal computer” as tan -1 ( -1) = 0.7853. The relative
error between the two is bounded by the machine precision. Thus, one can get the following
relationship between true value and the computer representation:

f ( a ) = f ( a ) (1 + e ) (B.22)

The numerical derivative is given by

f (a + h ) - f (a )
f ¢ (a ) = (B.23)
h
Subtracting the two, the net error is given by

Enet = f ¢ ( a ) - f ¢ ( a ) (B.24)

f (a + h ) - f (a ) h
= e+ f ¢¢ ( x ) (B.25)
h 2

2emach h
£ f ( x1 ) + f ¢¢ ( x ) (B.26)
h 2
 Appendix B: Numerical Differentiation   ◾    483

where both ξ, ξ1 ∈ [a, a + h]. The first term is the round-off error, and the second term is the
truncation error. The optimum value of h that minimizes the net error is obtained by dif-
ferentiating the above equation and equating it to zero:

d 2e
Enet = - mach f ( x1 ) + f ¢¢ ( x ) = 0
dh h2

Thus

f ( x1 )
hopt = 2 e mach (B.27)
f ¢¢ ( x )

A practical result for forward difference would then be

1/2
hopt ~ ëéemach ùû (B.28)

Arguing on similar lines, the truncation error in the central difference formula is

Etrunc = c1h2

whereas the round-off error is

c2
Er -off =
h

Since Enet = |Etrunc| + |Er − off|, it is easy to show that the optimum value of step-size for the
central difference formula is

1/3
hopt ~ ëéemach ùû (B.29)

Since the machine precision in MATLAB is 2 × 10−16, the optimum value of step-size is of
the order of hopt ∼ 0.6 × 10−5. The observation in Example B.1 is thus in agreement with the
optimal step-size value derived herein.
Appendix C: Gauss
Elimination for
Linear Equations

C.1 BASIC GAUSS ELIMINATION

C.1.1 A Simple Example
Gauss Elimination is a popular method for solving linear equations. The basic Gauss
Elimination is discussed here using the following example:

x1 + x2 + x3 = 4
2 x1 + x2 + 3x3 = 7 (C.1)
3x1 + 4 x2 - 2 x3 = 9

The aim in this example is to solve the system of linear equations given above. This can be
expressed in the following standard form:

é1 1 1 ù é x1 ù é 4 ù
ê úê ú ê ú (C.2)
ê2 1 3 ú ê x2 ú = ê7 ú
ê3 4 -2 ú ê x3 ú ê 9 ú
û ëû ëû
ë
A x b

The above system of equations has a unique solution if the determinant of A is nonzero.
A more general way of expressing the same statement is that a unique solution exists if A
is a full-rank matrix rank(A) = n. If the rank of A is not n, then the system of equations may
have infinitely many solutions or no solution. If rank(A) = m < n, it implies that only m rows
of A are linearly independent, whereas the other rows can be written as a linear combina-
tion of these m rows. If the vector b also satisfies the same linear combination, then there are
infinitely many solutions to the equations. Consider the following equations:

x1 + x2 = 1

2 x1 + 2 x2 = a

485
486   ◾    Appendix C: Gauss Elimination for Linear Equations

Clearly, the left-hand side of the second equation is twice that of the first. Thus, rank(A) =
1 and the system of equations does not have a unique solution. If the right-hand side, a, is
also twice that of the right-hand side of the first equation, then the two lines are collinear
and there are infinitely many solutions. If a ≠ 2, then there is no solution. Summarizing,

• The system of equations has a unique solution if rank(A) = n.

• Else, there are infinitely many solutions if rank([A  b]) = rank(A).
• There are no solutions otherwise.

Consider how we solve the above set of three equations given in Equation C.1. We will use
the first equation to eliminate x1 from the second and third equations, that is, R2 − 2R1 and
R3 − 3R1:

x1 + x2 + x3 = 4
0 - x2 + x3 = -1 (C.3)
0 + x2 - 5x3 = -3

Now, we can use the last two equations to eliminate x2 and obtain the value of x3:

-4 x3 = -4

Thus, we now have the following:

x1 + x2 + x3 = 4
0 - x2 + x3 = -1 (C.4)
0 + 0 - 4 x3 = -4

The above equation has reduced the overall system of equations to one where the matrix A
has an upper triangular form. The process we followed is called Gauss Elimination. The final
solution is obtained using a procedure called back-substitution. The final equation is used to
obtain the value of x3 = 1. Thereafter, this value can be substituted in the second equation.
This will yield the value of x2 = 2. Substituting these values in the first equation yields x1 = 1.
Let us revisit the steps used in solving the above set of equations:

• In the first sequence of steps, the first equation was used to eliminate x1 from all the
remaining equations.
• Thereafter, the second equation was used to eliminate x2 from the remaining equa-
tions. No change was made to the first equation.
• For a larger system of equations, the procedure continues until the right-hand side
involves an upper triangular matrix. In each sequence of steps, the ith equation is used
to eliminate xi from all subsequent equations.
 Appendix C: Gauss Elimination for Linear Equations   ◾    487

The following code demonstrates the use of Gauss Elimination with back-substitution
for this problem. This is not a generalized code. It simply follows the steps laid out in the
­example above.

Example C.1  Naïve Gauss Elimination* Only

Problem: Write a code for naïve Gauss Elimination with back-substitution for the lin-
ear system of Equation C.1.
Solution: The first step is to formalize the steps given above. The first step is to
obtain an augmented matrix, Ab = [A b].
The first row is used to eliminate x1 from rows 2 and 3. Here row-1 is called the pivot
row. Thereafter, the second row is used to eliminate x2 from the third row. With this,
the Gauss Elimination procedure is complete. The code for the same is given below:

% Solve Ax = b using Naive Gauss Elimination

A = [1 1 1; 2 1 3; 3 4 -2];
b = [4;7;9];
n = length(A);
%% Gauss Elimination
% Get augmented matrix
Ab = [A, b];

% With A(1,1) as pivot Element

k=1;
for i=2:3
alpha=Ab(i,1)/Ab(1,1);
Ab(i,1:end)=Ab(i,1:end) - alpha*Ab(1,1:end);
end

% With A(2,2) as pivot Element

k=2;
for i=3:3
alpha=Ab(i,2)/Ab(2,2);
Ab(i,2:end)=Ab(i,2:end) - alpha*Ab(2,2:end);
end

Let us verify the matrix Ab obtained after Gauss Elimination:

Ab
1 1 1 4
0 -1 1 -1
0 0 -4 -4

This is same as the result obtained in Equation C.4.

*  The reason why we call this naïve Gauss Elimination will be come clear in Section C.3.
488   ◾    Appendix C: Gauss Elimination for Linear Equations

Now that the above results are in the reduced upper triangular form of Equation C.4,
we can back-substitute the values to obtain x. First, x3 can be calculated from the last row:

Ab3,end
x3 = =1 (C.5)
Ab3,3

Thereafter, it can be used to calculate x2 as

Ab2,end - ( Ab2,3 x3 )
x2 = =2 (C.6)
Ab2,2

followed by calculation of x1 as

Ab1,end - ( Ab1,2 x2 + Ab1,3 x3 )

x1 = (C.7)
Ab1,1

This is shown in the continuation of the code in the example below.

Example C.1 (Continued)  (Back-Substitution)

The following code implements back-substitution, which is part of the same naïve
Gauss Elimination code.

%% Back-Substitution
x=zeros(3,1);
for i=n:-1:1
x(i)=( Ab(i,end)-Ab(i,i+1:n)*x(i+1:n) ) / Ab(i,i);
end

The result of running the above code with back-substitution is

x =
1
2
1

which is the solution obtained analytically earlier.

The strategy I have followed in Example C.1 is the following: The Gauss Elimination part of
the code is written for a specific 3 × 3 system example, whereas the back-substitution part is
written as a general-purpose code for any n × n system. This is intentional. Converting the
Gauss Elimination code to a general n × n system of equations is left as an exercise for the
reader. The building blocks are already present in the above code, and the algorithm for a
generic solver is discussed presently.
 Appendix C: Gauss Elimination for Linear Equations   ◾    489

C.1.2 Algorithm for Naïve Gauss Elimination

A few definitions are in order before we formalize the steps in Gauss Elimination. In the kth
sequence of steps, the kth equation is used to eliminate the coefficients of xk in subsequent
equations. In this kth step, the diagonal element Ak , k is called the pivot element, and the kth
row is the pivot row. The kth column is called the pivot column, with the procedure focusing
on elements below the diagonal only. Thus, the procedure for naïve Gauss Elimination is as
follows:

• Obtain an augmented matrix Ab = [A, b];.

• Set k = 1 so that Abk , k is the pivot element.
• Use the pivot element to eliminate coefficients Abi , k in the pivot column through row
operations for i = (k + 1) to n:
• Set i = k + 1
• Set

aik = Abi ,k /Abk ,k (C.8)

• Perform the row operation Ri ← Ri − αikRk where “←” represents the assignment
­operator.* Here, Ri represents the ith row, that is, Ab(i,:). Note that since the
pivot row elements Abk , 1 , Abk , 2 ,  …  , Abk , k − 1 are already zero due to previous row
operations, the above needs to be performed only for elements after the diagonal
element. In other words

Abi , j = Abi , j - aik Abk , j , for j = k to end (C.9)

In MATLAB, the above row operation can be done efficiently using the colon
notation to indicate entire row:

Ab(i,k:end)=Ab(i,k:end)-alpha*Ab(k,k:end);

Compare this with the underlined statements in Example C.1 to understand how
the row operation is coded to simplify the calculation of Equation C.9.
• Increment i and repeat the previous two steps until all the elements in the pivot
column are eliminated, that is, until i = n.
• Increment k so that the next row is the pivot row and Ak, k is the pivot element.
Repeat the elimination steps until Ab is an upper triangular matrix, that is, until
k reaches (n − 1).

*   I use the assignment operator ← in linear equations chapters to avoid ambiguity. This is to avoid readers interpreting
R2 = R2 − αR1 as a linear equation. When I need to use the notation R2( ) = R2( ) - aR1( ), the assignment operator is not
i +1 i i

required because there is little scope of ambiguity.

490   ◾    Appendix C: Gauss Elimination for Linear Equations

After the Gauss Elimination steps, Ab is an upper triangular matrix. Let us say that this
reduced matrix represents the following modified equation:

Ux = b (C.10)

Note that the matrix modified after row eliminations is related to the above as Ab = [U b].
Row eliminations do not affect the desired solution, x, as we have seen that in the reduction
for the example in Equation C.2. For this example, the reader may verify that

é1 1 1 ù é x1 ù é 4 ù
ê úê ú ê ú (C.11)
ê0 -1 1 ú ê x2 ú = ê -1ú
ê0 -4 úû êë x3 úû êë -4 úû
ë0 
U x b

Note the equivalence between row operations described in the algorithm above and the
familiar equation solving procedure through elimination that I described to reduce a set of
equations (C.1 through C.4).

C.1.3 Back-Substitution
Due to the upper triangular form of the matrix in Equation C.11, the solution is obtained
by starting from the last row. Specifically

b3 Ab
x3 = = 3,end = 1
U 3, 3 Ab3,3

Thereafter

Ab2,end - ( Ab2,3 x3 )
x2 = =2 (C.12)
Ab2,2

and

Ab1,end - ( Ab1,2 x2 + Ab1,3 x3 )

x1 = (C.13)
Ab1,1

Generalizing, the steps in back-substitution include

Abn,end
xn = (C.14)
Ab(n,n)

 Appendix C: Gauss Elimination for Linear Equations   ◾    491

Starting with the end, with i = (n − 1) down until i = 1

å
n
Abi ,end - Abi , j x j
j =i +1
xi = (C.15)
Ab(i ,i )

C.2 LU DECOMPOSITION WITHOUT PIVOTING

The idea of LU decomposition is that any matrix A can be factorized as a product of two
matrices, a lower triangular matrix L and an upper triangular matrix U:

A = LU (C.16)

It should be noted that the decomposition is not unique. Several different factorizations into
L and U matrices can be obtained. If we were to multiply Equation C.11 by L on both sides

(C.17)
x = L
LU b
A b

This is the algorithm behind the Doolittle method for LU decomposition. The upper trian-
gular matrix U is obtained using Gauss Elimination. It turns out that the elements of the
lower triangular matrix are the values of αik used during factorization, as per Equation C.8.
The lower triangular matrix to complete the LU decomposition is then given by

é 1 0 0  0ù
ê ú
êa21 1 0  0ú
L = êa31 a32 1  0ú (C.18)
ê ú
ê     ú
êan1 a n2 a n3  1 úû
ë

The following demonstrates LU decomposition for the previous example.

Example C.2  LU Decomposition

Problem: Perform LU decomposition for the problem in Example C.1.
Solution: The main idea of LU decomposition using the Doolittle algorithm is to
store the values of αki and store them in the correct location of the L matrix. This is
shown in the following code:

% Solve Ax = b using Naive Gauss Elimination

% Modified for LU decomposition
A = [1 1 1; 2 1 3; 3 4 -2];
b = [4;7;9];
n = length(A);
492   ◾    Appendix C: Gauss Elimination for Linear Equations

%% Gauss Elimination
% Get augmented matrix
Ab=[A, b];
L=eye(n);

% With A(1,1) as pivot Element

k=1;
for i=2:3
alpha=Ab(i,1)/Ab(1,1);
Ab(i,1:end)=Ab(i,1:end) - alpha*Ab(1,1:end);
L(i,k)=alpha;
end

% With A(2,2) as pivot Element

k=2;
for i=3:n
alpha=Ab(i,2)/Ab(2,2);
Ab(i,2:end)=Ab(i,2:end) - alpha*Ab(2,2:end);
L(i,k)=alpha;
end

%% Back-Substitution
x = zeros(3,1);
for i=n:-1:1
x(i)=( Ab(i,end)-Ab(i,i+1:n)*x(i+1:n) ) / Ab(i,i);
end

The core of the code has remained the same, with the addition of the underlined state-
ments: First, the matrix L is initialized as identity, followed by inserting values of αik in the
first column and then inserting αik in the second column. This completes the L matrix:

L =
1 0 0
2 1 0
3 -1 1

It is easy to verify that the product L*U indeed gives back the matrix A:

>> U=Ab(1:n,1:n);
>> Acheck=L*U;

Indeed, the matrix Acheck is equal to the original matrix A.

It should be noted that LU decomposition really needs to work on only the matrix
A and not the augmented matrix Ab. I retained the original code, which used the
Ab matrix for pedagogical reasons. LU decomposition is actually performed on the
matrix A itself.
 Appendix C: Gauss Elimination for Linear Equations   ◾    493

LU decomposition can be used to solve a linear equation Ax = b. It consists of three steps.
First, LU decomposition is used to obtain matrices L and U. Since Lβ = b, as per Equation
C.17, the second step is to obtain β from L and b. This is done using forward substitution,
which works exactly like backward substitution method but starting with the first row. Note
that the vector β resulting after forward substitution step is nothing but the last column of
the Ab matrix. Finally, the third step is backward substitution to solve Ux = β, which was
discussed earlier.
The utility of LU decomposition is not really in solving a single equation, Ax = b.
Instead, it is very useful if we need to solve a series of equations Ax[i] = b[i], where the
matrix A remains constant while vector b changes. The greatest effort in solving linear
equation is in factorization/elimination. Hence, factorizing a matrix once and using
forward/backward substitutions multiple times reduces the effort. An example of a sys-
tem where Ax[i] = b[i] is solved multiple times is covered in Chapter 7, where the right-
hand side is a nonlinear term; b[i + 1] = g(x(i)) is nothing but the function evaluated at
the current guess, followed by solving the nonlinear equation to obtain the new guess,
x(i + 1) ≡ x[i + 1].
Another use from a numerical methods perspective is that sparse matrices, of the
type discussed in Chapter 7, can sometimes be factorized into L and U using efficient
algorithms. Thus, this method becomes a computationally useful means to solve such
equations.
The MATLAB code for obtaining LU decomposition is lu(A). The result of this code is
different from the algorithm discussed here, since it uses partial pivoting (see next section).
Thus, the final result is of the form LU = PA, where P is a permutation matrix that accounts
for row exchanges done in the partial pivoting method.

C.3 PARTIAL PIVOTING
I have referred to partial pivoting method a couple of times. Let us look into what this
means. As a simple, motivating example, consider that the linear system of equations was
instead given as

x1 + x2 + x3 = 4
2 x1 + 2 x2 + 3x3 = 9 (C.19)
3x1 + 4 x2 - 2 x3 = 9

The first set of row operations using first row as the pivot row yields

é1 1 1 4ù
ê ú
Ab = ê0 0 1 1ú (C.20)
ê0 1 -5 -3úû
ë
494   ◾    Appendix C: Gauss Elimination for Linear Equations

The naïve Gauss Elimination, as discussed earlier, cannot continue from this stage because
the next pivot element A2 , 2 = 0. However, if we were to solve the equations manually, we
would just switch the last two equations and use the second equation to obtain the value
of x3. The matrix after exchange of the last two rows becomes

é1 1 1 4ù
ê ú
Ab = ê0 1 -5 -3ú (C.21)
ê0 0 1 1 úû
ë

This is the crux of Gauss Elimination with partial pivoting. Partial pivoting is basically a row
exchange operation carried out at each step. Unlike the example mentioned here, the aim of
partial pivoting is broader. A premature end to Gauss Elimination is not the only problem.
Another issue is round-off errors. In the case of examples where two large numbers are
subtracted, pivoting improves the performance of Gauss Elimination. For example, if the
second equation was

2 x1 + ( 2 + d ) x2 + 3x3 = 9. ´´´

the diagonal element, A2 , 2, would become δ ≪ 1. This can lead to round-off errors because
of the subtraction of a close number and/or division by a small number. Recall that in back-
substitution, we compute x2 = (numerator)/A2 , 2.
Theoretical guarantees exist for Gauss Elimination with full pivoting, where both row
and column interchanges are allowed. However, partial pivoting, where only row inter-
changes are executed, is found to be equally useful in practice. Hence, all the numerical
solvers use Gauss Elimination with partial pivoting.
In the algorithm given in Section C.1.2, at any kth step, Ak , k, is the pivot element. In
naïve Gauss Elimination, the pivot element is used to eliminate coefficients Ai , k in the pivot
column below the diagonal. In case of Gauss Elimination with pivoting, an additional step
is added before this:

• When k is incremented, Ak , k becomes the pivot element.

• Compare the values of all the subdiagonal elements, Ai , k, in the same column (i ≥ k).
Exchange row k with the row that has highest absolute value of Ai , k in that column.
This is the pivoting step.
• Thereafter, continue with elimination as before, using the (new) pivot element for the
elimination of elements in the pivot column below the pivot element.

Consider the original example from Equation C.1. In the first step, with k = 1, we per-
form the pivoting step. The largest absolute value in the pivot column (column 1) is A3 , 1.
 Appendix C: Gauss Elimination for Linear Equations   ◾    495

Therefore, rows 3 and 1 are interchanged so that the new pivot element is the dominant
element in that column. The matrix Ab after the row interchange is

Ab =
3 4 -2 9
2 1 3 7
1 1 4

The elimination is then performed with α21 = 2/3 and α3 , 1 = 1/3. After appropriate row oper-
ations, the matrix becomes

Ab =
3.0000 4.0000 -2.0000 9.0000
0 -1.6667 4.3333 1.0000
0 -0.3333 1.6667 1.0000

Next, A2 , 2 is the pivot element. The elements in column 2 at and below the diagonal as
−1.6667 and −0.3333. Since the former has the largest absolute value, no row interchange
needs to be performed. The algorithm continues with α3 , 2 = 0.2 and yields

Ab =
3.0000 4.0000 -2.0000 9.0000
0 -1.6667 4.3333 1.0000
0 0 0.8000 0.8000

The matrix is now in upper triangular form. We also note that the α values used were

é * * *
ù
ê * *
ú
a = ê0.6667 ú
ê *ú
ëê0.3333 0. 2 úû

The following code is a modification of Example C.1 with partial pivoting included.

Example C.3  Gauss Elimination with Partial Pivoting

Problem: Solve Example C.1 using Gauss Elimination with partial pivoting.
Solution: The code in Example C.1 is modified to include verification of dominance
of the diagonal pivot element and column exchange. The other parts of the code
remain unchanged:

% Solve Ax = b using Naive Gauss Elimination

A = [1 1 1; 2 1 3; 3 4 -2];
b = [4;7;9];
n = length(A);
496   ◾    Appendix C: Gauss Elimination for Linear Equations

%% Gauss Elimination
% Get augmented matrix
Ab = [A, b];
% With A(1,1) as pivot Element
k=1;
pivotCol=Ab(k:n,k);
[~,idx]=max(abs(pivotCol));
idx=(k-1)+idx;
if (idx~=k) % Row interchange
pivotRow=Ab(k,:);
Ab(k,:)=Ab(idx,:);
Ab(idx,:)=pivotRow;
end
for i=2:3
alpha=Ab(i,1)/Ab(1,1);
Ab(i,1:end)=Ab(i,1:end) - alpha*Ab(1,1:end);
end
% With A(2,2) as pivot Element
k=2;
pivotCol=Ab(k:n,k);
[~,idx]=max(abs(pivotCol));
idx=(k-1)+idx;
if (idx~=k) % Row interchange
pivotRow=Ab(k,:);
Ab(k,:)=Ab(idx,:);
Ab(idx,:)=pivotRow;
end
for i=3:3
alpha=Ab(i,2)/Ab(2,2);
Ab(i,2:end)=Ab(i,2:end) - alpha*Ab(2,2:end);
end

%% Back-Substitution
x = zeros(3,1);
for i = 3:-1:1
x(i) = ( Ab(i,end)-Ab(i,i+1:n)*x(i+1:n) ) / Ab(i,i);
end

The underlined block has been added. The first line in that block extracts the pivot col-
umn from the diagonal to the last row into a vector pivotCol. The next line uses the
max function to find the index of the largest value in pivotCol. Since pivotCol
contained elements from row k to n, the original index in Ab matrix is (k-1)+idx.
The next three lines perform the row interchange: the kth row is stored in a dummy
variable pivotRow, the idxth row overwrites the kth row, and the stored pivot-
Row overwrites the idxth row.
 Appendix C: Gauss Elimination for Linear Equations   ◾    497

The readers can verify that the results from this code match the one obtained from
hand calculations and described immediately preceding this example.

Recall that I had mentioned that the MATLAB function lu gives LU decomposition with
partial pivoting, in the form PA = LU. Permutation matrix P takes care of the row inter-
changes due to pivoting. In this example, only rows 3 and 1 were exchanged. Therefore

é0 0 1ù
ê ú
P = ê0 1 0ú
ê1 0 0 úû
ë

As described earlier in this appendix, the values of L and U would be

é3 4 -2 ù é 1 0 0ù
ê ú ê ú
U = ê0 -1.6667 4.3333ú , and L = ê0.6667 1 0ú
ê0 0 0.8 úû ê0.3333 0. 2 1 úû
ë ë

One can now verify the lu command in MATLAB:

>> [L,U,P]=lu(A)
L =
1.0000 0 0
0.6667 1.0000 0
0.3333 0.2000 1.0000
U =
3.0000 4.0000 -2.0000
0 -1.6667 4.3333
0 0 0.8000
P =
0 0 1
0 1 0
1 0 0

Most commercial linear algebra solvers use the Gauss Elimination method with partial piv-
oting. It is not recommended to use naïve Gauss Elimination. In any case, linear algebra is a
very strong suite of MATLAB. Unless you have reasons otherwise, I recommend only using
the inbuilt MATLAB methods for linear algebra since they are well optimized.

C.4 MATRIX INVERSION
Matrix inversion is done by writing the following linear equations:

Ac1 = e1 , Ac 2 = e 2 , ¼, Ac n = en
498   ◾    Appendix C: Gauss Elimination for Linear Equations

where ei is the ith unit vector (i.e., column vector with all zeros, except ith element is 1). The
inverse of the matrix A contains vector ci as its ith column. Thus, iA=[c1, c2, ...,
cn]. The inverse is obtained by writing

A Aug = [A | In´n ùû

Two methods are popular among students and practitioners to solve a linear problem Ax = b
in MATLAB:

>> x=inv(A)*b;

or

>> x=A\b;

If solving a linear equation is the aim, one should always prefer the second method.*
Calculating inverse, as described above, takes a lot more computational effort than solving
a linear equation using the slash operator.

*  Note that slash operator also solves a linear least squares problem (see Chapter 10) if A is a non-square “tall” matrix with
nrows > ncols. So be careful!
Appendix D: Interpolation

D.1 GENERAL SETUP
Consider a car moving on a city road. The speed of the car recorded at every 10 s interval
is given in Table D.1.
Interpolation is used if one is interested in knowing the speed of the car at any time
between 0 and 90 s. Interpolation involves “joining the dots” with a smooth curve and read-
ing off the data on this fitted curve at any time of interest.
The above example of interpolating vehicle speed might be closer to chemical engi-
neering than you think. It is indeed used in simulating exhaust emissions performance
of a vehicle under test conditions. For example, the U.S. FTP-75 cycle is U.S. Federal Test
Protocol for emission testing of light-duty vehicles.* It involves testing a vehicle under
simulated urban driving conditions. Numerical simulation of a process under U.S. FTP-75
cycle would involve simulating the behavior at any arbitrary computational point within
the entire cycle. Since discrete measurements are limited to the measurement frequency,
interpolation is used to obtain data as a smooth continuous function of time. Figure D.1
shows the U.S. FTP-75 test cycle. As can be seen from the figure, the vehicle speed changes
frequently in the 1833 s test cycle. The data may be sampled at a rate of 10 to 0.1 Hz. If
simulation requires data between the sampling instances, interpolation is used to fill in
that data.
Another example would be in the modeling of solar or wind power sources. Solar radia-
tion or wind speeds may be available at discrete time instances, whereas numerical simula-
tion would require the information as a continuous function of time. Similar to the example
above, the intermediate data may be filled in using interpolation.
Let the tabulated data above be represented as n pairs: (t1, y1) , (t2, y2) ,  …  , (tn, yn). Here, t
is the independent variable, y is dependent variable, and ti and yi represent the data points.
Furthermore, we will try to fit some functional form, y = p ( t ) to the above data, such that
the fitted function passes through all the data points. In other words, each of the n data
points exactly satisfies the equation yi = p ( t i ).

*  Retrieved from: https://www.dieselnet.com/standards/cycles/ftp75.php (June 2016).

499
500   ◾    Appendix D: Interpolation

TABLE D.1  Data for Speed of a Moving Vehicle in Moderate Traffic Urban Conditions
Time (s) 0 10 20 30 40 50 60 70 80 90
Speed (km/h) 45 32 0 0 7 12 20 15 29 55

70.0
Cold start phase Stabilized phase Hot start phase
60.0

50.0
Speed (mile/h)

40.0

30.0

20.0

10.0

0.0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Time (s)

FIGURE D.1  Vehicle speed vs. time in a U.S. FTP-75 test cycle.

D.2 INTERPOLATING POLYNOMIALS
One of the first attempts at interpolation was the fit a polynomial function for p ( t ). When
there are n data points, one can fit an (n − 1)th order polynomial exactly to these data
points. Indeed, we can choose to write this polynomial as

p ( t ) = a0 + a1t + a2t 2 +  + an-1t n-1

However, more efficient forms of polynomial function have been introduced so that the
coefficients ai can be obtained in a more straightforward manner. Newton’s interpolating
polynomials take the form

pN ( t ) = a0 + a1 ( t - t1 ) + a2 ( t - t1 ) ( t - t 2 ) +  + an-1 ( t - t1 ) ( t - t n-1 ) (D.1)

Thus, at the first point, only the first (constant) term on the right-hand side is retained;
at the second point, the first two terms are retained; and so on. The coefficients a0 to an − 1
can be obtained as Newton’s divided difference polynomials. While this formula is more
generic, it will not be discussed in this section. Instead, conceptually simpler Lagrange
interpolating polynomials will be discussed, followed by Newton’s forward difference for-
mula. The latter is applicable when the independent variable, t, is equispaced. In spite of
this strong requirement, this formula is useful for the derivation of integration and differ-
ential equation schemes discussed elsewhere.
 Appendix D: Interpolation   ◾    501

D.2.1 Lagrange Interpolating Polynomials

The function in Lagrange interpolation is written as a sum of n polynomials, each of which
are of order (n − 1):

pL ( t ) = a1
(t - t2 ) (t - t3 ) + a (t - t1 ) (t - t3 ) (t - t 4 ) +  (D.2)
(t1 - t2 ) (t1 - t3 ) 2 (t2 - t1 ) (t2 - t3 ) (t2 - t 4 )
n

pL ( t ) = åa L
i =1
i i ,n (t )

(D.3)

Consider the denominator of Li , n: It is a product of all terms, (ti − t1) , (ti − t2), and so on

until (ti − tn), except the term (ti − ti). The numerator is the same product, with the variable
t replacing ti. Thus

n
t -tj
Li ,n ( t ) = Õ t -t
j =1 i j
(D.4)

j ¹i

Since the polynomial pL ( t ) passes through the first point, (t1, y1) satisfies Equation D.2.
When we substitute t = t1, the numerator of the first term becomes exactly equal to the
denominator. Thus, the first term becomes a1. In all the other terms, the numerator is a
product of (t1 − t1) with other terms, whereas the denominator is nonzero. Thus the other
terms, except the first term, vanish. Thus, y1 = a1. One can easily see the same pattern repeat-
ing for other polynomials as well:

n
t -tj
Li ,n ( t i ) = Õ t -t
j =1 i j
=1

j ¹i

whereas

Li ,n ( t m ) =
(tm - t1 )(tm - tm )(tm - tn ) = 0, i¹m
Denominator

Consequently, the Lagrange interpolation formula is given by

pL ( t ) = åy L
i =1
i i ,n (t )

(D.5)
502   ◾    Appendix D: Interpolation

n
t -tj
where Li ,n ( t ) = Õ t -t
j =1 i j
(D.6)

j ¹i

The application is demonstrated in the following example. This example (for divided differ-
ence formula) is also shown in video lectures on NPTEL.

Example D.1  Lagrange Interpolating Polynomial

Problem: Use Lagrange interpolating polynomials for the data given in Table D.1 and
obtain the vehicle speed at 45 s.
Solution: There are 10 data points. The first step is to calculate and store the values of
polynomials L1(45) to L10(45) as per Equation D.6. This is easy to calculate using MATLAB’s
prod command within a for loop. The result is stored in a 10D vector ­lagPoly.
The interpolated value can then be computed using dot(yData,lagPoly).
The value of pL ( 45 ) obtained using Lagrange interpolation in MATLAB is 9.0107.

D.2.2 Newton’s Forward Difference Formula

Newton’s forward difference formula is applicable to equally spaced data, that is, the
independent variables, t1 , t2 , … are equally spaced. Let h = ti + 1 − ti be the interval length.
Furthermore, let the normalized distance on the t-axis be defined as

t - t1
a= (D.7)
h

With this definition, at t = t1 , α = 0; at t = t2 , α = 1; and so on at t = tn , α = (n − 1). Considering

an individual term in the polynomial (D.1)

(
t - t i = ( t - t1 ) - ( t i - t1 ) = h a - ( i - 1) )
Similar to Equation D.1, the interpolating polynomial is now written as follows:

(
pF ( a ) = a0 + a1ha + a2h2 a ( a - 1) +  + an-1hn-1 a ( a - 1) ( a - n + 2 ) ) (D.8)

The above polynomial passes through the point (t1, y1), which corresponds to α = 0. At this
value of α, all the terms on the right-hand side, except the constant term, drop out. Thus

y1 = a0 (D.9)

The polynomial also satisfies the condition y = y2 at α = 1. At this condition, the first two
terms on the right-hand side are retained, whereas the other terms drop out:

y2 = a0 + a1h (D.10)
 Appendix D: Interpolation   ◾    503

Subtracting Equation D.9 from this equation yields

Dy1 = a1h (D.11)

where Δ is a forward difference operator such that Δϕi = ϕi + 1 − ϕi.

Continuing the process for other data points,

y3 = a0 + a1h ( 2 ) + a2 h2 ( 2 )(1) (D.12)

y 4 = a0 + a1h ( 3 ) + a2h2 ( 3 )( 2 ) + a3 3 ! (D.13)



yi = a0 + a1h ( i - 1) + a2h2 ( i - 1) ( i - 2 ) +  + ai -1hi -1 ( i - 1) ! (D.14)

i!
yi +1 = a0 + a1h ( i ) + a2h2 ( i ) ( i - 1) +  + ai -1hi -1 + ai hi i ! (D.15)
1!

As before, the first-order forward differences can be computed by subtracting the consecu-
tive equations. From Equations D.12 and D.10, we obtain

Dy2 = a1h + 2a2h2 (D.16)

Repeating this procedure yields us the remaining first-order forward differences:

Dy3 = a1h + a2h2 ( 2 )( 2 ) + 3 ! a3h3 (D.17)

Dyi = a1h + a2h2 2 ( i - 1) + a3h3 3 ( i - 1) ( i - 2 ) +  + i ! ai hi (D.18)

So far, the values of the first two parameters are known from the original data (see
Equation D.9) and first-order forward difference Δy1 (see Equation D.11). The next Newton’s
forward difference parameters can be computed from the higher-order forward ­difference
­formula. Specifically,

D 2 y1 = ( Dy2 - Dy1 )

= 2a2h2 (D.19)

Continuing further,

D 2 y2 = 2a2h2 + 3 ! a3h3 (D.20)

504   ◾    Appendix D: Interpolation

and so on. Without going into further details, one can observe that a clear pattern
emerges:

y1 = a0 (D.9)

Dy1 = a1h (D.11)

D 2 y1 = 2a2h2 (D.19)

D 3 y1 = 3 ! a3h3
(D.21)


Di yi = i ! ai hi (D.22)

Newton’s forward difference formula of Equation D.8 may now be written as

n -2
D 2 y1 Dn-1 y1

pF ( a ) = y1 + Dy1a +
2!
a ( a - 1) +  +
(n - 1) ! Õ ( a - k )
k =0
(D.23)

Now consider that there exists some function f(t) from which the data points for the inter-
polation were generated. The difference between a value generated from the “true” function
f(t) and the interpolated polynomial pF ( a ) is the error in Newton’s forward difference for-
mula. Consider that a new point, (tn + 1, yn + 1) also becomes available. The error in ignoring
this additional data while computing pF ( a ) is given by the additional term

Dn y1
RF = a ( a - 1) ( a - n + 1) (D.24)
n!

Recall that from mean value theorem

dn Dn y1
f ( x ) = , t1 £ x £ t n (D.25)
dt n hn

Thus, the residual term in computing Newton’s forward difference formula from
Equation D.23 is

hn ( n )

RF =
n!
(
f ( x ) a ( a - 1) ( a - n + 1)

) (D.26)

Consider the interpolation problem again as below.

 Appendix D: Interpolation   ◾    505

Example D.2  Newton’s Forward Difference Interpolation

Problem: Solve Example D.1 using Newton’s forward difference interpolation formula
Solution: As before, the data is in the form of two vectors, tData and yData, of size
10. The value of α is computed from the definition (D.7). The forward differences can be
computed using the MATLAB command diff. The first use of diff(yData) yields
Δy1 ⋯ Δy9, whereas each subsequent use gives the higher-order forward differences.
Once the forward differences have been calculated, the interpolated value at α = 4.5
can be calculated using Equation D.23.
The value of pF obtained using Newton’s interpolation in MATLAB is 9.0107. Note
that this value is the same as the one obtained using Lagrange interpolating polynomials.

D.3 SPLINE AND INTERPOLATION FUNCTIONS IN MATLAB®

MATLAB provides various options for interpolation, which can be invoked using the func-
tion interp1. The syntax for this command can be obtained by typing
>> help interp1

The syntax for interp1 is as follows:

yq = interp1(tData,yData,tq,‘<method>’);

where, tData and yData form the original data, and the interpolated value yq is returned
for the query point, tq. From the help text for interp1, the following information is dis-
played about the available methods for interpolation:

'linear' - (default) linear interpolation

'nearest' - nearest neighbor interpolation
'next' - next neighbor interpolation
'previous' - previous neighbor interpolation
'spline' - piecewise cubic spline interpolation (SPLINE)
'pchip' - shape-preserving piecewise cubic interpolation

The first option fits a piecewise linear curve to the datapoints. For the data in Table D.1, the
value at tq = 45 is the average between the values at 40 and 50, as shown below:
>> yq = interp1(tData,yData,45,‘linear’)
yq =
9.5000

The method ‘previous’ provides the so-called zero-order hold (also known as piece-
wise constant) approximation, wherein the value of yq is kept constant at the value yi for the
entire interval ti ≤ t < ti + 1. Thus, the value of yq at tq = 45 is the same as the value at t = 40, that
is, yq=7. The most popular options, though, are cubic spline and piecewise cubic Hermite
interpolating polynomial (PCHIP). The preferred MATLAB functions for cubic spline and
PCHIP algorithms are spline and pchip, respectively. The following example illustrates
their use.
506   ◾    Appendix D: Interpolation

Example D.3  Spline and PCHIP Interpolation

Problem: Solve Example D.1 using Newton’s forward difference interpolation formula.
Solution: First, define vectors tData and yData to contain the data in Table D.1.
Thereafter, the following commands may be used:

>> y_sp = spline(tData,yData,45)

y_sp =
9.0185
>> y_pchip = pchip(tData,yData,45)
y_pchip =
9.4599

It is interesting to note that for this data, cubic spline happens to give interpolated
value close to that obtained using Lagrange and Newton’s interpolating polynomials,
whereas PCHIP provides a significantly different value.

Spline interpolation fits piecewise polynomial functions to successive points. The sim-
plest one is “linear spline.” Here, two successive points are connected by straight line. The
interpolating function is just a combination of these lines, given by the following piecewise
­linear function:

ì y2 - y1
ï y1 + ( t - t1 ) t - t , t1 £ t < t 2
ïï 2 1
(D.27)
y - y
f ( t ) = í y2 + ( t - t 2 ) 3 2
, t2 £ t < t3
ï t3 - t2
ï
ïî 

The first function above is clearly a straight line connecting (t1, y1) and (t2, y2). Any point
between t1 and t2 is then interpolated based on this equation. The same applies to the rest
of the data intervals.
The term spline is typically not used for the function above. Instead, this is referred to as
linear interpolation, or more appropriately, piecewise linear interpolation. The linear func-
tions result in a curve that is nonsmooth. The term “spline” evokes an idea similar to using
the Bezier curves in an art class to smoothly connect dots on a canvas. The connecting
curves are smooth. While different splines exist, the practically most relevant is cubic spline
interpolation. When the term “spline” is used without any qualifier, it usually means cubic
spline, where piecewise cubic polynomials are used for interpolation. Thus, a (cubic) spline
would be represented as

ì q1 ( t ) , t1 £ t £ t 2
ï
ï q2 ( t ) , t2 £ t £ t3
f (t ) = í (D.28)
ï 
ïqn-1 ( t ) , t n-1 £ t £ t n
î
 Appendix D: Interpolation   ◾    507

qi(t) is a cubic function. The choice of qi(t) can be any cubic function; however, as this func-
tion connects points (ti, yi) and (ti + 1, yi + 1), they satisfy the equation. Borrowing idea from
Lagrange interpolation, let us define

t - ti
i = (D.29)
t i +1 - t i

so that at xi, ℓi = 0 and at xi + 1 , (1 − ℓi) = 0. The cubic polynomial may then be written as

qi = yi (1 -  i ) + yi +1 i +  i (1 -  i ) éëai  i + bi (1 -  i ) ùû (D.30)

The above function has an advantage that two of the four coefficients of a cubic polynomial
are conveniently defined. Note that when ℓi = 0, only the first term remains and the other
three are zero; whereas when ℓi = 1, only the second term is nonzero.
A total of (n − 1) polynomials of the form (D.30) define the cubic spline. Hence, 2(n − 1)
parameters have to be obtained. There are two boundary nodes, t1 and tn and (n − 2) inter-
nal nodes. In order to ensure that the curve is smooth, the slope and curvature of the two
curves qi − 1(t) and qi(t) should be equal at each internal node ti. This leads to the following
2(n − 2) equations:

qi¢ ( t i ) = qi¢+1 ( t i ) , i = 1 to ( n - 1) (D.31)

qi¢¢( t i ) = qi¢¢+1 ( t i ) , i = 1 to ( n - 1) (D.32)

whereas the final two equations are obtained by imposing no curvature condition at the two
boundary nodes:

q1¢¢( t1 ) = 0 (D.33)

qn¢¢-1 ( t n ) = 0 (D.34)

The derivation of the above equations is straightforward, though tedious. I refer an inter-
ested reader to any numerical methods text for the derivation. The intent of this discussion
was to give a flavor of cubic spline interpolation.
The cubic spline option is available in the interp1 function discussed earlier in this
section. Rather than the generic interp1 function, the preferred means of using cubic
spline is the function spline, as demonstrated in Example D.3. It should be noted that all
these functions allow the independent query variable tq to be a vector. In such a case, the
code returns a vector yq of the same length such that each element of yq is the interpolated
value at the corresponding element of the vector tq. Thus, if interpolated values are required
at multiple points, the function spline or pchip may be used with a vector-valued tq.
508   ◾    Appendix D: Interpolation

The primary advantage of spline function is in the cases where interpolants are
required to be computed multiple times in any MATLAB application. Typically, if the val-
ues of independent variables are known a priori, a vector-valued tq can be used. However,
when the query points for interpolation may be generated within the code, the function
spline (or pchip) needs to be used multiple times. Since calling these functions involves
computing the parameters of Equation D.30 each time for the same data sets tData and
yData, this would be computationally inefficient. A better way to do this is to use the
spline function to define the piecewise cubic polynomials and store them:

>> splineParam = spline(tData,yData)

splineParam =
form: 'pp'
breaks: [0 10 20 30 40 50 60 70 80 90]
coefs: [9x4 double]
pieces: 9
order: 4
dim: 1

Invoking spline without the query vector tq returns a pp structure, which defines the
node points (original values of t in Table D.1) as well as coefficients of the nine cubic poly-
nomials; it also indicates that this pp structure is cubic spline interpolation (order: 4)
for 1D interpolation (dim: 1). Once this structure is obtained, it may be used multiple
times through the ppval command:

>> yq = ppval(splineParam,45)
yq =
9.0185

Note that this result is the same as that in Example D.3. The next example demonstrates the
use of spline interpolation through multiple applications.

Example D.4  Cubic Spline Interpolation

Problem: Obtain the interpolated values of vehicle speed for the data in Table D.1
using cubic spline at every randomly generated interval between 0 and 1 s. Use the
command rand to generate the next interval point.
Solution: The code below demonstrates the use of spline and ppval functions:

% Given data
tData = [0:10:90]';
yData = [45 32 0 0 7 12 20 15 29 55]';
plot(tData,yData,'bo'); hold on; % Plot original data

% Obtain interpolating polynomials

splineParam = spline(tData,yData);
 Appendix D: Interpolation   ◾    509

60

40

Speed (km/h)
20

–20
0 20 40 60 80
Time (s)

FIGURE D.2  Cubic spline interpolation for vehicle speed data.

% Interpolate and plot

tq(1)=0;
yq(1)= ppval(splineParam,tq(1));
for i=2:100
tq(i)=tq(i-1)+rand;
yq(i)=ppval(splineParam,tq(i));
end
plot(tq,yq,’-b’);

Figure D.2 shows the result of the above code. Spline interpolation results in a smooth
curve fitting to the initial data. The smoothness is due to the conditions of (D.31) and
(D.32) imposed at all interior nodes.

Spline interpolation is not guaranteed to be monotonic. In other words, the interpolated

values within an interval can lie outside the range of the y values at the bounding nodes. An
interesting thing to note is that the interpolated values of velocity fall below 0 between 20 and
30 s. However, the vehicle speed has to be nonnegative. This is where a “shape-preserving”
or monotonic interpolation is useful. The piecewise cubic Hermite interpolation polynomials
can be used if the dependent variable has to meet the requirement of monotonicity. MATLAB
provides the function pchip for this purpose. The next example demonstrates this, and a
comparison between spline and pchip is shown in Figure D.3.

Example D.5  Comparison between spline and pchip

Problem: Compare spline and pchip interpolation for the vehicle speed data
Solution: The two functions will be used to obtain interpolated values of vehi-
cle speed at a frequency of 1 s. Assuming that tData and yData are already
available, the functions spline and pchip can be called using a vector-valued
tq = 0:90.
510   ◾    Appendix D: Interpolation

60

Spline
40

Speed (km/h)
20

pchip
0

–20
0 20 40 60 80
Time (s)

FIGURE D.3  Comparison of cubic spline (solid line) and monotonicity shape preserving PCHIP
interpolation (dashed line) for vehicle speed data.

The resulting interpolated values are plotted in Figure D.3. The dashed line shows
that the pchip interpolation preserves monotonicity. Between t = 20 and t = 30, the
interpolated values remain at 0 km/h because the interpolant does not allow yq to get
values outside the range of the bounding points.

This completes our discussion on interpolation. While Newton’s difference formulae were
derived in this chapter, the practical implementation of interpolation in MATLAB is
through spline and pchip functions.
Appendix E: Numerical
Integration

E.1 GENERAL SETUP
Numerical integration aims to find an approximate solution to the problem:

ò
I = f ( x ) dx
a
(E.1)

where f(x) (known as an integrand) is an arbitrary function of the independent variable x.

The integral, I, is to be found between the limits of integration, that is, for x ∈ [a, b]. The dis-
cussion in this section will be limited to integration in a single independent variable. First,
the topic of (numerical) integration will be introduced, followed by a discussion on some
numerical techniques, and finally ending with MATLAB® implementation of numerical
integration.
The geometric interpretation of integration is that the integral, I, is the area under the
curve f(x) between the points x = a and x = b. This is represented as the shaded area in
Figure E.1. This region is split into multiple intervals, as delineated by vertical dotted lines,
to obtain integral I to the desired accuracy. Integration is the counterpart of differentiation
(covered in Appendix B). If we write

d
f (x) = y (x) (E.2)
dx

then integral I is equal to I = y(b) − y(a). Numerical methods for computing the integral
can be used if f(x) either is known as an explicit function of x, or can be calculated numeri-
cally or indirectly (for any given value of x), or is available as a tabulated pair (x, f(x)).
Additionally, note that Equation E.2 is an ordinary differential equation. The aim of an
ODE solver is to obtain y(x) given an initial value y(a) at a point x = a. Thus, evaluating
the integral I is equivalent to solving the ODE (E.2) for y(a) = 0. An equivalence between
numerical integration and solving ODE is provided in a plug flow reactor (PFR) case study
in Chapter 3.

511
512   ◾    Appendix E: Numerical Integration

f (x)

a b

FIGURE E.1  Geometric interpretation of integration.

E.1.1 Some Exemplary Applications

Numerical integration finds several applications in science and engineering, in general,
and in chemical engineering in particular. The first course in thermodynamics introduces
­students to enthalpy, where enthalpy at any temperature, T, is calculated as

ò
0 0
H = H + c p dT
T T0 (E.3)
T0

where cp is commonly expressed as a polynomial function of temperature.

Another application of integration is the inverse of the application covered in Appendix B:
to calculate net quantity when flux is known. For example, if the heat flux through a surface
is known, the net heat exchange is calculated by integrating the flux over the entire surface.
Likewise, in case of membrane separation, the flux of permeate through the membrane can
be computed; surface integral of the flux over the entire membrane surface gives the net
quantity of permeate flowing across the membrane.
Finally, an application unique to chemical engineering is the design equation of a PFR.
The volume of a PFR required to achieve a target conversion Xset is given by

Xset
FA0

Vpfr =
ò ( -r ( X )) dX
0
A
(E.4)

In the above equation, Vpfr is the desired volume of the PFR, whereas the rate of chemical
reaction taking place in the system depends on the concentration. It can be converted into
a function of conversion, X, and is given by the function −rA(X). In the rest of this chapter,
the example of PFR design equation will be used to demonstrate the concepts of numerical
integration.
 Appendix E: Numerical Integration   ◾    513

E.2 NEWTON-COTES INTEGRATION FORMULAE

Newton-Cotes integration formulae are so-called closed integration formulae, where we
attempt to find the area under the curve by dividing the region x ∈ [a, b] into several inter-
vals, as seen in Figure E.1. The integration formulae are then applied to individual inter-
vals. Higher-order formulae use multiple function evaluations and yield more accurate
results. Since a single application of the formula (even higher-order ones) has numerical
errors, usually multiple applications of the integral formulae are sought. The most popu-
lar Newton-Cotes integration formulae are discussed below. First, single application of
the integration formulae is discussed, followed by numerical derivation of the formulae.
Thereafter, multiple applications of the integration formulae to improve the numerical
accuracy will be discussed.

E.2.1 Single Application of Integration Formulae

E.2.1.1 Trapezoidal Rule
Consider a single application of the trapezoidal rule, where the integral (E.1) is approxi-
mated as the area under a straight line joining two endpoints. The interval size for the
trapezoidal rule is the entire domain length, that is, h = (b − a). The two endpoints, (a, fa)
and (b, fb), can be connected by a unique straight line. Figure E.2 shows the schematic of a
single application of the trapezoidal rule applied to the f(x) curve of Figure E.1. The straight
line, denoted as T in Figure E.2, is this line joining the two points. The value of integral, I, is
approximated as the area under the line T.
This is nothing but the area of the trapezoid bounded by x = a, x = b and line T, which
is given by

h
I»
2
( fa + fb ) (E.5)

Clearly, the area of trapezoid given in Equation E.5 is an approximation of integral, I.

All Newton-Cotes integration formulae can be derived by first finding the equation of the
polynomial curve connecting the points and then integrating this equation to approximate

T
f (x)

a b

FIGURE E.2  Schematic showing single application of the trapezoidal and Simpson’s 1/3rd rules.
514   ◾    Appendix E: Numerical Integration

the value of I. In case of trapezoidal rule, the polynomial connecting the two endpoints is a
straight line, T(x). The equation of this line is given by

T ( x ) - fa fb - f a
=
x -a b-a

Rearranging the above leads to the equation of the line:

fb - f a
T ( x ) = fa + (x - a) (E.6)
h

Integrating the above equation yields the approximate value of I using the trapezoidal rule:
b

ò
I » T ( x ) dx
a
(E.7)

b
é ù b
ê ú fb - f a é x 2 ù
I = fa ê x ú + ê - ax ú
h ë2 ûa
ê ú
ë ûa

f b - f a é b2 - a 2 ù
I = fah + ê - a (b - a )ú
h ë 2 û

Noting that (b2 − a2) = (b − a)(b + a) = h(a + b), the final equation above can be rearranged

to give

æ a +b ö
I » fa h + ( fb - f a ) ç -a÷ (E.8)
è 2
ø
h
2

It is easy to verify that this is the same as the trapezoidal rule written in Equation E.5. ■
Thus, the trapezoidal rule has been derived in two different ways: geometrically using the
analogy with the area of a trapezoid and algebraically integrating the equation of a straight
line connecting the two points. While these derivations are elegant, they still do not reveal
the numerical error in computing the approximate value of integral using Equation E.5.
A formal derivation of the trapezoidal rule including the error estimates will be discussed
presently in Section E.2.2. The overall trapezoidal rule may be written as follows (also see
Equation E.17):

h h3
I=
2
( f1 + f 2 ) -
12
f ¢¢ ( x ) (E.9)

This means that the error in the trapezoidal rule scales as a cube of the interval size. In other
words, the error reduces by a factor of 8 if the interval size, (b − a), is halved. Moreover,
 Appendix E: Numerical Integration   ◾    515

the integral is exact if f″(ξ) = 0, ξ ∈ [a, b]. Obviously, when f(x) is a straight line, then the
trapezoidal rule is exact. Practical implementation of the trapezoidal rule, including dem-
onstration of the error analysis is presented in Example E.1.

Example E.1  Trapezoidal Rule

Problem: For various values of b, compute the following integral, as well as the numer-
ical error, using a single application of the trapezoidal rule:
b

ò (2 - x + ln ( x )) dx
1

Solution (direct): The solution to the problem will involve computing fa, fb and hence
use Equation E.5 to compute the integral. The true value of integral is
2
x

y (x) =
ò (2 - x + ln ( x )) dx = x ln ( x ) + x - 2
Thereafter, the true value is computed as y(b) − y(1) and the absolute error can be
found. The MATLAB code to do this is given below:

% Single application of Trapezoidal Rule for Integration

% f(x) = 2 - x + ln(x)
a=1;
b=2;
trueVal = (b-b^2/2+b*log(b)) - (a-a^2/2+a*log(a));
%% Trapezoidal Rule (single application)
h = (b-a);
fa= 2-a+log(a);
fb= 2-b+log(b);
I_trap=h/2*(fa+fb);
err_trap=abs(trueVal-I_trap);

The value of integral for b = 2 is 0.8466, whereas the numerical error is 3.9721E-2.
Thus, using the trapezoidal rule with a large step-size of 1 results in nearly 4% error.
Next, the error behavior is analyzed for various values of b. The results are given
below:

b h error
2 1 3.972e-2
1.5 0.5 6.831e-3
1.1 0.1 7.569e-5

Thus, when the interval width is decreased by one order of magnitude, from 1 to 0.1,
the error decreases by almost three orders of magnitude. This is because, as seen in
Equation E.9, the trapezoidal rule has an accuracy of O h3 . ( )
516   ◾    Appendix E: Numerical Integration

While the above solution works, it can be made more elegant using MATLAB function. A
separate MATLAB function fun4Int may be defined to calculate f(x) = 2 − x + ln(x) as a
function of independent variable x. There are two ways to do this:

Using Anonymous Function: fun4Int = @(x) 2-x+log(x);

Using Function File (fun4Int.m):
function fval = fun4Int(x)
fval = 2-x+log(x);
end

Once the function has been defined, the code in Example E.1 may be modified as follows :

Solution to Example E.1 using functions:

% Problem Setup
a=1; b=2;
h = (b-a);
% Trapezoidal Rule (single application)
I_trap=h/2*(fun4Int(a)+fun4Int(b));
err_trap=abs(trueVal-I_trap);

The solution above is more elegant than the “direct” solution. It is modular, in that it allows the
core integration code to be used for integrating other functions with little change. Since the
function f(x) is written once and called multiple times as needed, it is prone to lesser errors.

E.2.1.2 Simpson’s 1/3rd Rule

The trapezoidal rule was derived using only the two endpoints and joining them with a
straight line. The accuracy of the numerical integration method can be improved by includ-
ing additional intermediate points. The next method in Newton-Cotes sequence of methods
is known as Simpson’s 1/3rd rule. This is shown schematically in Figure E.2, where in addi-
tion to the two endpoints, a and b, a third point is chosen as the midpoint. A quadratic curve
is fitted to the three points. The step-size for a single application of Simpson’s 1/3rd rule is
now half of the original domain length. Thus, the following three points are used:

t1 = a, f1 = f ( t1 )
a +b
t2 = , f2 = f (t2 ) (E.10)
2
t 3 = b, f 3 = f ( t 3 )

Simpson’s 1/3rd rule along with the numerical error is given by the following expression:

h h5
I=
3
( f1 + 4 f 2 + f 3 ) -
90
f ²² ( x ) (E.11)

 Appendix E: Numerical Integration   ◾    517

Simpson’s 1/3rd rule requires, for each interval, one additional function evaluation than
the trapezoidal rule. However, the accuracy of the numerical integration formula increases
( ) ( )
by two orders of step-size, from O h3 in case of the trapezoidal rule to O h5 in case of
Simpson’s 1/3rd rule. The derivation of Simpson’s 1/3rd rule and error estimate will be dis-
cussed in Section E.2.2. Use of this method for numerical integration will be demonstrated
in the next example.

Example E.2  Simpson’s 1/3rd Rule

Problem: Solve Example E.1 using Simpson’s 1/3rd rule.
Solution: The code for Simpson’s 1/3rd rule is similar to that of the trapezoidal
rule. It involves calculating step-size, h=(b-a)/2, and the midpoint, t2=a+h.
The three function values are fun4Int(a), fun4Int(t2), and fun4Int(b),
which are plugged in Equation E.11 to compute the integral.
The result of applying Simpson’s 1/3rd rule is given below:

b h error
2 0.5 4.598e-4
1.5 0.25 2.772e-5
1.1 0.05 1.718e-8

In this example, when the interval width is decreased by one order of magnitude, from
1 to 0.1, the error decreases between four and five orders of magnitude: The ratio of
the two errors is 3.7 × 10−5, consistent with the observation that Simpson’s 1/3rd rule
( )
is O h5 accurate.

Direct comparison between the trapezoidal and Simpson’s 1/3rd rules reveals that the latter
is more accurate. This rather significant improvement in accuracy comes at a cost of only
one additional function evaluation. Another example, discussed in Section E.2.3, will dem-
onstrate the significance of the order of accuracy: The additional computational require-
ment is justified by highly significant reduction in accuracy of the numerical method.

E.2.1.3 Simpson’s 3/8th Rule

The trapezoidal rule uses the two endpoints of the region of integration, fits a straight line,
and approximates the integral as the area under the line. In Simpson’s 1/3rd rule, an addi-
tional point, midpoint of the region, is introduced and the integral is approximated as the
area under a second-order curve passing through these three points. Continuing this idea
further, Simpson’s 3/8th rule finds an area under a cubic curve passing through four equi-
spaced points. The step-size is h = (b − a)/3 and the three points include t1 = a , t2 = a + h ,
t3 = a + 2h, and t4 = b. The function values f(ti) are represented as fi. Then, the integral is
approximated using Simpson’s 3/8th rule as

3h 3h5
I=
8
( f1 + 3 f 2 + 3 f 3 + f 4 ) -
80
f ²² ( x ) (E.12)

518   ◾    Appendix E: Numerical Integration

Equation E.12 gives Simpson’s 3/8th rule. Comparing with Equation E.11, Simpson’s 3/8th
rule has the same order of accuracy as the 1/3rd rule, since the error in both these methods
( )
scales as O h5 . Note that Simpson’s 1/3rd rule gives the same order of accuracy as the 3/8th
rule, but with one less function evaluation in each application.
Since Simpson’s 3/8th rule follows the same general pattern as the trapezoidal and
Simpson’s 1/3rd rules, a demonstration will be skipped for brevity. The reader can verify
that the error using Simpson’s 3/8th rule for Example E.1 is of the same order of magnitude
as the 1/3rd rule, albeit slightly lower.

E.2.2 Derivation of Integration Formulae

The derivation of Newton-Cotes integration formulae can be done using Newton’s inter-
polating polynomial (see Appendix D for more details). The interpolating polynomial is
fitted to an appropriate number of equispaced data, and the resulting polynomial integrated
between the limits, x = a to x = b. Thus, the integral may be approximated as
b b

òa
ò
I = f ( x ) dx » p ( x ) dx
a
(E.13)

In case of trapezoidal rule, a first-order interpolating polynomial is fitted to two data points.
Thus, the polynomial p takes the following form:
f ¢¢ ( x )
p ( a ) = f1 + Df1a + a ( a - 1) h2 (E.14)
2
Recall from Appendix D that for Newton’s forward difference interpolation, we define

x -a
a= , with h = ( b - a ) (E.15)
h

From the above equation, it is clear that

dx = hda

Change the variable of integration to α, the limits of integration are from α = 0 to α = 1:
1

ò
I = p ( a ) × h da
0

Substituting

f ¢¢ ( x )
1
æ ö
ò
I = h ç f1 + Df1a +
ç
0è
2!
a ( a - 1) h2 ÷ da
÷
ø
1
é a2 f ¢¢ ( x ) 2 æ a3 a2 ö ù
= h ê f1a + Df1 + h ç - ÷ú (E.16)
êë 2 2! è 3 2 ø úû
0
 Appendix E: Numerical Integration   ◾    519

éf +f ù f ¢¢ ( x ) é 1 ù
I = h ê 1 2 ú + h3 - (E.17)
2 2 êë 6 úû
ëû  
Formula Error

( )
This demonstrates the O h3 accuracy of the trapezoidal rule mentioned in Section E.2.1
and demonstrated in Example E.1.
In a similar manner, Simpson’s 1/3rd rule may also be derived. Here, the step-size is given by

b-a
h=
2

With the same definition of α as before, the limits of integration, x = a and x = b, correspond
to α = 0 and α = 2, respectively. Thus, integral I in Simpson’s 1/3rd rule is written as
2

ò
I = p ( a ) × h da
0

Substituting second-order polynomial expansion yields

f ¢¢¢ ( x )
2
æ 1 ö
ò
I = h ç f1 + Df1a + D 2 f1a ( a - 1) +
ç
0è
2 3!
a ( a - 1) ( a - 2 ) h3 ÷ da
÷
ø
2
é a2 æ a3 a2 ö f ¢¢¢ ( x ) 3 æ a 4 öù
= h ê f1a + Df1 + D 2 f1 ç - ÷+ h ç - a3 + a2 ÷ ú (E.18)
êë 2 è 6 4 ø 6 è 4 ø úû 0

é æ 4 öù f ¢¢¢ ( x )
I = h ê2 f1 + 2Df1 + D 2 f1 ç - 1 ÷ ú + h 4 éë 4 - 8 + 4 ùû (E.19)
ë  è3  ø û  6  
Is Error = 0?
Formula

The above equation gives a surprising result. The first part gives Simpson’s 1/3rd rule.
However, notice that in the final term in the above equation, the expression in brackets
equates to zero. Does that mean that Simpson’s 1/3rd rule is accurate and does not have any
numerical error? As demonstrated in Example E.2, there is a numerical error in implement-
ing Simpson’s 1/3rd rule. So, what the above derivation implies is that the leading error term
is not the third-order term; instead, the analysis needs to be done including an additional
term in Newton’s forward difference polynomial used in (E.18). Doing so yields

2
æ 1 1
è ò
I = h ç f1 + Df1a + D 2 f1a ( a - 1) + D 3 f1a ( a - 1) ( a - 2 )
0
2! 3!

f ²² ( x ) ö
+ a ( a - 1) ( a - 2 ) ( a - 3 ) h 4 ÷ da (E.20)
4! ø
520   ◾    Appendix E: Numerical Integration

Note that the first four terms are the same as the one obtained in Equation E.19. Thus

2
é 1 f ²² ( x ) 4 æ a5 3 4 11 3 öù
I = h ê2 f1 + 2Df1 + D 2 f1 + D 3 f1 × 0 + h ç - a + a - 3a2 ÷ ú
êë 3 24 è 5 2 3 ø úû 0

Substituting the expressions for Δf1 and Δ2f1 yields

é 1 ù
I » h ê2 f1 + 2 ( f 2 - f1 ) + ( f 3 - 2 f 2 + f1 ) ú
ë 3 û

and

f ²² ( x ) æ 32 88 ö f ²² ( x )
E = h5 ç - 24 + - 12 ÷ = -h5
24 è 5 3 ø 90

Thus, Simpson’s 1/3rd rule may be written as

h f ²² ( x )
I= éë f1 + 4 f 2 + f 3 ùû - h5 (E.21)
3  90
  
Formula Error

The above equation shows Simpson’s 1/3rd rule along with the error estimate. This justi-
fies the observation in Example E.2 regarding the effect of interval size on the accuracy of
Simpson’s 1/3rd rule.

E.2.3 Multiple Applications of Newton-Cotes Formulae

A single application of Newton-Cotes integration formulae can have significant errors. In
Example E.1, the error in computing integral for b = 2 using the trapezoidal rule was nearly
4%. While the error drops significantly when Simpson’s 1/3rd rule is used, error of the order
of ∼10−4 may still be high for a number of applications. One way to improve the accuracy of
numerical integration is to divide the region of integration into multiple intervals and apply
the method of choice multiple times to obtain an appropriate numerical integral. As shown
schematically in Figure E.1, the region of integration may be divided into n intervals. Thus

b-a
h= , x1 = a, xn+1 = b
n

and (x1, f1) , (x2, f2) ,  …  , (xn + 1, fn + 1) form the nodes used in obtaining the integral.

Multiple implementation of the trapezoidal rule can be performed for any choice of
number n of intervals. The value of total integral may then be written as

I = I1trap + I 2trap +  + Intrap (E.22)

 Appendix E: Numerical Integration   ◾    521

where Iitrap is the integral obtained at the ith interval using data at ith and (i + 1)th nodes:

h -h3
Iitrap =
2
( fi + fi +1 ) +
12
f ¢¢ ( xi ) (E.23)

where ξi ∈ [xi, xi + 1]. Substituting in Equation E.22

n
h -h3

I= åi =1
2
( fi + fi +1 ) +
12
f ¢¢ ( xi )

(E.24)

n
h h3

I = éë( f1 + f 2 ) + ( f 2 + f 3 ) +  + ( fn + fn+1 ) ùû -
2 12 å f ¢¢ ( x )
i =1
i (E.25)

h h3

I=
2
éë f1 + 2 ( f 2 +  + fn ) + fn+1 ùû -
12
nf ¢¢ ( x ) (

) (E.26)

The last term in the above equation is derived using mean value theorem, with x Î éëa, b ùû.
The first sum gives the integral using multiple applications of the trapezoidal rule. Using the
relationship of h, the error term may be written as

(b - a )
3

Enet =- nf ¢¢ ( x ) (E.27)
12n3

This may then be written as

(b - a ) h2 f ¢¢

Enet = -
12
( x ) (E.28)

There are a few things to note from the error analysis of multiple applications of the trapezoidal
rule. The first thing is that the net error is proportional to h2 and not h3. This means that the
error reduces by two orders of magnitude when the step-size is reduced by one order of magni-
tude. This issue of local vs. global truncation errors (GTEs) is discussed at length in Chapter 1.
Another important point to note is regarding this drop in order of accuracy for GTE.
Throughout this book, I have discussed the importance of the order of accuracy, that
( )
O hn method would often be a preferred numerical method over O hm , when n > m. ( )
So, what does it mean when the local truncation error (LTE) scales as O h3 while the ( )
( )
GTE scales as O h2 ? Does that mean that multiple applications of the trapezoidal rule
are not useful? In reality, this is not the case because for a single application, h = (b − a),
whereas for multiple applications of the trapezoidal rule, h = (b − a)/n. So, the compar-
ison between two options is valid only if the step-size h refers to the same quantity.
In LTE, h refers to the entire interval size, whereas in GTE it refers to individual step-
size. On the other hand, comparison between the trapezoidal and Simpson’s rules is still
valid because in both these cases h refers to the same thing.
522   ◾    Appendix E: Numerical Integration

So, how does one compare single and multiple applications of the trapezoidal rule?
In case of the former, n = 1 in Equation E.27. Thus the error in a single application of the
trapezoidal rule is

(b - a )
3

Enet = - f ¢¢ ( x ) (E.29)
12

whereas that in multiple applications is

(b - a )
3

Enet =- f ¢¢ ( x ) (E.27)
12 n2

Thus, the error in multiple applications of the trapezoidal rule is expected to improve by a
factor of 4 when two intervals are used, and by two orders of magnitude when n ∼ 10 inter-
vals are used. The next example demonstrates this.

Example E.3  Multiple Applications of the Trapezoidal Rule

Problem: Compute the following integral, as well as the numerical error:

ò (2 - x + ln ( x )) dx
1

using multiple applications of the trapezoidal rule.

Solution: The following code may be used for multiple applications of the trapezoidal
rule. First, the array of nodal points, [x1,  … , xn + 1], is used to obtain the corresponding
function values, [f1,  … , fn + 1], followed by the implementation of Equation E.26.

% Multiple applications of Trapezoidal Rule

% f(x) = 2 - x + ln(x)
%% Problem Setup
a=1; b=2;
trueVal = (b-b^2/2+b*log(b)) - (a-a^2/2+a*log(a));
n=20;
%% Trapezoidal Rule (multiple applications)
h=(b-a)/n;
xVec=a:h:b;
fVec=fun4Int(xVec);
I_trap=(h/2)*(fVec(1)+2*sum(fVec(2:n))+fVec(n+1));
%% Results
err=abs(trueVal-I_trap);
disp(['For h=', num2str(h), ', Error=', num2str(err)]);
 Appendix E: Numerical Integration   ◾    523

When the code is executed for n = 10, the error in the trapezoidal rule is 4.164 × 10−4.
Comparing with Example E.1, the error has fallen by nearly two orders of magnitude,
as predicted in Equation E.27.
Next, the step-size was halved (with n = 20). The resulting error was

For h=0.05, Error=0.00010415

Finally, decreasing the step-size to 0.01 (i.e., n = 100) yields

For h=0.01, Error=4.1666e-06

In summary, the error decreased by a factor of 4 when the step-size was reduced by
half, whereas it decreased by two orders of magnitude when the step-size was reduced
by one order of magnitude. This observation is a consequence of the fact that the GTE
of the trapezoidal rule scales as O h2 . ( )
Another interesting observation on comparing the above results with Example E.2 is
that the error in a single application of Simpson’s 1/3rd rule happened to be similar to the
error using 10 applications of the trapezoidal rule. This demonstrates the power of using
higher-order formulae: Three function evaluations in Simpson’s 1/3rd rule were sufficient
to provide similar accuracy as eleven function evaluations in the trapezoidal rule.

Consequently, it is advantageous to use multiple applications of Simpson’s 1/3rd rule as

well. Unlike the trapezoidal rule, there is a restriction that n has to be an even number.
This is because single application of Simpson’s 1/3rd rule involves two intervals. Thus, first
application of the rule will involve nodes (x1, x2, x3), and the next application would involve
(x3, x4, x5), followed by nodes (x5, x6, x7) and so on. Figure E.3 shows a schematic to further
explain this.
As in the trapezoidal rule, multiple applications of Simpson’s rule can be derived as

h
I= é( f1 + 4 f 2 + f 3 ) + ( f 3 + 4 f 4 + f 5 ) +  + ( fn-1 + 4 fn + fn+1 ) ùû + Enet (E.30)
3ë
f (x)

a b

FIGURE E.3  Schematic of multiple applications of Simpson’s 1/3rd rule.

524   ◾    Appendix E: Numerical Integration

The reader can verify that the formula for and the error in Simpson’s 1/3rd rule is given by

h
I= é f1 + 4 ( f 2 + f 4 +  + fn ) + 2 ( f 3 + f 5 +  + fn-1 ) + fn+1 ùû + Enet (E.31)
3ë

(b - a ) f ²²

Enet = -h 4
90
( x ) (E.32)

where h = (b − a)/n. Thus, the GTE in Simpson’s 1/3rd rule scales as O h 4 . ( )

In the same manner, a formula for multiple applications of Simpson’s 3/8th rule can be
derived. An interested reader may read advanced text on numerical techniques to learn
about higher-order Newton-Cotes integration formulae that use a larger number of nodes
to provide higher accuracy.

Example E.4  Comparison of the Trapezoidal and Simpson’s Rules

Problem: Compare the three methods described above for the same step-size.
Solution: For this comparison, choose n = 6, so that h = 1/6. This corresponds to six
applications of the trapezoidal rule, three applications of Simpson’s 1/3rd rule, and
two applications of Simpson’s 3/8th rule. As before, choose
h=(b-a)/n;
xVec=[a:h:b];
fVec=fun4Int(xVec);

With fVec available, Equation E.26 is used for the trapezoidal rule, Equation E.31
for Simpson’s 1/3rd rule, and a similar equation (derivation is left as an exercise to the
reader) for Simpson’s 3/8th rule. With the true value of the integral known, the errors
can also be computed. The results are given below.
Value of integral using the three methods
0.8851 0.8863 0.8863

Error using the three methods

1.1555e-3 7.20e-6 1.56e-5

This completes the comparison of the three methods.

E.3 QUADRATURE AND MATLAB® FUNCTIONS

MATLAB provides several functions to compute an integral. The trapezoidal rule can be
invoked using the function trapz:
>> I_trap=trapz(xVec,fVec);

will give the exact same result as the trapezoidal rule implemented in Example E.3 earlier.
Simply replacing the third line from the end from Example E.3 will provide the same results
as multiple implementation of the trapezoidal rule.
 Appendix E: Numerical Integration   ◾    525

A more powerful computation of integral is provided by the command quad. The syntax
for quad is

>> I=quad(@(x) fun4Int(x),a,b);

where the first argument passes the function fun4Int that calculates f(x), while the last
two arguments are limits of integration. This uses Simpson’s quadrature method.
In later versions of MATLAB, quad will be superseded by an improved algorithm inte-
gral. This uses global adaptive quadrature method. The regular implementation is similar:

>> I=integral(@(x) fun4Int(x),a,b);

There are two main differences between trapz and the two quadrature methods men-
tioned here. The first one is that trapz takes actual values [x1  x2  ⋯   xn + 1] and corre-
sponding function values éë f1 f 2  fn+1 ùû as input arguments. On the other hand, quad
and integral require the actual function f(x), in the form of a MATLAB function file
(or MATLAB anonymous function) as an input argument, and compute the integral for the
specified integration limits (also input arguments). The second difference is that trapz
simply calculates the numerical integral value as such; quad and integral calculate
the numerical integral such that the error E < tol. In other words, if Inum is the numerical
integration value and Itrue is the true value of the integral, then the step-size h is chosen such
that the error |Itrue − Inum| < εtol.
The error tolerance value εtol can be specified by the user. If it is not specified (as in the
example above), a default value of εtol = 10−6 is used.
Recall that according to Equation E.32, it is possible to know the error Enet. However, in
most practical examples, it is either not possible or not convenient to know f ²² ( x ). Hence,
there needs to be an alternate method to estimate the error.
Simpson’s quadrature method, implemented in quad, utilizes the fact that although the
error cannot be known exactly, there are ways to estimate it even when f ²² ( x ) is unknown.
I will use Simpson’s 1/3rd rule to explain the concept behind this.
The true value of integral and its relationship with Simpson’s 1/3rd rule is

I true = I simp ( h ) + c1,h h 4 (E.33)

1
where c1 = - ( b - a ) f ²² ( x ) is a constant.
90
If the same calculation is repeated using a step-size of h/2

h4
I true = I simp ( h/2 ) + c1,h /2 (E.34)
24

1
where again c1 = -
90
(b - a ) f ²² ( x ).
526   ◾    Appendix E: Numerical Integration

Usually, f ²² ( x ) from Equation E.33 and f ²² ( x ) from Equation E.34 are reasonably con-
stant for most practical problems. Thus, the difference between the two will provide an
estimate of the error:

15h 4
0 = I simp ( h ) - I simp ( h/2 ) + c1 (E.35)
16

Since
Enet = c1h 4

hence, the term

16
Enet ~ I simp ( h ) - I simp ( h/2 ) (E.36)
15

gives an estimate of the error. Simpson’s quadrature method involves calculating the integral
at a chosen value of h, then repeating the calculations with half step-size h/2. Thereafter, the
error is estimated as per Equation E.36. If this value is above the required tolerance, the
algorithm sets h ← h/2 and the procedure is repeated until the error tolerance is met.
When this condition is met, the more accurate of the two values is returned as the integral.
The command integral uses a different algorithm. Since it is not aligned with the
objective of this textbook, it will not be discussed further. This chapter ends with the fol-
lowing example of implementation of quad and integral.

Example E.5  Demonstrate the Use of quad and integral Functions

Problem: Demonstrate the use of quad and integral functions for the same problem.
Solution: Command-line use of the two functions is very straightforward. First,
integration using quad is shown as follows:

>> I1=quad(@(x) fun4Int(x),a,b)

I1 =
0.8863
>> err = abs(trueVal-I1)
err =
2.6783e-08

Similarly, integral may be used as follows:

>> I2=integral(@(x) fun4Int(x),a,b)

I2 =
0.8863
>> err = abs(trueVal-I2)
err =
0
Bibliography

Bequette, B.W., Process Dynamics: Modeling, Analysis, and Simulation (1998), Prentice Hall PTR,
Upper Saddle River, NJ.
Butcher, J.C., Numerical Methods for Ordinary Differential Equations, 2nd edn. (2008), Wiley, West
Sussex, England.
Carslaw, H.S. and Jaeger, J.C., Conduction of Heat in Solids, 2nd edn. (1986), Oxford University Press,
Oxford, U.K.
Chapra, S.C. and Canale, R., Numerical Methods for Engineers, 5th edn. (2006), McGraw-Hill, Inc.,
New York.
Cutlip, M.B. and Shacham, M., Problem Solving in Chemical and Biochemical Engineering with
POLYMATH, Excel, and MATLAB, 2nd edn. (2008), Prentice Hall, Upper Saddle River, NJ.
Fausett, L.V., Applied Numerical Analysis Using MATLAB, 2nd edn. (2007), Pearson Inc., New York.
Fogler, H.S., Elements of Chemical Reaction Engineering, 5th edn. (2008), Prentice Hall, Pearson
Education, Boston, MA.
Golub, G.H. and Van Loan, C.F., Matrix Computations, 3rd edn. (1996), Johns Hopkins University
Press, Baltimore, MD.
Gupta, S.K., Numerical Methods for Engineers, 3rd edn. (2013), New Academic Press, New Delhi,
India.
Petzold, L.R. and Ascher, U.M., Computer Methods for Ordinary Differential Equations and Differential-
Algebraic Equations (1998), Society for Industrial and Applied Mathematics, Philadelphia, PA.
Press, W.H., Teukolsky, S.A., Vetterling, W.T., and Flannery, B.P., Numerical Recipes: The Art of
Scientific Computing, 3rd edn. (2007), Cambridge University Press, New York.
Pushpavanam, S., Mathematical Methods in Chemical Engineering (2004), Prentice-Hall India Pvt.
Ltd (Verlag), New Delhi, India.
Shampine, L.F. and Reichelt, M.W., The MATLAB ODE suite, SIAM Journal on Scientific Computing,
18 (1997), 1–22.
Shampine, L.F., Reichelt, M.W., and Kierzenka, J.A., Solving index-1 DAEs in MATLAB and
Simulink, SIAM Review, 41 (1999), 538–552.
Skogestad, S., Dynamics and control of distillation columns: A tutorial introduction, Transactions of
IChemE (UK), 75, Part A (1997), 539–562.
Strang, G., Linear Algebra and Its Applications, 4th edn. (2006), Cengage Learning—India Edition,
New Delhi, India.

527
Index

A Bisection method
convergence order, 229
Adams-Bashforth (AB) methods
failure, 231
coefficients, 321–322
function values, 228
definition, 320–321
iteration value, 228
second-order, 92
MATLAB® code, 232–233
stability, 325
Redlich-Kwong equation, 229–231
Adams-Moulton (AM) methods
Blasius equation, 391
first-order method, 318
Boundary value problems (BVPs), 71–72
higher-order method, 319–320
Bracketing method, 228–233, 235
second-order method, 318–319
Brent’s method, 235–236
stability, 325
Broyden’s method, 246
Adaptive step-size methods, 329–330
Brusselator system, 384–387
Antoine’s equation, 410, 431
Butcher’s tableau, 87, 94
linear regression, 439–440
BVPs, see Boundary value problems
nonlinear regression, 440–442
vapor-liquid equilibrium, 253–254
Array functions, 461
C
Cartesian coordinate system, 341
Catalyst pellet
B
Langmuir-Hinshelwood kinetics, 308–311
Backward difference formula (BDF) methods Thiele modulus, 305–307
first-order method, 322 Chemostat analysis
formula for, 323 eigenvalues and eigenvectors, 188–189
NDF, 324 Jacobian value, 188
second-order method, 322–323 multivariate Taylor’s series expansion, 187
stability, 325–326 phase portrait, 190
Banded system, 277–278, 288–289 stability condition, 189–190
Batch distillation model, 356–357 trivial steady state, 190–191
Antoine’s equation, 354 Chemostat model, 261
benzene and ethylbenzene, 353–354 bifurcation analysis, 366–368
definition, 355 multivariate Newton-Raphson technique,
flowrates, 358–359 243–244
process, 354–355 phase-plane analysis, 365–366
Raoult’s law, 354 steady state multiplicity and stability,
temporal variations, 358 364–365
vapor fraction, 354–355 stiff system, 120–124
BDF, see Backward difference formula methods transcritical bifurcation
Belusov-Zhabotinsky (B-Z) reaction, 384 bifurcation plot, 371
Bifurcation point, 367 dilution rate, 369

529
530   ◾    Index

graphical method, 368 D

linear stability analysis, 370–371
Differential algebraic equations (DAEs)
steady state, 368–370
CSTR, 338
Complex kinetics, 266–268
direct substitution, 338
Constants and special variables,
formulating and solving, 339
451–452
heterogeneous reactor models
Continuous stirred tank reactor (CSTR)
algebraic equation, 342
DAEs, 338
concentration driving force, 341
nonisothermal
differential equation, 342
bifurcation diagram, 378
mass transfer coefficient, 341
extinction point, 377
single complex reaction, 351–353
graphical method, 372–374
index of, 340–341
inlet temperature, 115–116
ode15s, 348–350
jacket temperature, 112–113
pendulum model, 341
parameters, 111
solution methodology
parametric continuation, 378–379
algebraic variable, 342
phase-plane analysis, 376–377
combined approach, 345–348
stability analysis, 374–376
first-order kinetics, 342
steady state multiplicity, 257–261
nested approach, 343–345
T-axis, 377
Differential equations
transient simulations, 113–115
Adams-Bashforth methods, 320–322
Convective systems
Adams-Moulton methods, 318–320
finite differences, space and
BDF, 322–324
time, 136
non-self-starting property, 318
FTCS differencing, 138–139
RK methods, 317
higher-order upwind method, 140
Diffusive systems
Lax-Friedrichs scheme, 139
Crank-Nicolson method, 153–154
Lax-Wendroff method, 140
MOL using MATLAB® ODE solvers, 154–157
leapfrogging method, 139–140
packed bed reactor, 151
MOL
Dirichlet boundary condition, 274, 280, 285, 304–305
central difference in space,
Discrete-time model, 212–215
142–145
Doolittle method, 491
driver script, 144–145
Dynamical systems, 3
upwind difference in space,
145–148
numerical diffusion, 148–150
E
second-order implicit method, 140–141
stability methods, 157 Eigenvalues and eigenvectors
upwind difference in space, 136–138 applications, 58–62
Crank-Nicolson method, 316 characteristic equation, 55–56
analytical solution, 336 chemostat analysis, 188–189
central difference formula, 331–332 complex eigenvalues, 56
exploiting sparse structure, 337 decomposition, 56–58
function argument, 333 definitions, 54–56
ith equation, 331 linear difference equations, 64–65
MATLAB function, 333–334 linear differential equations, 63–64
ODEs, 331 similarity transform, 62–63
outlet concentration, 336 Elliptic PDEs, 276–277, 289–290
overall driver function, 335–336 Equation of state (EOS), 253
PER, 332–333 Ergun’s equation, 391
pfrCN_Stepper function, 334 Error analysis
pfrCrankNicolFun function, 334 convergence and stability, 20–21
CSTR, see Continuous stirred tank reactor global truncation error, 21–23
 Index   ◾    531

Euler’s explicit method, 74–76, 315 Lax-Wendroff method, 140

Euler’s implicit method, 76–77, 325 leapfrogging method, 139–140
MOL
central difference in space, 142–145
F
driver script, 144–145
Finite element methods (FEM), 135 upwind difference in space, 145–148
Finite volume methods (FVM), 134–135 numerical diffusion, 148–150
First-order kinetics, 263–265 second-order implicit method, 140–141
First same as last (FSAL) method, 105 upwind difference in space, 136–138
Fixed point iteration, 236–238
Flash separation, see Batch distillation model
I
Forward in time central in space (FTCS), 138–139,
152–153 Implicit methods
Fredholm integral equations, 262 Adams-Bashforth methods
fsolve method, 250–252 coefficients, 321–322
Function handles, 472–473 definition, 320–321
fzero method, 249–250 stability, 325
Adams-Moulton methods
first-order method, 318
G
higher-order method, 319–320
Gauss Elimination second-order method, 318–319
back-substitution, 486, 488, 490–491 stability, 325
LU decomposition, 491–493 batch distillation model, 356–357
naive Gauss Elimination, 487–490 Antoine’s equation, 354
partial pivoting method, 493–497 benzene and ethylbenzene, 353–354
Gauss-Siedel method definition, 355
diagonal dominance, 292–293 flowrates, 358–359
fixed point iteration, 292 process, 354–355
kth equation, 291 Raoult’s law, 354
tridiagonal system, 294–295 temporal variations, 358
Ghost-point method, 154 vapor fraction, 354–355
Global truncation errors (GTEs), 521–522 BDF
first-order method, 322
formula for, 323
H
NDF, 324
Harmonic oscillations, 382–383 second-order method, 322–323
Heat conduction, 304–305 stability, 325–326
Héron’s method, 10–11 Crank-Nicolson method
Heterogeneous reactor models analytical solution, 336
algebraic equation, 342 central difference formula, 331–332
concentration driving force, 341 exploiting sparse structure, 337
differential equation, 342 function argument, 333
mass transfer coefficient, 341 ith equation, 331
single complex reaction, 351–353 MATLAB function, 333–334
Heun’s method, 82, 84–86 ODEs, 331
Hybrid two-tank heater system, 116–120 outlet concentration, 336
Hyperbolic functions, 461 overall driver function, 335–336
Hyperbolic PDEs PER, 332–333
finite differences in space and time, 136 pfrCN_Stepper function, 334
FTCS differencing, 138–139 pfrCrankNicolFun function, 334
higher-order upwind method, 140 DAEs
Improve stability methods, 157 algebraic variable, 342
Lax-Friedrichs scheme, 139 combined approach, 345–348
532   ◾    Index

CSTR, 338 L
definition, 316–317
Langmuir-Hinshelwood-Hougen-Watson (LHHW)
direct substitution, 338
model
first-order kinetics, 342
different initial concentrations, 444–445
formulating and solving, 339
rate expression, 441
heterogeneous reactor models, 341–342,
single concentration, 442–444
351–353
Langmuir-Hinshelwood (LH) kinetics, 308–311
index of, 340–341
Lax-Friedrichs scheme, 139
nested approach, 343–345
Lax-Wendroff method, 140
ode15s, 348–350
Linear algebra
pendulum model, 341
eigenvalues and eigenvectors
distributed parameter
applications, 58–62
systems, 316
characteristic equation, 55–56
Euler’s implicit method, 325
complex eigenvalues, 56
MATLAB® nonstiff solvers, 326
decomposition, 56–58
MATLAB® stiff solvers, 326
definitions, 54–56
non-self-starting property, 318
linear difference equations, 64–65
RK methods, 317
linear differential equations, 63–64
stiff system
similarity transform, 62–63
linearized model, 314
overview, 28–30
ODE-IVP method, 315
SVD
phase-plane plot, 314
condition number, 47
Runge-Kutta (RK) methods, 313
directionality, 51–54
single variable, 315
MATLAB command, 45–46
trapezoidal methods, 325
orthonormal vectors, 41–42
adaptive step-sizing, 329–330
rank of a matrix, 47
AM-2, 327–329
sensitivity of solutions, 47–51
multivariable, 330
system of equations, 27–28
Integral equations
vector space
complex kinetics, 266–268
blending operations, 40–41
first-order kinetics, 263–265
change of basis, 34–35
Fredholm integral equations, 262
definition and properties, 30–32
Interpolation
image space and column space, 39
polynomial function
linear independence, 32–33
Lagrange interpolation, 501–502
natural basis, 34
Newton’s forward difference formula,
null and image spaces in MATLAB, 39–40
502–505
null and image spaces of matrix, 35–38
speed data, 499–500
span, 32
spline
subspace, 33
cubic spline interpolation,
Linear difference equations, 64–65
508–509
Linear differential equations, 63–64
methods, 505
Linear least squares regression
vs. pchip interpolation, 506–510
error and coefficient
U.S. FTP-75 test cycle, 499–500
quantitative information, 420
Inverse quadratic interpolation, 236
sample standard deviation, 419
Iterative methods
statistics, 420–423
Gauss-Siedel method, 293–297
general matrix approach, 415–416
with under-relaxation, 297
maximum likelihood solution, 418–419
straight line
error, 414–415
J
N discrete points, 414
Jordan canonical form, 63 specific heat data, 417–418
 Index   ◾    533

Linear multi-step methods Matrix inversion, 497–498

Adams-Bashforth methods, 320–322 Matrix operations and vector functions
Adams-Moulton methods, 318–320 array operations, 459
BDF, 322–324 basic mathematical operations, 456–458
non-self-starting property, 318 building, 453–454
RK methods, 317 creation, 452–453
Linear systems matrix divisions and slash operators, 458
catalyst pellet querying elements, 455–456
Langmuir-Hinshelwood kinetics, 308–311 special matrices, 454
thiele modulus, 305–307 Methanol synthesis
chemostat analysis copper/zinc catalyst, 387
eigenvalues and eigenvectors, 188–189 equilibrium constants, 388
Jacobian value, 188 input parameters and initial processing,
multivariate Taylor’s series expansion, 187 389–390
phase portrait, 190 reaction kinetics, 388–389
stability condition, 189–190 steady state PFR model, 391–394
trivial steady state, 190–191 transient reactor model, 396–397
convective/radiative heat losses, 304–305 axial profiles, 397–398
elliptic PDEs, 274–275 driver script, 397
mass-spring system, 197 gas-phase system, 395
ODE-BVPs, 274 pseudohomogeneous reactor, 394
ODEs steady state and transient simulations,
mass-spring system, 197 397–398
qualitative responses, 197–198 volumetric flowrate, 395
real and distinct eigenvalues, 192–197 water-gas shift reaction, 387
transient growth Method of lines (MoL), 134
normal and nonnormal matrices, 198–199 central difference in space, 142–145
normal and nonnormal systems, 199–201 driver script, 144–145
Line search method, 247–249 upwind difference in space, 145–148
Lineweaver-Burke plot, 430 using MATLAB® ODE solvers, 154–157
Local truncation error (LTE), 521–522 Mixed boundary condition, 274
Loops and execution control
conditional if block, 471–472
for and while loops, 468–471 N
LU decomposition, 491–493
Naive Gauss Elimination, 487–490
Neumann boundary condition, 274, 285,
M
290, 304
Mass-spring-damper system, 379–380 Newton-Cotes integration formulae
Mass-spring system, 197 derivation, 518–520
Mathematical functions multiple applications, 520–524
array functions, 461 Simpson’s 1/3rd rule, 516–517
common matrix, 459–460 Simpson’s 3/8th rule, 517–518
trigonometric functions, 461 trapezoidal rule, 513–516
MATLAB® code Newton-Raphson method, 476
array operations, 9–10 line search method, 247–249
functions, 7–9 multivariate, 241–245
loops and execution control, 10–11 numerical methods, 240–241
script, 5–6 secant method, 245–246
MATLAB file, 466–468 in single variable, 238–240
MATLAB® functions, 465–466, 524–526 Nonlinear algebraic equations
MATLAB script, 464–465 chemostat, 261
MATLAB® Solver ode23, 100–101 EOS, 253
534   ◾    Index

integral equations Nonlinear banded systems; see also Linear systems

complex kinetics, 266–268 fsolve, sparse systems, 304
first-order kinetics, 263–265 Gauss-Siedel method, 304–305
Fredholm integral equations, 262 linearization–based approach, 298–302
multiple variable solver, 250–252 ODE-BVP model, 296–297
single variable Nonlinear estimation
bisection method, 228–233 Lineweaver-Burke plot, 430
Brent’s method, 235–236 Michaelis-Menten kinetics, 429
fixed point iteration, 236–238 monod kinetics, 430–432
Newton-Raphson method, 238–240 optimization toolbox
numerical methods, 240–241 error bounds and confidence intervals, 434
Redlich-Kwong EOS method, 234–235 least squares fitting, 435
Regula-Falsi method, 235 lsqnonlin, lsqcurvefit and
single variable solver, 249–250 fmincon, 435–437
steady state, CSTR, 257–261 prediction model, 435
VLE power-law models, 429
bubble temperature calculation, 254 Nonnormal matrices, 198–199
dew temperature calculation, 254 Normal matrix, 198–199
T–x–y diagram, 255–257 Numerical difference formula (NDF), 324
Nonlinear analysis Numerical differentiation
chemostat model first derivative
bifurcation analysis, 366–368 backward difference formula, 478
phase-plane analysis, 365–366 central difference formula, 476, 478
steady state multiplicity and stability, error term, 479–480
364–365 forward difference formula, 476–477, 480
transcritical bifurcation, 368–371 representation, 475
cricket ball trajectory Taylor’s series expansion, 477–479
animation, 403–404 heat flux, 477
ODE, 399–400 Newton-Raphson method, 476
time and location, 400–403 round-off errors, 482–483
limit cycle oscillations second derivative, 481
Brusselator system, 384–387 central difference formula, 480
B-Z reaction, 384 definition, 475
linear systems, 379–381 forward difference formula, 481–482
van der Pol oscillator, 381–383 Numerical integration
methanol synthesis geometric interpretation, 511–512
copper/zinc catalyst, 387 Newton-Cotes integration formulae
equilibrium constants, 388 derivation, 518–520
input parameters and initial processing, multiple applications, 520–524
389–390 Simpson’s 1/3rd rule, 516–517
reaction kinetics, 388–389 Simpson’s 3/8th rule, 517–518
steady state PFR model, 391–394 trapezoidal rule, 513–516
transient reactor model, 394–398 quadrature and MATLAB® functions,
nonisothermal CSTR 524–526
bifurcation diagram, 378 volume of PFR, 512
extinction point, 377 Numerical methods
graphical method, 372–374 errors, 12
parametric continuation, 378–379 machine precision, 12–14
phase-plane analysis, 376–377 round-off errors, 14–15
stability analysis, 374–376 Taylor’s series, 15–16
T-axis, 377 trade-off, 18–20
temperature, 377–378 truncation error, 16–18
 Index   ◾    535

O Output display and plotting

basic plotting functions, 463–464
Optimization toolbox, 434–437
results, 463
Ordinary differential equation (ODE)
text display, 461–462
BVPs, 69–70
chemostat, 120–124
classical RK-4 method, 102–103
P
Euler’s explicit method, 74–76
Euler’s implicit method, 76–77 Parabolic PDEs
fourth-order RK method, 101–102 Crank-Nicolson method, 153–154
geometric interpretation, 72–73 MOL using MATLAB® ODE solvers, 154–157
Higher-order RK methods packed bed reactor, 151
Butcher’s tableau, 94 polymer curing
error estimation, 97–100 driver script, 205–206
explicit RK methods, 95–96 1D transient heat equation, 202
MATLAB® Solver ode23, 100–101 spatial temperature profile, 206
step-size adaptation, 100 temporal variations, 207–208
Kutta’s 3/8th rule RK-4 method, 103 thermosetting polymer, 203–205
MATLAB® Solver ode23, 100–101 Partial differential equations (PDEs)
multivariable case, 80–81 Dirichlet condition, 132–133
nonlinear case, 81 elliptic, 129–130
PFR hyperbolic, 130–132; see also Convective
comparison, 110–111 systems
idealized reactor, 106 initial conditions, 132
as ODE-IVP, 106–108 linear vs. nonlinear, 128
second-order methods mixed condition, 133
Adams-Bashforth methods, 92 Neumann condition, 133
BDF formula, 93 nonisothermal plug flow reactor, 157–164
overview, 82 numerical methods
predictor-corrector method, 92 FEM, 135
Richardson’s extrapolation method, finite difference techniques, 134–135
89–91 FVM, 134–135
RK-2 method, 83–89 MOL, 134
trapezoidal rule, 91–92 packed bed reactor with multiple reactions,
stability and step-size, 78–80 164–170
Ordinary differential equation– parabolic, 132; see also Diffusive systems
boundary value problems Steady Graetz problem
(ODE-BVPs), 276 heat transfer, 170–174
boundary conditions, 285–288 Nusselt number calculation, 174–176
convective/radiative heat losses, 304–305 parabolic velocity profile, 174
nonlinear banded systems, 296–297 Partial pivoting method, 493–497
Ordinary differential equation–initial value problem PCHIP, see Piecewise cubic Hermite interpolating
(ODE-IVP), 179 polynomial
Ordinary differential equations (ODEs) PDEs, see Partial differential equations
model Pendulum model, 341
binary distillation column Peng-Robinson EOS, 253
description, 181–183 PFR, see Plug flow reactor
equations and simulation, 183–185 pfrCrankNicolFun function, 334
parameters effect, 185–186 Phase-plane analysis
mass-spring system, 197 chemostat model, 365–366
qualitative responses, 197–198 nonlinear CSTR, 376–377
real and distinct eigenvalues, 192–197 Piecewise cubic Hermite interpolating polynomial
Orth command, 40 (PCHIP), 505–508
536   ◾    Index

Plug flow reactor (PFR), 2, 332–333 general matrix approach, 415–416

boundary constraints, 216–219 maximum likelihood solution, 418–419
comparison, 110–111 straight line, 414–415, 417–418
idealized reactor, 106 linear regression, 432–434
integral equations methane, specific heat, 437–438
complex kinetics, 266–268 nonlinear estimation
first-order kinetics, 263–265 Lineweaver-Burke plot, 430
Fredholm integral equations, 262 Michaelis-Menten kinetics, 429
as ODE-IVP, 106–108 monod kinetics, 430–432
Polymer curing process optimization toolbox, 434–438
driver script, 205–206 power-law models, 429
1D transient heat equation, 202 orientation, 410–411
spatial temperature profile, 206 polynomial regression, 413
temporal variations, 207–208 Chi-squared value, 426
thermosetting polymer, 203–205 definition, 424
Polynomial function parity and error plots, 426–427
Lagrange interpolation, 501–502 polynomial fit, 425–426
Newton’s forward difference formula, 502–505 second-order curve, 427
Polynomial regression, 413 third-order polynomial, 427–428
Chi-squared value, 426 singularity and SVD, 428–429
definition, 424 statistics, 411–412
parity and error plots, 426–427 temperature dependence, 409
polynomial fit, 425–426 Regula-Falsi method, 235
second-order curve, 427 Relative volatility, 185–186
third-order polynomial, 427–428 Relaxation oscillations, 382–383
Richardson’s extrapolation method, 89–91
Runge-Kutta (RK) methods, 313, 317
Q
Butcher’s tableau, 87, 94
Quadrature methods, 524–526 classical RK-4 method, 102–103
error estimation, 97–100
explicit RK methods, 95–96
R
fourth-order method, 101–102
Radiative heat losse, 304–305 Heun’s method, 84–86
Redlich-Kwong (RK) EOS method, 226, 234–235, Kutta’s 3/8th rule RK-4 method, 103
249–250 MATLAB® Solver ode23, 100–101
Redlich-Kwong (RK) equation, 229–231 Ralston’s method, 86
Reflux ratio (RR), 185–186 step-size adaptation, 100
Regression and parameter estimation Step-Size Halving, 87–89
Antoine’s equation, 410, 431
linear regression, 439–440
S
nonlinear regression, 440–442
differential approach Secant method
concentration vs. time data, 446 Brent’s method, 235–236
constant volume batch reactor, 446 Newton-Raphson method, 245–246
kinetic analysis, 446–448 Redlich-Kwong EOS, 234–235
power-law model, 445–446 Regula-Falsi method, 235
general multilinear regression, 423–424 Simpson’s 1/3rd rule, 516–517
LHHW model Simpson’s 3/8th rule, 517–518
different initial concentrations, 444–445 Singular value decomposition (SVD)
rate expression, 441 condition number, 47
single concentration, 442–444 directionality, 51–54
linear least squares regression MATLAB command, 45–46
error and coefficient, 419–423 orthonormal vectors, 41–42
 Index   ◾    537

rank of a matrix, 47 Trapezoidal rule, 513–516

sensitivity of solutions, 47–51 trapz function, 524
spHeat function, 473 Tridiagonal matrix algorithm (TDMA), 277–284
Stability analysis, see Linear systems Tridiagonal system
Steady Graetz problem elliptic PDEs, 289–290
heat transfer, 170–174 Gauss-Siedel method, 294–295
Nusselt number calculation, 174–176 ODE-BVP, 287–290
parabolic velocity profile, 174 TDMA, 277–281
Stiff system Trigonometric functions, 461
chemostat model, 120–124 Turning-point bifurcation
linearized model, 314 bifurcation diagram, 378
ODE-IVP method, 315 extinction point, 377
phase-plane plot, 314 graphical method, 372–374
Runge-Kutta (RK) methods, 313 parametric continuation, 378–379
single variable, 315 phase-plane analysis, 376–377
Successive over-relaxation, 295 stability analysis, 374–376
T-axis, 377
temperature, 377–378
T
T-x-y diagram, 255–257
TDMA, see Tridiagonal matrix algorithm
Thomas algorithm, 277–284
V
Time-varying inlet conditions
chemostat, 208–212 van der Pol oscillator, 381–383
zero-order hold reconstruction, 212–215 Vapor-liquid equilibrium (VLE)
Transcritical bifurcation bubble temperature calculation, 254
bifurcation plot, 371 dew temperature calculation, 254
dilution rate, 369 T–x–y diagram, 255–257
graphical method, 368 Vector spaces
linear stability analysis, 370–371 blending operations, 40–41
steady state, 368–370 change of basis, 34–35
Transient reactor model, 396–397 definition and properties, 30–32
axial profiles, 397–398 image space and column space, 39
driver script, 397 linear independence, 32–33
gas-phase system, 395 natural basis, 34
pseudohomogeneous reactor, 394 null and image spaces in MATLAB, 39–40
steady state and transient simulations, null and image spaces of matrix, 35–38
397–398 span, 32
volumetric flowrate, 395 subspace, 33
Trapezoidal methods, 325
adaptive step-sizing, 329–330
Z
AM-2, 327–329
multivariable, 330 Zero-order hold reconstruction, 212–215