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Liliane Maria Ferrareso Lona

A Step by Step
Approach to the
Modeling of Chemical
Engineering
Processes
Using Excel for Simulation
A Step by Step Approach to the Modeling
of Chemical Engineering Processes
Liliane Maria Ferrareso Lona

A Step by Step Approach

to the Modeling of Chemical
Engineering Processes
Using Excel for Simulation
Liliane Maria Ferrareso Lona
School of Chemical Engineering
University of Campinas
Campinas, S~ao Paulo, Brazil

ISBN 978-3-319-66046-2 ISBN 978-3-319-66047-9 (eBook)

https://doi.org/10.1007/978-3-319-66047-9

Library of Congress Control Number: 2017953385

© Springer International Publishing AG 2018

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or
information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt
from the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the
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in published maps and institutional affiliations.

Printed on acid-free paper

This Springer imprint is published by Springer Nature

The registered company is Springer International Publishing AG
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
“To Natassia, Alessandra and Jayme”
Preface

The aim of this book is to present the issue of modeling and simulation of chemical
engineering processes in a simple, didactic, and friendly way. In order to reach this
goal, it was decided to write a book with few pages, simple language, and many
illustrations. Sometimes, the rigor of the mathematical nomenclature has been a
little simplified or relaxed, to not lose focus on the modeling and simulation. The
idea was not to scare readers but to motivate them, making them feel confident and
sure they are able to learn how to model and simulate even complex chemical
engineering problems. The book is split into two parts: the first one (Chaps. 2, 3,
and 4) deals with modeling, and the second (Chaps. 5, 6, and 7) deals with
simulation.
To simplify the understanding of how to develop mathematical models, a
“recipe” is proposed, which shows how to build a mathematical model step by
step. This procedure is applied throughout the entire book, from simpler to more
complex problems, progressively increasing the degree of complexity. For each
concept of chemical engineering added to the system being modeled (kinetics,
reactors, transport phenomena, etc.), a very simple explanation is given about its
physical meaning to make the book understandable to students at the start of a
chemical engineering course, to students of correlated areas, and even to engineers
who have been away from academia for a long time.
The second part of this book is dedicated to simulation, in which mathematical
models obtained from the modeling are numerically solved. There are many
numerical methods available in the literature for solving the same equations. The
focus of this book is not to present all of the existing methods, which can be found
in excellent books about numerical methods. In this book, a few effective alterna-
tives are chosen and applied in several practical examples. For each case, the
numerical resolution is presented in detail, up to obtaining the final results. The
idea is to avoid the reader getting lost in many alternatives of numerical methods,
and to focus on how exactly to implement the simulation to obtain the desired
results.

vii
viii Preface

When using numerical methods, the simulation step can involve computational
packages and programming languages. There are several computational tools for
simulation, and it is not possible to say that one is better than another; however,
since in most cases a chemical engineering student will work in chemical industries,
this book adopts the Excel tool, which is widely used and has a very friendly
interface and almost no cost. To develop computational codes, the programming
language Visual Basic for Applications (VBA), available in Excel itself, will
be used.
It is expected that, with this book, chemical engineering students will feel
motivated to solve different practical problems related to chemical industries,
knowing they can do so in an easy and fast way, with no need for expensive
software.

Campinas, Brazil Liliane Maria Ferrareso Lona

Organization of the Book

Chapter 1 of the book gives a short introduction and shows the importance of the
modeling and simulation issues for a chemical engineer. Important concepts needed
to understand the book will also be presented.
Chapter 2 presents a “recipe” (a step-by-step procedure) to be followed to build
models for chemical engineering systems, using a very simple problem. The same
recipe is used throughout the entire book, to solve more and more complex
problems.
Chapter 3 deals with lumped-parameter problems (in steady-state or transient
regimes), in which the modeling generates a system of algebraic or ordinary
differential equations. The chapter starts by applying the recipe seen in Chap. 2
to simple lumped-parameter problems, but as new concepts of chemical engineer-
ing are presented throughout the chapter, the complexity of the problems starts
increasing, although the recipe is always followed.
Chapter 4 deals with distributed-parameter systems in steady-state and transient
regimes, in which variables such as concentration and temperature change with the
position. This kind of problem generates ordinary or partial differential equations.
In this chapter, the complexity of examples increases little by little as they are
presented, but all of them use the same recipe presented in Chap. 2. In this way,
readers can easily understand how to build complex models.
Chapters 5, 6, and 7 are dedicated to numerically solving algebraic equations,
ordinary differential equations, and partial differential equations, respectively.
There are many different numerical methods available, but in these three chapters
a few alternatives will be used because the main purpose of this book is to obtain a
fast, robust, and simple way to simulate chemical engineering problems, not to
study in detail the different numerical methods available in the literature. All
simulations will be done using Excel spreadsheets or codes in VBA.
Chapter 5 uses the Newton–Raphson method to solve nonlinear algebraic equa-
tions and presents the concepts of inversion and multiplication of a matrix, avail-
able in Excel, to solve linear algebraic equations. Chapter 5 also presents an
alternative based on the Solver tool available in Excel for both linear and nonlinear

ix
x Organization of the Book

algebraic equations. Chapter 6 uses Runge–Kutta methods to solve ordinary differ-

ential equations, and Chap. 7 adopts the finite difference method to solve partial
differential equations.
I hope this book will be understandable to many people and can motivate all who
wish to learn the art of modeling and simulating chemical engineering processes.
Good reading!
Acknowledgments

I would like to thank Prof. Maria Aparecida Silva from the Chemical Engineering
School at the University of Campinas, who recently retired but, even so, agreed to
read the entire book and made valuable corrections and suggestions.
I would also like to thank Prof. Jayme Vaz Junior from the Department of
Applied Mathematics at the University of Campinas, who kindly provided the
analytical solution shown in Fig. 7.11.
I am very grateful to Prof. Nicolas Spogis who suggested a more didactical way
to present one of the subroutines of Chap. 6, and Prof. Roniérik Pioli Vieira, who
recommended two examples presented in this book.
I am also deeply grateful to my undergraduate students and teaching assistants,
who, in some way or other, made this book better—in particular, Jo~ao Gabriel
Preturlan, Natalia Fachini, and Carolina Machado Di Bisceglie.

xi
Contents

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 The Recipe to Build a Mathematical Model . . . . . . . . . . . . . . . . . . 5
2.1 The Recipe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2 The Recipe Applied to a Simple System . . . . . . . . . . . . . . . . . . 8
3 Lumped-Parameter Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.1 Some Introductory Examples . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2 Some Concepts About Convective Heat Exchange . . . . . . . . . . . 21
3.3 Some Concepts About Chemical Kinetics and Reactors . . . . . . . 28
3.3.1 Some Concepts About Kinetics
of Chemical Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.3.2 Some Concepts About Chemical Reactors . . . . . . . . . . . . 30
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4 Distributed-Parameter Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.1 Some Introductory Examples . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.2 Concepts About Transfer by Diffusion . . . . . . . . . . . . . . . . . . . . 58
4.2.1 Diffusive Transport of Heat . . . . . . . . . . . . . . . . . . . . . . 58
4.2.2 Diffusive Transport of Mass . . . . . . . . . . . . . . . . . . . . . . 59
4.2.3 Diffusive Transport of Momentum . . . . . . . . . . . . . . . . . 60
4.2.4 Analogies Among All Diffusive Transports . . . . . . . . . . . 62
4.2.5 Examples Considering the Diffusive Effects
on the Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.3 Examples Considering Variations in More
than One Dimension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

xiii
xiv Contents

5 Solving an Algebraic Equations System . . . . . . . . . . . . . . . . . . . . . 89

5.1 Problems Involving Linear Algebraic Equations . . . . . . . . . . . . . 89
5.2 Problems Involving Nonlinear Algebraic Equations . . . . . . . . . . 96
5.2.1 Demonstration of the NR Method to Solve
a Nonlinear Algebraic Equations System . . . . . . . . . . . . 97
5.2.2 Numerical Differentiation . . . . . . . . . . . . . . . . . . . . . . . 101
5.2.3 Using Excel to Solve a Nonlinear Algebraic Equation
Using the NR Method . . . . . . . . . . . . . . . . . . . . . . . . . . 102
5.3 Solving Linear and Nonlinear Algebraic Equations
Using the Solver Tool . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
6 Solving an Ordinary Differential Equations System . . . . . . . . . . . . 113
6.1 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
6.2 Runge–Kutta Numerical Methods . . . . . . . . . . . . . . . . . . . . . . . 116
6.2.1 First Order Runge–Kutta Method, or Euler Method . . . . . 116
6.2.2 Second Order Runge–Kutta Method . . . . . . . . . . . . . . . . 117
6.2.3 Runge–Kutta Method of the Fourth Order . . . . . . . . . . . . 120
6.3 Solving ODEs Using an Excel Spreadsheet . . . . . . . . . . . . . . . . 122
6.3.1 Solving a Single ODE Using Runge–Kutta Methods . . . . 122
6.3.2 Solving a System of Interdependent ODEs
Using Runge–Kutta Methods . . . . . . . . . . . . . . . . . . . . . 126
6.4 Solving ODEs Using Visual Basic . . . . . . . . . . . . . . . . . . . . . . . 129
6.4.1 Enabling Visual Basic in Excel . . . . . . . . . . . . . . . . . . . 130
6.4.2 Developing an Algorithm to Solve One ODE
Using the Euler Method . . . . . . . . . . . . . . . . . . . . . . . . . 130
6.4.3 Developing an Algorithm to Solve One ODE
Using the Runge–Kutta Fourth-Order Method . . . . . . . . . 135
6.4.4 Developing an Algorithm to Solve a System
of ODEs Using the Euler and Fourth-Order
Runge–Kutta Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 136
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
7 Solving a Partial Differential Equations System . . . . . . . . . . . . . . . 145
7.1 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
7.2 Finite Difference Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
7.3 Introductory Example of Finite Difference
Method Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
7.4 Application of the Finite Difference Method . . . . . . . . . . . . . . . 149
7.4.1 PDEs Transformed into an Algebraic
Equations System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Contents xv

7.4.2 PDEs Transformed into an ODE System . . . . . . . . . . . . . 154

7.4.3 Solving a System of PDEs . . . . . . . . . . . . . . . . . . . . . . . 155
7.4.4 PDEs with Flux Boundary Conditions . . . . . . . . . . . . . . . 160
Appendix 7.1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
Appendix 7.2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
About the Author

Liliane Maria Ferrareso Lona received her bachelor’s (1991), master’s (1994),
and PhD (1996) degrees in chemical engineering from the University of Campinas
(Unicamp). She pursued her postdoctoral studies at the Institute for Polymer
Research at the University of Waterloo, Canada, from 2001 until 2002. The subject
matter in her master’s and PhD courses was related to modeling and simulation of
petrochemical processes, while her postdoctoral studies focused on the area of
modeling, simulation, and optimization of polymerization reactors. In 1996, Liliane
became professor at the School of Chemical Engineering–Unicamp, and in 2010
she became full professor with a specialization in the analysis and simulation of
chemical processes. Liliane Lona taught for more than 20 times an undergraduate
course related to the area of this book. She supervised dozens of grade and
undergraduate students in the modeling and simulation area, and many of these
works received awards, such as (i) the BRASKEM/Brazilian Association of Chem-
ical Engineering Award (2007), (ii) the Petrobras Award Pipeline Technology
(2000 and 2003), and (iii) the Regional Council of Chemistry Award (2000).
Liliane published many scientific papers in reputed journals and also served as
postgraduate coordinator (2006–2010) and director (2010–2014) of the School of
Chemical Engineering–Unicamp.

xvii
Chapter 1
Introduction

In chemical engineering, modeling and simulation are important tools for engineers
and scientists to better understand the behavior of chemical plants. Modeling and
simulation are very useful to design, to scale up and optimize pieces of equipment
and chemical plants, for process control, for troubleshooting, for operational fault
detection, for training of operators and engineers, for costing and operational
planning, etc. A very important characteristic of modeling and simulation is its
advantageous cost–benefit ratio because with a virtual chemical plant, obtained
from the modeling and simulation, it is possible to predict different scenarios of
operations and to test many layouts at almost no cost and in a safe way.
A model can be developed using deterministic or phenomenological modeling
when mathematical equations, based on conservation laws (mass, energy, and
momentum balances), are used to represent what physically happens in a system.
When conservation laws cannot be applied and an uncertainty principle is intro-
duced, stochastic or probabilistic models can be used, like population balance or
empirical models. This book will address only deterministic or phenomenological
models.
A model can be classified as a lumped-parameter or distributed-parameter
model. In a lumped-parameter model, spatial variations in a physical quantity of
interest are ignored and the system is considered homogeneous throughout the
entire volume. An example of a system that can be modeled using a lumped-
parameter model is a perfectly stirred tank, in which variables, such as temperature,
concentration, density, etc, are uniform at all points inside the tank, due to the
mixing. On the other hand, a distributed-parameter model assumes variations in a
physical quantity of interest from one point to another inside the volume. One
example of a system that could be modeled using a distributed-parameter model is a
tubular reactor, in which the concentration of the reactant decreases along the
reactor length. In fact, every real system is distributed; however, if the variations
inside the system are very small, they can be ignored and lumped-parameter models
can be used. For example, if the agitation in the tank mentioned above was not
perfect, small dead zones inside the tank could be generated. However, even so, we

© Springer International Publishing AG 2018 1

L.M.F. Lona, A Step by Step Approach to the Modeling of Chemical
Engineering Processes, https://doi.org/10.1007/978-3-319-66047-9_1
2 1 Introduction

could use a lumped-parameter model if we consider—as a simplifying hypothesis—

perfect agitation, with the small dead zones ignored. Realistic simplifying hypoth-
eses can always be assumed when we are developing models, in order to make them
easier to solve.
Another classification used for models is steady-state versus transient regimes.
A system is in a steady state when it does not change over time, which means it is
static or stationary. On the other hand, a system is in a transient regime when it
changes with respect to time. A transient regime is also called a non-steady-state,
unsteady-state, or dynamic regime.
A system modeled by lumped-parameter models is homogeneous and does
not present variation throughout the volume, so it is easy to imagine that the final
mathematical equation that represents this system (the mathematical model) does
not show a derivative with respect to any spatial coordinate. In addition, if this
system is in a transient regime (changing over time), the mathematical model must
present a derivative with respect to time, while a system in a steady state (static)
must not. In this way, it is easy to conclude that a lumped-parameter model in a
steady state is represented by algebraic equations (AEs), while a lumped-parameter
model in a transient regime is represented by ordinary differential equations
(ODEs).
A distributed-parameter model assumes variation inside the volume, so its
mathematical equation (generated from the modeling) will present at least one
derivative with respect to spatial coordinates. If the system is in a steady state
and there is variation in only one spatial coordinate, the mathematical model will be
represented by ODEs, but if this system is in a transient regime, it will be
represented by partial differential equations (PDEs), with derivatives with respect
to time and one spatial coordinate. Finally, if the distributed-parameter model
assumes variation in more than one spatial coordinate, it will be represented by
PDEs for both steady-state and transient regimes. Fig. 1.1 summarizes all situations
analyzed.
Obtaining mathematical equations that represent a system is the modeling step.
After that, the mathematical equations must be solved. This second part is the
simulation of the system. The simulation can be done using analytical and numer-
ical methods. This book will focus on numerical solutions.

Lumped-parameter Distributed-parameter
models models

Steady State Transient Regime Steady State Transient Regime

AE ODE ODE or PDE PDE

Fig. 1.1 Types of mathematical equations generated from lumped- and distributed-parameter
models in steady-state and transient regimes
1 Introduction 3

If the model and simulation are used to predict the behavior of a system that
already exists, we say we are doing an analysis of the system. On the other hand, if
the modeling and simulation are used to define the layout of a system that does not
yet exist, we say we are doing synthesis.
In this book, Chaps 2, 3, and 4 will focus on how a deterministic mathematical
model is developed. Chapter 2 will present a simple recipe that can be used to
obtain mathematical models from simple to very complex systems. Chapter 3 will
be devoted to lumped-parameter models, and Chap. 4 to distributed-parameter
models. Chapters 5, 6, and 7 will address how the mathematical equations gener-
ated from the modeling can be solved. Chapters 5, 6, and 7 will focus on numerical
solutions for AEs, ODEs, and PDEs, respectively. Despite the huge number of
numerical methods available in the literature, this book will focus on just a few
numerical methods and will use Excel to solve them. The main idea of this book is
to provide a simple and fast tool to obtain numerical solutions for even complex
mathematical equations in a targeted and simple way using Excel, which is a very
friendly and available tool.
Chapter 2
The Recipe to Build a Mathematical Model

Most chemical engineering students feel a shiver down the spine when they see a set
of complex mathematical equations generated from the modeling of a chemical
engineering system. This is because they usually do not understand how to achieve
this mathematical model, or they do not know how to solve the equations system
without spending a lot of time and effort.
Trying to understand how to generate a set of mathematical equations to
represent a physical system (to model) and how to solve these equations
(to simulate) is not a simple task. A model, most of the time, takes into account
all phenomena studied during a chemical engineering course (mass, energy and
momentum transfer, chemical reactions, etc.). In the same way, there is a multitude
of numerical methods that can be used to solve the same set of equations generated
from the modeling, and many different computational languages can be adopted to
implement the numerical methods. As a consequence of this comprehensiveness
and the combinatorial explosion of possibilities, most books that deal with this
subject are very comprehensive, requiring a lot of time and effort to go through the
subject.
This book tries to deal with this modeling and simulation issue in a simple, fast,
and friendly way, using what you already know or what you can intuitively or easily
understand to build a model step by step and, after that, solve it using Excel, a very
friendly and widely used tool.
This chapter starts by showing that even if you are a lower undergraduate
student, you already known how to do mental calculations to model and simulate
simple problems. To prove that, let us imagine a cylindrical tank initially containing
10 m3 of water. Let us also imagine that the input and output valves in this tank
operate at the same volumetric flow rate (2 m3/h), as shown in Fig. 2.1. Assume that
the density of water remains constant all the time.
The first question is: 2 h later, what is the volume of water inside the tank? If you
say 10 m3, you are correct. The flow rate that enters the tank is equal to the flow rate
that exits (2 m3/s), so the volume of water in the tank remains constant (10 m3).

© Springer International Publishing AG 2018 5

L.M.F. Lona, A Step by Step Approach to the Modeling of Chemical
Engineering Processes, https://doi.org/10.1007/978-3-319-66047-9_2
6 2 The Recipe to Build a Mathematical Model

2 m3/h
Initial volume of water = 10 m3

2 m3/h

Fig. 2.1 Tank of water with an initial volume equal to 10 m3

Now, if the input volumetric flow rate changes to 3 m3/h and the flow rate at the
exit remains at 2 m3/h, what is the volume of water in the tank after 2 h? If you
correctly say 12 m3, it is because you mentally develop a model to represent this tank
and after that you simulate it. When the inflow rate becomes 3 m3/h, by inspection
one can conclude easily that the volume of water will increase 1 m3 in each hour.
Unfortunately, you only know how to do mental modeling and simulation if the
problem is very simple. In order to understand how to model and simulate complex
systems, let us try to understand what was mentally done in this simple example and
transform that into a step-by-step procedure that is robust enough to successfully
work also for very complex systems.

2.1 The Recipe

In order to build a mathematical model, three fundamental concepts are used:

1. Conservation Law: The conservation law says that what enters the system (E),
minus what leaves the system (L), plus what is generated in the system (G),
minus what is consumed (C) in the system, is equal to the accumulation in the
system (A); or:

E
LþG
C¼A

The accumulation is the variation that occurs in a period of time. This

accumulation can be positive or negative, i.e., if what enters plus what is
generated in the system is greater than what leaves plus what is consumed in
this system, there is a positive accumulation. Otherwise, there is a negative
accumulation.
When developing mass and energy balances in the problems presented in this
book, we will assume that terms of generation and/or consumption can exist if
there are chemical reactions. For example, there is energy generation if there is
an exothermic chemical reaction, which will result in an increase in temperature.
2.1 The Recipe 7

Fig. 2.2 Variation of the dependent variable y with the independent variable x

2. Control volume: The control volume is the volume in which the model is
developed and the conservation law is applied. All variables (concentration,
temperature, density, etc.) have to be uniform inside the control volume. In the
example of the tank presented previously, all variables do not change with the
position inside the tank (a lumped-parameter problem), so the control volume is
the entire tank.
3. Infinitesimal variation of the dependent variable with the independent variable:
Imagine that a dependent variable y varies with x (an independent variable)
according to the function shown in Fig. 2.2. Also imagine that in an initial
condition x0 the initial value of y is y0. To estimate the value of the dependent
variable y after an infinitesimal increment in x (Δx), one can draw a tangent line
to the curve starting from the point (x0, y0), as shown in Fig. 2.2.
The tangent line reaches v1 at x ¼ x1 (x1 ¼ x0 þ Δx). If the increment Δx is
sufficiently small, it follows that y1 ffi v1, and it is possible to obtain the value of
y1 using the concept tangent of α:


y1
y0 dy


tan α ¼ ¼
x1
x0 dx
x0 , y0

so:


dy


y1 ¼ y0 þ Δx

dx x0 , y0
8 2 The Recipe to Build a Mathematical Model

Generalizing and simplifying the way to show the index of the derivative:

dyi
yiþ1 ¼ yi þ Δx ð2:1Þ
dx
Equation (2.1) could be also obtained using the first term of a Taylor series
expansion (Eq. 2.2):

dyi 1 d 2 yi 1 d 3 yi 1 d 4 yi
yiþ1 ffi yi þ Δx þ 2
ðΔxÞ2 þ 3
ðΔxÞ3 þ ðΔxÞ4 þ    ð2:2Þ
dx 2! dx 3! dx 4! dx4
For all systems presented in this book, the same recipe will be used to obtain the
mathematical model, following the three steps:

Definition of Control volume

Application of conservation law

Application of the concept of Infinitesimal variation of the dependent variable with the
independent variable (if there is changing with time and/or space)

2.2 The Recipe Applied to a Simple System

Keeping in mind the three fundamental concepts presented in Sect. 2.1, let us apply
the step-by-step procedure (the recipe) to model the tank presented previously. This
procedure, used to model this simple system, will be the same used throughout the
entire book, in order to solve more and more complex problems.
As stated in Sect. 2.1, the entire tank must be considered as the control volume
because we are dealing with a lumped-parameter problem. The dashed line in
Fig. 2.3 shows the control volume considered in this case.

Fig. 2.3 Tank of water 3 m3/h

with the control volume Initial water volume= 10 m3
used in the modeling

2 m3/h
2.2 The Recipe Applied to a Simple System 9

The application of the conservation law to the control volume yields the expres-
sion presented by Eq. (2.3) (observe that there is neither generation nor consump-
tion of water):

E
L¼A ð2:3Þ

The E and L terms can be easily obtained, since the flow rates that enter and
leave the tank are known (3 m3/h and 2 m3/h, respectively); however, how can the
accumulation term be obtained?
In order to obtain the accumulation term, we can use the concept of the
infinitesimal variation of the dependent variable with the independent variable. So
if we say that at a time t the mass of water in the tank is M (kg), after an infinitesimal
period of time (Δt) the mass of water in the tank will be M þ dM dt Δt (kg) (see
analogy with Eq. (2.1)). The table below summarizes this information.

t t þ Δt Dimension
dM kg
M Mþ Δt
dt

The amount of water accumulated in the tank in a period of time Δt is the mass of
water at the time t þ Δt minus the mass of water at the time t, so the accumulation
term (A) is given by:

dM
A¼Mþ Δt
M
dt
or:

dM
A¼ Δt ðkgÞ
dt
Since the mass is the density times the volume (M ¼ ρV) and the density remains
constant, the accumulation term can also be written as:

dV
A¼ρ Δt ðkgÞ
dt
A very important tool to check if a model is correct is to do a dimensional
analysis on all terms of the conservation law equation.
If we calculate how much water accumulates in the tank in a period of time Δt,
we have to consider how much water enters and leaves the tank in this same interval
of time (Δt). So, in a period of time Δt, the amount of water that enters and leaves
the tank is:

E ¼ 3ðm3 =hÞ ρðkg=m3 Þ ΔtðhÞ ! E ¼ 3ρ ΔtðkgÞ

L ¼ 2ðm3 =hÞ ρðkg=m3 Þ ΔtðhÞ ! L ¼ 2ρ ΔtðkgÞ
10 2 The Recipe to Build a Mathematical Model

so applying the conservation law for the period of time Δt yields:

dV
3ρΔtðkgÞ
2ρΔtðkgÞ ¼ ρ ΔtðkgÞ ð2:4Þ
|fflfflfflfflffl{zfflfflfflfflffl} |fflfflfflfflffl{zfflfflfflfflffl} dt ffl{zfflfflfflfflfflfflfflffl}
|fflfflfflfflfflfflffl
Enters ðEÞ Leaves ðLÞ
Accumulation ðAÞ

Observe that the density (ρ) is present in the three terms of the mass balance, so
Eq. (2.4) can be simplified. In this way, we can conclude that when the density
remains constant, we can directly do the volume balance (instead of mass balance).
In this case, the accumulation term, as well as the terms E and L, could be obtained
as shown below:

t t þ Δt Accumulation Dimension
dV dV m3
V V þ Δt Δt
dt dt

E ¼ 3ðm3 =hÞΔtðhÞ ! E ¼ 3Δtðm3 Þ

L ¼ 2ðm3 =hÞΔtðhÞ ! L ¼ 2Δtðm3 Þ

so the balance becomes:

    dV  3 
3Δt m3
2Δt m3 ¼ Δt m ð2:5Þ
|fflfflfflfflffl{zfflfflfflfflffl} |fflfflfflfflffl{zfflfflfflfflffl} dt ffl{zfflfflfflfflfflfflffl}
|fflfflfflfflfflffl
Enters ðEÞ Leaves ðLÞ
Accumulation ðAÞ

Observe that Eqs. (2.4) and (2.5) are the same, and after simplifying terms this
yields:

dV
¼1 ð2:6Þ
dt
Equation (2.6) represents the model for this simple system and agrees with the
mental calculation you did previously. Having completed the modeling stage, we
need to do the simulation, which is nothing more than solving, by analytical or
numerical methods, the equations generated from the modeling. In our case, as the
system is greatly simplified, a single and very simple ordinary differential equation
(ODE) is generated from the modeling, and it will be solved by direct integration.
To solve this ODE, one initial condition is necessary. In our case, we know that
in the beginning of the operation, the volume of water in the tank is 10 m3. So the
initial condition is:

At t ¼ 0, V ¼ 10 m3

Solving Eq. (2.6) using the initial conditions yields:

V ¼ 10 þ t ð2:7Þ
2.2 The Recipe Applied to a Simple System 11

Equation (2.7) shows how the volume of liquid in the tank varies with time,
making it possible to predict, for example, the time it takes for the liquid to overflow
the tank (also observe that the equation says that after 2 h, the volume of water is
12 m3, as predicted previously).
The procedure adopted for this simple example will be used from now on for
more and more complex examples.
Proposed Problem
2.1) Develop a model for the tank presented in Fig. 2.3, but consider that the flow
rate of water that leaves the tank (Qout, m3/h) depends on the level of the water (h)
inside the tank, in the way Qout ¼ 1 þ 0.1h (m3/h). This can be a real situation
because as the column of water increases, the pressure on the exit point also
increases, and consequently the exit flow rate becomes greater. Assuming that the
initial volume of water inside the tank is equal to 10 m3 and the cross-sectional area
of this tank is equal to 1 m2, the initial level of water (h) is 10 m, so in the beginning,
the flow rate that leaves the tank (Qout) is equal to 2 m3/h. In the beginning, the input
flow rate is equal to 2 m3/h, so the volume of water remains constant, in a steady-
state regime. If for some reason the inflow rate varies from 2 to 3 m3/h, develop a
mathematical model to represent how the level of water inside the tank varies with
time. Define the initial condition needed to solve the equation generated from the
modeling.
Chapter 3
Lumped-Parameter Models

This chapter uses the recipe presented in Chap. 2 to develop models for different
systems related to chemical engineering. The examples presented in this chapter
deal with lumped-parameter problems, in which spacial variations in a physical
quantity of interest are ignored. As shown in Fig. 1.1, lumped-parameter problems
in a steady state are represented by algebraic equations, and, in a transient regime,
by ordinary differential equations. In this chapter, we will only develop mathemat-
ical models using the recipe presented in Chap. 2. Numerical solution (using Excel)
of algebraic and ordinary differential equations will be seen in Chaps. 5 and 6,
respectively.
As mentioned in Chap. 1, one example of a lumped-parameter problem is a
perfectly stirred tank, in which we assume that the agitation is so perfect that the
system can be considered homogeneous (no internal profiles of concentration,
temperature, etc).
Section 3.1 will present three introductory examples of lumped-parameter
modeling involving mass, energy, and volume balances. Sections 3.2 and 3.3 will
revisit some concepts about heat transfer and chemical reactions, needed to model
problems with a somewhat greater complexity level, and will show five practical
examples of how to model systems involving these concepts.

3.1 Some Introductory Examples

This section will be presented in the form of three introductory examples, which
will explore mass, energy, and volume balances.
Example 3.1 Mass Balance in a Perfectly Stirred Tank
Let us consider a perfectly stirred tank initially containing 10 m3 of pure water.
Assume that the tank contains inlet and outlet valves, both operating at the same
flow rate (2 m3/h), so the volume of water inside the tank does not change over time

© Springer International Publishing AG 2018 13

L.M.F. Lona, A Step by Step Approach to the Modeling of Chemical
Engineering Processes, https://doi.org/10.1007/978-3-319-66047-9_3
14 3 Lumped-Parameter Models

Fig. 3.1 Perfectly stirred 2 m3/h

tank being fed with a NaOH 0.02 kg/m3
solution

x kg/m3 2 m3/h
x kg/m3

(assuming an incompressible fluid, i.e., constant density). In the beginning, the inlet
stream contains just water. At some point, a solution of NaOH at a concentration of
0.02 kg/m3 is fed instead, at the same flow rate (2 m3/h). What is the concentration
of NaOH in the liquid leaving the tank?
Solution:
By inspection, one can imagine that the concentration of NaOH in the tank is
initially zero (pure water) and when the solution of NaOH starts being fed,
the concentration of NaOH in the tank starts increasing, but it does not exceed
0.02 kg/m3.
One can also imagine that, if the agitation is perfect, the concentration of NaOH
at all points inside the tank is the same, including the point very close to the outlet
valve, so we can conclude that the concentration of NaOH inside the tank is equal to
the concentration of NaOH that leaves the tank. As we do not know the value of this
concentration (and remember, it will change over time), we will assume its value is
equal to x (kg/m3).
As this is a lumped-parameter problem, the entire tank must be considered as the
control volume. A scheme that represents our problem, from the point at which a
solution of NaOH starts being fed, can be seen in Fig. 3.1.
Let us start doing the mass balance of NaOH inside the tank (the control
volume). As there is no generation or consumption of NaOH (no chemical reac-
tion), the conservation law applied to this case yields E
L ¼ A.
The accumulation term can be obtained by the concept of the infinitesimal
variation of the dependent variable with the independent variable, considering
the amount of NaOH at time t and at time t + Δt. The amount of NaOH in the
tank is the concentration (x) of NaOH in the tank (kg/m3) multiplied by the volume
(V) of the tank (m3).

t t + Δt Dimension
dðVxÞ kg
Vx Vx þ Δt
dt

The amount of NaOH that accumulates in a period Δt is the amount of NaOH at

time t + Δt minus the amount of NaOH at time t.
3.1 Some Introductory Examples 15

d ðVxÞ
A¼ Δt ðkgÞ
dt
All terms of the conservation law (the amounts of NaOH that enter, leave, and
accumulate) must be considered in the same period of time, in this case, Δt (h).
The amount of NaOH (kg) that enters the tank in Δt (h) can be obtained
by multiplying the volumetric inflow rate (2 m3/h), the inflow concentration
(0.02 kg/m3), and the period of time Δt (h):

3

m kg
E¼2 0:02 ΔtðhÞ
h m3
E ¼ 0:04 Δt ðkgÞ

In the same way, one can obtain the amount of NaOH that leaves the tank in the
same period of time Δt (h):

3

m kg
L¼2 x ΔtðhÞ
h m3
L ¼ 2 x Δt ðkgÞ

The mass balance can be obtained by substituting the terms E, L, and A in the
conservation law:

d ðVxÞ
0:04Δt
2xΔt ¼ Δt ð3:1Þ
dt
Observe that all terms have the same dimension (kg). Simplifying the Δt term
yields:

dðVxÞ
¼ 0:04
2x
dt

In our case, the volume of the tank remains constant and is equal to 10 m3, so the
final equation to represent the concentration of NaOH in the tank (and leaving the
tank) is:

dx 0:04
2x
¼
dt 10
This ordinary differential equation (ODE) is the mathematical model that rep-
resents the stirred tank. The simulation of this system is obtained by solving this
ODE analytically or numerically. In order to solve this ODE, an initial condition is
needed. In our problem the initial condition available is: at t ¼ 0 h, x ¼ 0 kg/m3
(pure water).
After solving the ODE, one can obtain a profile of the concentration of NaOH
inside the tank over time, as shown in Fig. 3.2. As mentioned before, the NaOH
16 3 Lumped-Parameter Models

0.020

Concentration (kg/m3) 0.015

0.010

0.005

0.000
0 5 10 15 20 25 30 35
Time (h)

Fig. 3.2 Concentration profile of NaOH leaving the tank over time

concentration indeed starts at zero and tends toward the value 0.02 kg/m3, which is
the concentration of the stream fed into the tank. When the concentration of NaOH
inside the tank does not vary anymore with time, we say the system reaches a steady
state. So, in our case, the system is in a transient state (when the concentration of
NaOH changes with time) and then reaches a steady state (when the concentration
of NaOH remains constant over time).
We can also obtain the NaOH concentration inside the tank in a steady state
directly (with no need to draw a graph) by setting a value of the accumulation term
in the conservation law equal to zero (E
L ¼ 0). This is possible because in a
steady state the concentration of NaOH stays the same over time. In this way, the
mass balance becomes (compare this with Eq. 3.1):

0:04
2x ¼ 0

This equation is easily solved and yields x ¼ 0.02 kg/m3 (as expected;
see Fig. 3.2).
It is important to observe that some systems do not reach a steady state. Note that
in the example presented in Chap. 2, the volume of the liquid inside the tank will
increase indefinitely with time, until the tank overflows.
In the next example, there will be a small increase in complexity because the two
examples previously presented will be combined (changes in volume and in
concentration), and the system will be represented by two ODEs.
Example 3.2 Mass and Volume Balance in a Perfectly Stirred Tank
Assume now a situation in which there are variations with time of both volume and
NaOH concentration. In this case, the models developed in Chap. 2 and in Example
3.1 have to be combined. The system can be represented by Fig. 3.3. At the
beginning, a perfectly stirred tank contains 10 m3 of pure water. Shortly thereafter,
the tank starts to be fed at a rate of 3 m3/h with a NaOH solution at a concentration
of 0.02 kg/m3. Simultaneously, an outlet valve is opened, allowing the fluid to leave
3.1 Some Introductory Examples 17

3 m3/h Initial water volume = 10 m3

0.02 kg/m3 Initial NaOH concentration = 0 kg/m3

x kg/m3 2 m3/h
x kg/m3

Fig. 3.3 Perfectly stirred tank with variations in NaOH concentration and volume

the tank at a rate of 2 m3/h. How do the volume and the concentration of NaOH vary
with time inside the tank?
Solution:
Chapter 2 develops the volume balance for this tank and obtains:

dV
¼1
dt
Developing the mass balance of NaOH for the tank, as per Example 3.1, we
obtain:

dðVxÞ
¼ 0:06
2x
dt
If the volume changes with time, this yields:

d ðVxÞ dx dV
¼V þx
dt dt dt
So the equation system that represents this tank is:

dV
¼1
dt
dx 0:06
3x
¼
dt V
and the initial conditions are: At t ¼ 0, V ¼ 10 m3 and x ¼ 0 kg/m3.
Both equations have to be solved simultaneously to generate profiles of the
volume and NaOH concentration inside the tank over time.
Example 3.3 Energy Balance in an Insulated Stirred Tank
Now let us take a step further by considering a simple energy balance. Variations in
temperature in chemical plants can occur basically due to generation or consump-
tion of energy as a consequence of exothermic or endothermic chemical reactions,
Exploring the Variety of Random
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 Žilin vastasi:

— No, jos käy sääliksi, niin tuohan sitten minulle pitkä seiväs.

Tyttö pudisti vain päätään: — En voi!

Žilin rukoili häntä kädet ristissä:

— Hyvä, kiltti Dina, tuo seiväs!

— En voi, vastasi tyttö. Näkevät, kaikki ovat kotona. — Samalla

hän juoksi pois.

Ilta tuli, ja Žilin istui miettien: — Mitenhän tässä käy? Yhtämittaa

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vielä noussut. Mulla huusi iltahuutonsa, sitten pii taas kaikki hiljaista.
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— Mitä? kysyi Žilin.

— Kaikki muut ovat menneet, kaksi on vain jäänyt kotiin.

 Žilin virkkoi Kostylinille:

— No, lähdetäänpäs, yritetään viimeisen kerran; minä kyllä nostan

sinut.

Kostylin ei ottanut puhetta kuuleviin korviinsa.

— Ei, ei minusta ole lähtijäksi. Mihinkä minä tästä, kun en kykene

edes kääntymäänkään.

— No, hyvästi sitten, erotaan ikiystävinä! Hän suuteli Kostyliniä.

Žilin tarttui seipääseen, pyysi Dinaa pitämään sitä pystyssä ja alkoi

kiivetä ylös. Mutta jalkapuut tekivät haittaa, ja hän luiskahti pari
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Žilin ojensi seipään Dinalle sanoen:

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Dina vei seipään pois, ja Žilin lähti kulkemaan vuoren juurelle päin.
Kompuroituaan jyrkänteen alle hän haki terävän kiven ja koetti
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Kaiketi taas Dina! hän ajatteli. Tyttönen juoksikin hänen luokseen ja
otti häneltä kiven virkkaen:

— Annahan kun minä!

 Dina laskeutui polvilleen ja alkoi kivellä nakutella lukkoa. Mutta
kädet olivat hennot kuin varvut, eikä niissä ollut voimaa ollenkaan.
Hän heitti kiven kädestään ja puhkesi itkuun. Žilin kävi taas
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kavahtaa häneen kiinni ja kopeloi käsillään löytääkseen paikan,
mihin pistäisi hänelle piirakoita. Žilin otti ne tytöltä.

— Kiitos, kaikkea sinä keksitkin. Kuka sinulle tästälähtien

leikkikaluja tekee, puheli hän silittäen tytön hiuksia.

Dina purskahti itkuun ja kätki kasvot käsiinsä. Hän juoksi sitten

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Mutta kajastus kirkastui kirkastumistaan, ja rotkon toinen puoli kävi
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koko ajan. Varjon turvissa Žilin samosi eteenpäin. Hän kiiruhti
kulkuaan, mutta kuu näytti vielä nopeammin kohoavan; oikeallakin
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alhaalta.

Žilin pääsi metsän suojaan kohtaamatta mitään tiellä. Hän valitsi

metsässä pimeimmän paikan ja istuutui lepäämään.

Syötyään kakkaran ja levähdettyään hän haki kiven ja rupesi

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 Žilin katseli tarkemmin, näki pyssyjen vilahtelevan, kasakoita,
sotamiehiä.

Hänen mielensä kävi iloiseksi, ja hän ponnisti viimeiset voimansa

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pakoon, vaikka jo olenkin lähellä!

Tuskin hän ehti tätä ajatella, kun huomasi vasemmalla kummulla,

muutaman kivenheiton päässä kolmen tatarin seisovan. Nämä
huomasivat hänet ja lähtivät kiitämään häntä kohti. Häneltä oli sydän
ihan pakahtua. Hän viittoili käsillään ja huusi minkä suinkin ääntä sai
tovereilleen:

— Hyvät miehet! Pelastakaa! Toverit!

Ja kasakat kuulivat, he keikahtivat hevostensa selkään ja

ratsastivat häntä kohti ja tatareja vastaan.

Kasakat olivat etäällä, tatarit aivan lähellä. Žilin ponnisti viimeiset

voimansa, piteli jalkapuistaan kiinni ja juoksi kasakoita kohti.
Nääntyneenä hän teki ristinmerkin ja huusi:

— Hyvät miehet! Ystävät! Ystävät!

Kasakoita oli noin viisitoista.

Tatarit pelästyivät ja pysähtyivät, ennenkuin olivat hänet

tavoittaneet. Žilin riensi suinpäin kasakkain luo.

Kasakat ympäröivät hänet joka puolelta kysellen:— Kuka? Mitä

miehiä? Ja mistä? Mutta väsymyksestä ja mielenliikutuksesta
menehtyneenä Žilin vain itki ja toisti yhtenään:
 — Ystävät! Ystävät!

Sotamiehetkin saapuivat paikalle ja ympäröivät hänet. Kuka antoi

leipää, kuka puuroa, kuka viinaa, joku peitteli päällysnutullaan, joku
alkoi särkeä jalkapuita.

Upseerit tunsivat hänet ja veivät linnoitukseen. Sotamiesten

kesken syntyi suuri riemu, toverit kokoontuivat kaikki Žilinin luo.

Žilin kertoi heille tarkoin, miten hänelle oli käynyt, ja virkkoi lopuksi:

— Semmoinen oli minun naimamatkani. Eipä näyttänyt olevan

Luojan tahto.

Ja hän jäi edelleen palvelemaan Kaukasiaan.

Kostylinista vaaditut viisituhatta saatiin suoritetuksi vasta

kuukauden kuluttua. Mies-parka oli silloin melkein kuoleman kielissä.
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