INTRODUCTION TO

NUMERICAL
METHODS IN
CHEMICAL
ENGINEERING
dCj
dx

A+B

= 0, j = A,B,C,D

B+C

k1
k2

C
D

d 2CA
dCA
D 2 u
k1CACB = 0
dx
dx
D

d 2CB
2

dx
D

d 2CC
2

dx
u

dx
D

d 2CD
2

dx

dCB
dCC
dx

dCD
dx

k1CACB k2CBCC = 0

+ k1CACB k2CBCC = 0

=D

dx

dCi
dx

=u

Ci + 1 2Ci + Ci 1
D
x2
Ci Ci 1
D
x

+ k2CBCC = 0

uCj,in = uCj D

d 2Ci

dCj
dx

Pradeep Ahuja

Introduction to
Numerical Methods in Chemical Engineering

Introduction to

Numerical Methods in
Chemical Engineering

PRADEEP AHUJA
Associate Professor
Department of Chemical Engineering and Technology
Institute of Technology, Banaras Hindu University
Varanasi

New Delhi-110001
2010

Rs. 275.00
INTRODUCTION TO NUMERICAL METHODS IN CHEMICAL ENGINEERING
Pradeep Ahuja
2010 by PHI Learning Private Limited, New Delhi. All rights reserved. No part of this book may
be reproduced in any form, by mimeograph or any other means, without permission in writing from
the publisher.
ISBN-978-81-203-4018-3
The export rights of this book are vested solely with the publisher.
Published by Asoke K. Ghosh, PHI Learning Private Limited, M-97, Connaught Circus,
New Delhi-110001 and Printed by Jay Print Pack Private Limited, New Delhi-110015.

To

my Mother
Kamla Ahuja
and
All my Students

Contents
Preface

ix

1.

Linear Algebraic Equations

1.1 Tridiagonal Matrix Algorithm (TDMA)
1.2 Gauss Elimination Method
5
1.3 GaussSeidel Method
10
Exercises
12

2.

Nonlinear Algebraic Equations

2.1 Newtons Method
17
2.2 Pressure Drop in Pipe
20
2.3 Minimum Fluidization Velocity
2.4 Terminal Velocity
23
2.5 System of Nonlinear Equations
Exercises
29

3.

116

1730
21
25

Chemical Engineering Thermodynamics

3.1 Solution of Cubic Equations of State
31
3.2 Bubble Point and Dew Point Temperature Calculations
Using Raoults Law
33
3.2.1 Bubble Point Temperature Calculation
33
3.2.2 Dew Point Temperature Calculation
34
3.3 Flash Calculations Using Raoults Law
35
3.4 Bubble Point and Dew Point Temperature Calculations Using Modified
Raoults Law
37
3.5 Flash Calculations Using Modified Raoults Law
40
3.6 Vapour Pressure Using Cubic Equation of State
42
3.7 P-x-y Diagram Using GammaPhi Approach
43
3.8 P-x-y Diagram Using Cubic Equation of State
44
3.9 Chemical Reaction EquilibriumTwo Simultaneous Reactions
47
3.10 Adiabatic Flame Temperature
49
Exercises
50
vii

3152

viii
4.

Contents

Initial Value Problems

4.1 Solution of Single Ordinary Differential Equation
53
4.2 Double Pipe Heat Exchanger
55
4.3 Stirred Tank with Coil Heater
57
4.4 Pneumatic Conveying
60
4.5 Solution of Simultaneous Ordinary Differential Equations
4.6 Series of Stirred Tanks with Coil Heater
66
4.7 Initial Value Problems in Chemical Reaction Engineering
4.8 Batch and Stirred Tank Reactors
69
4.9 Plug Flow Reactor
74
4.10 Nonisothermal Plug Flow Reactor
76
Exercises
80

5384

63
68

5.

Boundary Value Problems

5.1 Discretization in One-Dimensional Space
5.2 One-Dimensional Steady Heat Conduction
5.3 Chemical Reaction and Diffusion in Pore
Exercises
99

85104

6.

ConvectionDiffusion Problems
6.1 Upwind Schemes
105
6.1.1 First Order Upwind Scheme
105
6.1.2 Second Order Upwind Scheme
106
6.2 Comparison of CDS and UDS
113
Exercises
114

7.

Tubular Reactor with Axial Dispersion

7.1 Boundary Value Problems in Chemical Reaction Engineering
7.2 First Order Reaction
120
7.3 Second Order Reaction
129
7.4 Multiple Reactions
131
Exercises
153

8.

Chemical Reaction and Diffusion in a Spherical Catalyst Pellet

8.1 First Order Reaction
155
8.2 Second Order Reaction
158
8.3 Non isothermal Conditions
161
Exercises
169

155170

9.

One-Dimensional Transient Heat Conduction

9.1 Classification of Partial Differential Equations
171
9.2 Explicit and Implicit Discretization
172
9.3 CrankNicolson Discretization
173
9.4 Von Neumann Stability Analysis
174
9.5 Transient Conduction in Rectangular Slab
176
9.6 Transient Conduction in Cylinder
181
9.7 Transient Conduction in Sphere
183
9.8 Transient Diffusion in Sphere
186
Exercises
188

171191

85
93
97

105118

119

119154

Contents

10.

Two-Dimensional Steady and Transient Heat Conduction

10.1 Discretization in Two-Dimensional Space
192
10.2 GaussSeidel Method
194
10.3 Relaxation Parameter
194
10.4 RedBlack GaussSeidel Method
195
10.5 ADI Method for Steady Heat Conduction
208
10.6 ADI Method for Transient Heat Conduction
214
Exercises
220

Appendix:

Programs in C++

ix

192223

225283

Bibliography

285286

Index

287289

Preface
This book entitled Introduction to Numerical Methods in Chemical Engineering is designed for
a course on Numerical Methods in Chemical Engineering and the associated Computer
Applications Laboratory course offered as part of undergraduate programmes in chemical
engineering. Also, for the courses on Chemical Engineering Mathematics or Applied
Mathematics in Chemical Engineering, this book can be used for the numerical solution aspects
of chemical engineering problems.
The computer programs are listed in C++. The author assumes that the students are at
least moderately familiar with the C++ language. In addition to the computer examples, there
are several much shorter examples appearing throughout the text. These shorter examples
usually illustrate a particular point by means of hand calculations. 33 sample programs in C++,
arranged by chapter, are presented in the Appendix and about 148 exercises (including chapterend exercises with answers) are solved. The numerical solutions of algebraic (linear and
nonlinear) and differential (ordinary and partial) equations encountered in subjects such as
General Chemical Engineering, Chemical Engineering Thermodynamics, Chemical Reaction
Engineering, and Heat Transfer are discussed using introductory but efficient numerical
methods. The students can also use the programs and build up their own programs to solve
specific Design Project problems in chemical engineering. The author feels that before using
chemical engineering software (which use advanced numerical methods), the students should
have some hands-on experience on small programs and introductory numerical methods as well
as their usage in chemical engineering. The experience gained from using these programs helps
in the development of basic understanding of numerical methods and confidence in handling
numerical techniques. Some problems whose analytical solutions are available are also solved
and the numerical and analytical results are compared. By changing various parameters the
student can find out the conditions under which correct results are obtained as well as those
under which correct results are not obtained.
For the solution of linear algebraic equations, the tridiagonal matrix algorithm (TDMA),
Gauss elimination, and GaussSeidel methods are discussed. For the solution of nonlinear
equation(s), Newtons method is discussed and for initial value problems in ordinary
differential equations the RungeKutta fourth order method is discussed. For the solution of
boundary value problems the Finite Difference method is used. The Finite Difference method
is a simple yet very powerful tool for the solution of boundary value problems, but requires
a structured grid. It is the basis for the Advanced Finite Volume and Finite Element methods.
In this book the following Finite Difference methods are discussed: Central Difference Scheme
(CDS) for discretization of diffusion terms, Upwind Difference Scheme (UDS) for
xi

xii

Preface

discretization of convection terms, Forward in Time and Central in Space (FTCS) difference
scheme for discretization of the one-dimensional transient conduction/diffusion equation
adopting the Explicit, Implicit and CrankNicolson methods, and the Alternating Direction
Implicit (ADI) method for the numerical solution of two-dimensional steady and transient heat
conduction.
Chapter 1 contains an introduction to the numerical solution of a system of linear
algebraic equations. The numerical solution of a single as well as two (simultaneous) nonlinear
algebraic equation(s) and the calculation of pressure drop in a pipe under nonlaminar
conditions, minimum fluidization velocity and terminal velocity are all discussed in Chapter
2. The numerical solution of computer-oriented problems in Chemical Engineering
Thermodynamics is discussed in Chapter 3. Various problems in vapourliquid and chemical
reaction equilibria are discussed. Vapourliquid equilibrium calculations are done for systems
following Raoults law, modified Raoults law, GammaPhi approach and PhiPhi approach.
The numerical solution of initial value problems in ordinary differential equations, along with
the initial value problems in double pipe heat exchanger and stirred tanks with coil heater, and
in batch, stirred and plug flow reactors are discussed in Chapter 4. The numerical solution of
boundary value problems in ordinary differential equations and convectiondiffusion problems
are discussed in Chapters 5 and 6 respectively. The numerical solution of tubular reactors with
axial dispersion and simultaneous chemical reaction and diffusion in spherical catalyst pellets
are discussed in Chapters 7 and 8 respectively. The numerical solution of one-dimensional
transient heat conduction/diffusion is discussed in Chapter 9, and that of two-dimensional
steady and transient heat conduction is discussed in Chapter 10. The Finite Difference method
is used for the solution of boundary value problems in Chapters 510.
The books referred to by the author for the preparation of class notes, on which the
contents of this book are principally based, is given in the Bibliography. The author expresses
his thanks to all those authors, too numerous to acknowledge individually. The author is
indebted to all his colleagues for many positive interactions and discussions and also to all his
friends for their constant appreciation, invaluable advice and encouragement. The author
would like to thank the Department of Science and Technology, New Delhi, for providing
partial financial support and Prof. S.N. Upadhyay, Director, Institute of Technology, Banaras
Hindu University, Varanasi, for providing the major part of the funds for the purchase of
Fluent 25 Users Perpetual License software in the Department of Chemical Engineering and
Technology, which proved immensely useful in the process of writing this book.
The author is also thankful to all his B.Tech. Chemical Engineering students who have
taken up the Computer Laboratory course and various computational and other chemical
engineering courses so enthusiastically and helped in many ways in developing this work.
Their inquisitive questions and enthusiasm towards the numerical solution of algebraic and
differential equations in chemical engineering inspired the author to create a work of this kind,
in which the numerical solution of various equations in chemical engineering is provided under
one cover. Feedback from students has critically guided the development and evolution of the
book, taking it from a handwritten collection of notes to the present form. The book is thus
dedicated to all his students. The author is grateful to Mr. Sudarshan Das, Mr. Abhjit Baroi
and Mr. Pankaj Manohar of PHI Learning for their cooperation.

Preface

xiii

The author is indebted and extremely thankful to his mother Kamla Ahuja, to his father
A.D. Ahuja, and his wife Preeti Bala Ahuja, for their care, help and understanding, as without
their support this work could never have been completed.
In spite of all efforts to the contrary, some errors might have crept into the book. The
author would be rather grateful if such errors are pointed out. He would also very much
appreciate any criticism or suggestion for improvement of the contents of the book from the
readers.
Pradeep Ahuja

Chapter 1

Linear Algebraic Equations

A system of linear algebraic equations can be solved by direct or iterative methods. The direct
methods discussed in this chapter are the TriDiagonal Matrix Algorithm (TDMA) and Gauss
Elimination methods, and the iterative method discussed is the Gauss-Seidel method.
A tridiagonal or block tridiagonal set of linear algebraic equations is formed during the
discretization of ordinary and partial differential equations. The discretization of differential
equations using the finite difference method is discussed in Chapters 5 to 10. All types of linear
algebraic equations can be solved using the Gauss Elimination method, but if the equations are
of tridiagonal type, then TDMA is very fast as compared to the Gauss Elimination method. The
GaussSeidel method is used for the solution of two-dimensional steady heat transfer, which
is discussed in Chapter 10.

1.1 Tridiagonal Matrix Algorithm (TDMA)

TDMA is a direct method. Consider the following tridiagonal set of linear algebraic equations:

D
C


E
D
C

E
D
C

E
D


E
 


 
 

C0  D0 
C0

Z
Z

Z

Z





E0  Z 0 

D0 Z 0

F
F

F

F





F 0 

F0

(1.1)

N linear algebraic equations can be written in the form Ax = d. The matrix A contains elements
on the diagonal (bi, i = 1 to N), sub-diagonal (ai, i = 2 to N), and super-diagonal (ci, i = 1 to
N 1), and thus is called a tridiagonal matrix. The algorithm for the solution of this sort of
linear algebraic equation is called the TriDiagonal Matrix Algorithm or the Thomas algorithm.
1

Introduction to Numerical Methods in Chemical Engineering

The equations are of the type

C Z   D Z  E Z 
K

where a1 = 0, cN = 0

Let us write the solution at xi in terms of xi+1 as

E Z 
Z H 
K

E  Z

H K  

(1.3a)

CK

Then we can also write

Z 

(1.2)

(1.3b)

C K 

where bi and gi are obtained by substituting Eq. (1.3b) into Eq. (1.2). Thus we get

E Z
C H     D Z  E Z 
C 

The above equation can be written as

K

C E 
D 
Z
C 

F  CH

 E Z 



Thus
F  C H 
E

Z 

C E 
C E 
D 
D 

C 
C 

Comparing with Eq. (1.3a), we get

C E 
C D 
Z

C 

(1.4)

HK

F  CH
K

F  CH



C E 
D 

C 



CK

(1.5)

a1 = 0; therefore

b1 = b1

and

(1.6)

F
D

(1.7)

H

The algorithm for the solution of a tridiagonal set of linear algebraic equations is given below:
(i) Calculate bi and gi for i = 1 to N.
(ii) Calculate Z 0
(iii) Calculate Z

E Z
H 0  0 0 
C0
HK 

E Z 
K

CK

. Since cN = 0, therefore xN = g N.

for i = N 1, N 2, , 3, 2, 1.

Linear Algebraic Equations

EXAMPLE 1.1

Solution

Solve the following set of linear algebraic equations using TDMA

We have



Z
 
Z


Z
 


 


Z

Z
 


 
 Z

  Z












C D  
H

F
D

C

D 

H

C

H

C

H

C



C E

C

F  CH 
C

D 

C E

C

F  CH 
C

D 

C E

C

F  CH 

C

D 

C E

C










   u 



 












 

 






  






























Introduction to Numerical Methods in Chemical Engineering

H

C

H

C

H

F  CH 

C

D 

C E

C

F  CH 

  



 

C E

C

F  CH 












 

C

D 




 





















 

C




Now let us compute the solution starting with x7.




Z

H

Z

E Z
H   
C

  

u




Z

E Z
H   
C

  u 




Z

E Z
H   
C

 

 u 


Z

E Z
H   
C

 

 u 


Z

E Z
H   
C

 




Z

H

E Z

C



 













Linear Algebraic Equations

Program 1.1 uses the above method for solving the tridiagonal system of linear algebraic
equations and is given in the Appendix.

1.2 Gauss Elimination Method

Gauss Elimination is a direct method. The Gauss Elimination method reduces the system of
equations to an upper triangular system which can then be solved by back substitution.
Consider the following system of three linear algebraic equations:
C Z  C Z  C Z
C Z  C Z  C Z

The augmented matrix is

F
F

C Z  C Z   C Z

F

C

C
C

C
C
C

C F

C F
C F

(1.8)

C
Take the element a11 as the pivot. Multiply the first equation by   and then add it to the
C
second equation, which then becomes

CC
CC
C
F
C 
Z  C 
Z F 
C
C
C

Thus x1 is eliminated from the second equation. Similarly, eliminate x1 from the third
C
and then adding it to the third equation.
C
At the end of the first stage the augmented matrix becomes

equation by multiplying the first equation by 

C




C
c
C
c
C

C F

c c
C F
c c
C F

(1.9)

C




C
c
C


C
c
C
cc
C

F

c
F
cc
F

(1.10)

c
C
and then
Now take the element a 2 as the new pivot. Multiply the second equation by 
2
c
C
add it to the third equation. Thus x2 is eliminated from the third equation. At the end of the
second stage the augmented matrix becomes

The values of x1, x2, and x3 can be obtained by back substitution. The pivots should be chosen
in such a way that they are nonzero. Rows can be exchanged so that the pivot is nonzero. This
procedure is called partial pivoting.

Introduction to Numerical Methods in Chemical Engineering

EXAMPLE 1.2 Solve the following set of three linear algebraic equations in three variables
using the Gauss Elimination method:
 Z  Z    Z
 Z   Z   Z

Solution

The augmented matrix is




Z   Z    Z



   

   
   

Multiply the first equation by 


and then add it to the second equation. We get







Multiply the first equation by 


 

  


 


and then add it to the third equation. We get




 

   

   


This completes the first stage. Multiply the second equation by 
and then add it to the

third equation. We get








 

  

From the previous equation we get

9.68367x3 = 48.418367
Solving, we get x3 = 5.
From the second equation we get
9.8x2 + 0.6x3 = 42.2
Thus
From the first equation we get

Z

   u 


10x1 + x2 + 2x3 = 44

Linear Algebraic Equations

Thus

Z

     u 


.

Program 1.2 uses the Gauss elimination method for solving a system of linear algebraic
equations and is given in the Appendix.
EXAMPLE 1.3 Solve the following set of three linear algebraic equations in three variables
using the Gauss Elimination method:
 Z  Z    Z

 Z   Z   Z

Solution

The augmented matrix is

Z  Z    Z




   

   
   

Multiply the first equation by


and then add it to the second equation. We get




 

   

 


Multiply the first equation by 


and then add it to the third equation. We get




 

  

   

Multiply the second equation by 0.3076923 and then add it to the third equation. We get






  

  

From the previous equation, we get

3.5384x3 = 3.5384
Solving, we get x3 = 1.

Introduction to Numerical Methods in Chemical Engineering

From the second equation, we get

4.3333x2 3.6667x3 = 5
Thus

Z

From the first equation, we get

  


 .

3x1 + x2 2x3 = 9

Thus

Z




.

EXAMPLE 1.4 Benzene (1), toluene (2), styrene (3), and xylene (4) are to be separated in
the sequence of distillation columns shown in Fig. 1.1. Determine molar flow rates of streams
D1, B1, D2, and B2. The composition of the feed stream and the streams D1, B1, D2, and B2 is
shown in the figure. Also, determine the molar flow rates and compositions of streams B and
D. The molar flow rate of the feed stream is 70 mol/min.
D1

x1
x2
x3
x4

=
=
=
=

0.35
0.54
0.04
0.07

x1
x2
x3
x4

=
=
=
=

0.16
0.42
0.24
0.18

x1
x2
x3
x4

=
=
=
=

0.21
0.54
0.10
0.15

x1
x2
x3
x4

=
=
=
=

0.01
0.10
0.65
0.24

x1
x2
x3
x4

=
=
=
=

B1

0.20
0.40 70 mol/min
0.25
0.15

D2

B2
Fig. 1.1

Schematic diagram for Example 1.4.

Solution The material balance equations for benzene (1), toluene (2), styrene (3), and xylene
(4) are given below.

Linear Algebraic Equations

 u 

&   $  &  $

 u 

 &   $   &   $

 u 

 &   $   &  $

 u 

 &  $  &   $

The above equations can be written as

   &

   $

   &

   $















Solving by using the Gauss Elimination method, we get

D1 = 26.25 mol/min
B1 = 17.5 mol/min
D2 = 8.75 mol/min
B2 = 17.5 mol/min.
B = D2 + B2 = 26.25 mol/min.
The composition of stream B is given by
Z$

&  $
$



Z $

 &   $

$



Z$

 &  $

$



&   $

$
D = D1 + B1 = 43.75 mol/min.
Z $

The composition of stream D is given by

Z&

&   $
&



Z &

 &   $

&



10

Introduction to Numerical Methods in Chemical Engineering

Z &

 &   $

&



 &  $


&
Now, let us check the solution obtained. B + D is 70 mol/min, which is correct. Now, let us
back-calculate the feed composition.
Z&

&Z&  $Z$




&Z  &  $Z  $




&Z &  $Z $





&Z  &  $Z  $




1.3 GaussSeidel Method

GaussSeidel is an iterative method. Consider a system of N linear algebraic equations in N
variables. The first equation can be written with variable x1 on the left hand side and the rest
of the terms on the right hand side. Similarly, the second equation can be written with variable
x2 on the left hand side and the rest of the terms on the right hand side, and so on. Now we
can assume some values of the variables, and compute the new value of x1 from the first
equation and the new value of x2 from the second equation, and so on. In the GaussSeidel
method, when the new value of x2 is computed from the second equation then on the right hand
side for the variable x1 the updated value calculated from the first equation, is used. Similarly,
when the new value of x3 is calculated from the third equation, then on the right hand side for
the variables x1 and x2 the updated values calculated from the first and second equations are
used. By doing this a higher convergence rate is obtained. So the latest values of the variables
are always used.
In the above explanation it is assumed that in the first equation the coefficient of x1 is
the highest among the coefficients of the other variables, and in the second equation the
coefficient of x2 is the highest among the coefficients of the other variables. All the equations
have many variables in them. A survey of the given system of linear algebraic equations is
made and that variable which has the highest coefficient is kept on the left hand side. The
variable whose coefficient is the largest is used to express that variable in terms of the others.
The GaussSeidel method has the disadvantage of not always converging to a solution
and of sometimes converging very slowly. However, this method will always converge to a
solution when the magnitude of the coefficient on the left hand side is sufficiently dominant
with respect to the magnitudes of the other coefficients in that equation.

Linear Algebraic Equations

11

EXAMPLE 1.5 Solve the following set of three linear algebraic equations in three variables
using the GaussSeidel method:
10x1 + x2 + 2x3 = 44
2x1 + 10x2 + x3 = 51
x1 + 2x2 + 10x3 = 61
Solution It can be seen that the coefficient of x1 is dominant in the first equation, and the
coefficient of x2 and x3 are dominant in the second and third equations, respectively. Thus
P
Z 

P
P
  Z   Z


P
Z 

P
P
   Z   Z


P
P
  Z    Z 

Let us assume x2 = 0, x3 = 0. The initial values used will not affect the converged solution, but
will affect the number of iterations required for convergence.
First Iteration:
P
Z 

Z
Z
Z

Second Iteration:

    


   u   


     



     u 


   u   
Z


     u 
Z


The final converged solution is x1 = 3, x 2 = 4, x3 = 5.
Z

Program 1.3 uses the GaussSeidel method for solving a system of linear algebraic equations
and is given in the Appendix.
EXAMPLE 1.6 Solve the following set of three linear algebraic equations in three variables
using the GaussSeidel method:
 Z  Z    Z 
 Z   Z   Z  
Z  Z    Z 

12

Introduction to Numerical Methods in Chemical Engineering

Solution

Let us write the first, second and third equations in the form
P
Z 

P
P
  Z   Z


P
Z 

P
P
  Z    Z


P
Z 

P
P
  Z   Z 


Let us assume x2 = 0, x3 = 0.
First Iteration:
Z
Z
Z




    
 

    
 


Second Iteration:
     u 


     u 
Z
 

    
Z
 

The final converged solution is x1 = 3, x2 = 2, x3 = 1.
Z

Exercises
1.1

Solve the following using TDMA:

 
Z 
  
Z 

Z 
  

   

Z 

Z 
   

  

Z 

   Z 

  Z 

(Ans: x1 = 111.11, x2 = 122.22, x3 = 133.33, x4 = 144.44, x5 = 155.55,

x6 = 166.66, x7 = 177.77, x8 = 188.88)

Linear Algebraic Equations

1.2

Solve the following linear algebraic equations using the Gauss elimination method:
2x1 x2 = 100
x1 + 2x2 x3 = 0
x2 + 2x3 x4 = 0
x3 + 2x4 x5 = 0
x4 + 2x5 x6 = 0
x5 + 2x6 x7 = 0
x6 + 2x7 x8 = 0
x7 + 2x8 = 200
Note that the augmented matrix for this problem is
        

        
        

        
        

         
        

        

(Ans: x1 = 111.11,
x6 = 166.66,

1.3

13

x2 = 122.22, x3 = 133.33, x4 = 144.44, x5 = 155.55,

x7 = 177.77, x8 = 188.88)

Solve the equations in Problem 1.2 using the GaussSeidel method.

Note that the equations are expressed in the form
P
Z 

P
  Z


P
Z 

P
P
Z   Z


P
Z 

P
P
Z   Z


P
Z  

P
P
Z   Z


P
Z 

P
P
Z   Z


14

Introduction to Numerical Methods in Chemical Engineering

P
Z 

P
P
Z   Z 


P
Z  

P
P
Z   Z


P
  Z  

x2 = 122.22, x3 = 133.33, x4 = 144.44, x5 = 155.55,
x7 = 177.77, x8 = 188.88)
P
Z 

(Ans: x1 = 111.11,
x6 = 166.66,
1.4

Solve the following linear algebraic equations using the Gauss elimination method:
4x1 + 2x2 + x3 = 11
x1 + 2x2 = 3
2x1 + x2 + 4x3 = 16
Note that the augmented matrix is
   

   
   

(Ans: x1 = 1,
1.5

x2 = 2,

x3 = 3)

Solve the linear algebraic equations of Problem 1.4 using the GaussSeidel method:
Note that for GaussSeidel to converge the equations are expressed in the form
P
Z 

P
P
   Z  Z


P
Z 

P
  Z 


P
P
   Z   Z 

x3 = 3)

P
Z 

(Ans: x1 = 1,
1.6

x2 = 2,

Solve the following linear algebraic equations using the Gauss elimination method:
 Z   Z   Z

Z   Z  Z

(Ans: x1 = 1.2857,





 Z   Z   Z 
x2 = 1.9286, x3 = 2.8571)

Linear Algebraic Equations

1.7

15

Solve the linear algebraic equations of Problem 1.6 using the Gauss-Seidel method:
Note that for GaussSeidel to converge the equations are expressed in the form
P
Z 

P
P
   Z   Z


P
Z 

P
P
  Z   Z


P
P
   Z    Z 

x2 = 1.9286, x3 = 2.8571)
P
Z 

(Ans: x1 = 1.2857,
1.8

Solve the following linear algebraic equations using the Gauss elimination method:
 
      6


 
 
     6


   
    6

 
   6
   

 
 
 
  6

 
   
 6
 
  
   
  6

 
 
 6
   

 
  6
    

































Note that for using the Gauss elimination method the equations have to expressed
in the form of augmented matrix as

 
      

 
     
 

   
    

 
   
   

 
 
 
 


 
  

 
 
  
 
 
  

  

 
 
 

 
 
  
  

(Ans: T1,1 = 47.14, T1,2 = 91.25, T1,3 = 182.86, T2,1 = 57.32, T2,2 = 115.00,
T2,3 = 220.18, T3,1 = 47.14, T3,2 = 91.25, T3,3 = 182.86)

16

Introduction to Numerical Methods in Chemical Engineering

1.9

Solve the following linear algebraic equations using the GaussSeidel method:
6  6  6



6  6








 6  6







6 6








6  6

6



6





 6

6



6



 6

6







6







6 6












 6  6




 6  6


6








6  6  6

Note that for GaussSeidel to converge the equations are to be expressed in the
form


6 P



6P   6 P  6 P  




6P  6 P  





6P  6 P  6 P  




6P  6 P  6 P  6 P




P
6 

P
6 

(Ans: T1,1
T2,3



6P   6 P   6 P  








P
6 





6 P





6 P





6 P





6 P



  6P  6 P



6 P



P
P
  6   6


P
P
P
6   6   6  


P
P
6   6   


= 47.14, T1,2 = 91.25, T1,3 = 182.86, T2,1 = 57.32, T2,2 = 115.00,
= 220.18, T3,1 = 47.14, T3,2 = 91.25, T3,3 = 182.86)

Chapter 2

Nonlinear Algebraic Equations

Newtons (or NewtonRaphson) method for the numerical solution of a nonlinear algebraic
equation is described first in this chapter. Examples discussed include the calculation of
pressure drop in a pipe in nonlaminar range, and the calculation of minimum fluidization
velocity and terminal velocity. Thereafter the solution of two simultaneous nonlinear algebraic
equations is discussed using Newtons method.

2.1 Newton's Method

The function f is formulated in such a way that the polynomial or the expression whose root
is to be determined is of the form f (x) = 0. Newtons method is given by
Z P 

ZP 

H
Hc

(2.1)

where xn is the value of x at the start of the iteration and xn+1 is the updated value after the
iteration. First an initial value of x is assumed, and the function value and its derivative are
determined at this assumed value. The assumed value is updated by using Newtons formula,
and again the function value and its derivative are determined at this new value of x (see
Fig. 2.1). The value of x is again updated and the procedure is repeated till there is no change
in the previous and updated values of x. By taking different starting (old) values, different roots
can be obtained, if more than one real root occurs. Note that when the root is obtained, there
is no change in the value of x. That is, xn+1 = xn, which implies f = 0, which is the required
condition, that function value should become zero at the root. Note that Newtons method
works only if, at f = 0, the derivative of the function is not zero. In Fig. 2.1, the function value
becomes zero at the root xs. In this case the starting value is taken to be x1.
The algorithm of Newtons method is:
(i) Take an initial value of xn,
FH
(ii) Calculate f and H c
at the value of xn,
FZ
H
(iii) Calculate the new value of x, using Z P  Z P  ,
Hc
P 
P
(iv) Check if Z  Z  F ; if yes, stop, else
17

18

Introduction to Numerical Methods in Chemical Engineering

(v) Make xn = xn+1 and go to Step (ii) and repeat the procedure till the condition stated
in (iv) is satisfied. e is the convergence criterion and may be of the order of 106.
f

f1

f2
f3
0

x1

x2

Fig. 2.1

x3

xs

Concept of Newtons method.

The derivation of Newtons formula is presented below. Let a nonlinear algebraic equation be
represented as f (x) = 0. Let us start with an initial guess x0 of the solution and let us assume
that it is close to the actual solution xs. We make a Taylor series to approximate f(x) in the
vicinity of x0 as follows:
H Z

H Z 

FH
FZ


Z  Z    F H Z  Z 
FZ


Z

 

"

Z

At the solution, H
Z 5  = 0 and the Taylor series yields


H Z 

FH
FZ

Z

 Z 

 F H
 FZ 

If x0 is sufficiently close to xs, then

Z5  Z   Z5  Z 

 Z

"

 Z5  Z   "

In this case, as long as the first derivative is nonzero at x0, we obtain a reasonable
approximation of the solution, x1, from the rule

H Z 

FH
FZ

 Z

(2.2)

Successive application of this rule yields Newtons method for solving a single nonlinear
algebraic equation in the form

P 

Z 

 
H c Z 
H ZP

Nonlinear Algebraic Equations

19

where f denotes the derivative of the function with respect to x. The iterations are stopped
when the previous and updated values of x are less than eabs, that is
Z P   Z P  F CDU

(2.3)

Z P   Z P
 F TGN
Z P 

(2.4)

or

Consider that the real roots of the equation x3 2x2 x + 2 = 0 have to be determined.
Different roots are obtained by taking different starting values of x. Newtons method
discussed here determines only the real roots. For the above equation the starting values taken
and the corresponding roots are listed in Table 2.1.
Table 2.1

Different roots obtained by taking different starting values in Newtons method

Real root of x3 2x2 x + 2 = 0 by Newtons method

Starting value
4.0
1.5
0.5
0.25
0.0
1.0
2.0
4.0
100.0

2.0
1.0
1.0
1.0
2.0
1.0
1.0
1.0
1.0

100.0

2.0

Thus the three roots on which the solution converges are (2, 1, 1). Various iterations in
Newtons method to determine the real root of the equation x3 2x2 x + 2 = 0 with starting
value x = 4 are listed in Table 2.2.
Table 2.2

Various iterations in Newtons method for starting value of

Iteration number

Starting point

1
2
3
4
5
6
7

4.0
2.92857
2.38803
2.10969
2.01297
2.00022
2.00000

30.0
7.03533
1.82478
0.37852
0.03959
0.00066
0.00000

28.0
13.01529
6.55594
3.91362
3.10426
3.00176
3.00000

In Table 2.2, f = x3 2x2 x + 2, and f = 3x2 4x 1 .

P 

4
P

Z 

2.92857
2.38803
2.10969
2.01297
2.00022
2.00000
2.00000

H
Hc

20

Introduction to Numerical Methods in Chemical Engineering

EXAMPLE 2.1

Apply Newtons method to determine a real root of the equation

f (x) = x3 5x + 1 = 0

Take the initial approximation as x0 = 0.5.

Solution

With an initial value of 0.5, it can be checked that the solution is 0.201640.

2.2 Pressure Drop in Pipe

The pressure drop in a pipe of length L is given by the relation
H.8  S
(2.5)
&
where 8 is the average velocity in the pipe of internal diameter D and the fluid density is r.
When the pressure drop is given by Eq. (2.5), the friction factor under laminar flow conditions
is given by

H
(2.6)
4G
S8&
where 4G
. For the entire nonlaminar range the friction factor is given by the Colebrook
N
relation
'2

F &

  NQI

 4G H


H

(2.7)

For the laminar conditions the friction factor can be easily determined. But for nonlaminar
conditions the Colebrook equation has to be solved using Newtons method as described in the
example below.
EXAMPLE 2.2 Air at 25C and 1 atm flows through a 4 mm diameter tube with an average
velocity of 50 m/s. The roughness is e = 0.0015 mm. Calculate the friction factor using the
Colebrook equation
F &

  NQI

 4G H


H

Determine the pressure drop in a 1 m section of the tube using the relation
H.8  S
&
3
Density of air at 25C and 1 atm is 1.23 kg/m and viscosity is 1.79 105 kg/m-s.
'2

Solution

We have
F

&






Nonlinear Algebraic Equations

S8&
N

4G

 u  u  u  
 u  

21



Thus


  NQI



 H


H

or

 u  
  NQI  u   


H

Let us define a function, F, as

(

 u  
  NQI  u   

H
H

The derivative of the function with respect to the friction factor is given by
(c

  H  

 u  u   u    H 

 u     u   H 

Using Newtons method, we get f = 0.0291. Under these conditions the pressure drop in a 1 m
section of the pipe is given by

'2

 u  u   u 
 N/m2 = 11.19 kPa
 u 

Program 2.1 for calculating the pressure drop in a pipe under nonlaminar conditions is given
in the Appendix.

2.3 Minimum Fluidization Velocity

Ergun proposed the following general equation applicable for low, medium and high Reynolds
number for pressure drop across a packed bed:


'2

 N X'.   F 
 S X  '.   F 

 


GU F R
GU F R
F
F

(2.8)

where n is the superficial velocity of the fluid, dp is the particle diameter, fs is the sphericity
of the particle, e is the voidage in the packed bed, and DP is the pressure drop across the
packed bed of length DL . r and m are respectively the density and viscosity of the fluid. At
the point of incipient fluidization the force obtained from the pressure drop across the fluidized
bed (DP A) is equal to the gravitational force exerted by the mass of the particles minus the
buoyancy force. If Lmf is the height of the packed bed at the point of minimum fluidization

22

Introduction to Numerical Methods in Chemical Engineering

and emf is the voidage of the packed bed at minimum fluidization, then the total volume of the
bed at minimum fluidization is Lmf A and thus the volume of solids at minimum fluidization
is Lmf A(1 emf). The gravitational force of the particles minus the buoyancy force is given
by volume of the solid particles (rp r)g. Thus at minimum fluidization conditions

'2 u #

.OH #   F OH   S R  S  I

(2.9)

or
'2
.OH

  F OH   S R  S  I

(2.10)

Substituting this value in the Ergun equation for packed bed, we get

 N   F 
 S   F OH  
OH
XOH    F OH   S R  S  I 

XOH   


F OH
F OH
GU F R

GU F R

(2.11)

The real roots of the minimum fluidization velocity can be obtained using Newtons
method.
EXAMPLE 2.3 Solid particles having a diameter of 0.12 mm, shape factor fs = 0.88, and
a density of 1000 kg/m3 are to be fluidized using air at 2.0 atm and 25oC. The
voidage at minimum fluidization is 0.42. The viscosity of air under these conditions is
1.845 105 kg/m-s. The molecular weight of air is 28.97.
Solution

The density of air at 2.0 atm and 25C is given by

2/
46

 u  u  u  
 u 

 kg/m3

The diameter of the particle is d p = 1.2*10-4 m. The function is

 N   F 
 S   F OH  
OH
XOH    F OH   S R  S  I

XOH   


F OH
F OH
GU F R

GU F R

and the derivative of the function with respect to nmf is

 S   F OH 
 N   F OH 
H c 
XOH   


F OH
GU F R
F OH
GU F R

Starting with an initial value of nmf = 0.1 m/s, the converged value is nmf = 0.0046 m/s.
Program 2.2 for calculating the minimum fluidization velocity is given in the Appendix.

Nonlinear Algebraic Equations

23

2.4 Terminal Velocity

Consider a particle of mass m kg falling at velocity of v m/s (see Fig. 2.2). The momentum
balance equation is given by
O

FX R

(I  (D  (&
FV
Gravitational force minus the buoyancy force on the particle is given by

(I  (D

8R  S R  S  I

SR

 SR  S  I

(2.12)

(2.13)

where VP is the volume of the particle and m is the mass of the particle.

FD

Fg Fb = (rp r)Vpg

Fig. 2.2

Various forces acting on particle falling in stationary fluid.

The terminal velocity or free settling velocity is a constant velocity fall and is given when
FX R
FV

 ; thus

CD is given by % &

(I  (D

(&

(& # R
. Thus Eq. (2.14) becomes
 
S XV

O
 S R  S  I  S #R%& XV

SR

(2.14)

(2.15)

where Ap is the projected area of the particle on a plane at right angles to the direction of
motion and nt is the terminal velocity of the falling particle. As the velocity of particle rises
the drag force also increases till the drag force balances the (gravitational buoyancy) force.
Thus,
XV

I  S R  S  O

S R #R% & S

24

Introduction to Numerical Methods in Chemical Engineering

For spherical particles,

 
Q TR S R


Q


F SR
R

and the projected area is given by

#R


TR

Q F
R


Thus for spherical particles the expression for terminal velocity becomes
  S R  S  IF R

(2.16)

% S

&

For laminar flow (Rep < 1), that is, in the Stokes law region

%&


4G R

(2.17)

where Rep is the particle Reynolds number and is given by 4G R

S XF R

. We get the

following expression for terminal settling velocity in the laminar flow regime

IF   S R  S 
R

(2.18)

 N

For turbulent flow, CD = 0.44 (Rep > 1000 to 2 105). But for intermediate values of the
particle Reynolds number, there are many correlations. The Schiller and Nauman correlation
is applicable for Rep < 800 and is given by

%&


   4G 
R
4G R

(2.19)

The terminal velocity for the case of intermediate values of particle Reynolds number is
determined using the following steps:
(i) A value of terminal velocity is assumed.
(ii) At the assumed value the particle Reynolds number is calculated and thereafter CD
is determined.
(iii) The terminal velocity is recalculated using X

  S R  S  IF R
% S

&

If the assumed value and recalculated values are different, the new calculated value becomes
the starting value for the next iteration. The procedure is repeated till the absolute value of the
difference between the new value and the previous value of the terminal velocity in an iteration
is negligible.

Nonlinear Algebraic Equations

25

EXAMPLE 2.4 Oil droplets of diameter 2 mm are to be settled from air at 25C and 1 atm.
The density of oil is 900 kg/m3. Calculate the terminal settling velocity of the particles. For
air at these conditions, m = 1.85 105 kg/m-s. CD is given by

%&


  4G 
R
4G R

Solution The following data are given: dp = 2 103 m, m = 1.85 105 kg/m-s. The density
of air under the given conditions is given by

2/
46

 u  u  
 u 

 kg/m3

The particle Reynolds number is given by

4G R

SI XV F R
N

 u XV u  u  
 u  

XV

The calculations are presented in Table 2.3.

Table 2.3
Assumed nt

Calculations in Example 2.6

Rep

CD

nt

0.03
1.5
4.9
6.2

3.83
191.35
625.0
790.0

8.63
0.82
0.52
0.47

1.5
4.9
6.2
6.47

6.47

825.38

0.47

6.52

The terminal velocity obtained is 6.5285 m/s.

Program 2.3 for calculating the terminal velocity is given in the Appendix.

2.5 System of Nonlinear Equations

We now extend Newtons method to solve a set of N simultaneous nonlinear algebraic
equations for N unknowns.
H  Z  Z  Z !  Z 0  

H  Z  Z  Z !  Z 0  
H  Z  Z  Z !  Z 0  

"
H 0  Z  Z  Z !  Z 0  

We define the vector of unknowns

26

Introduction to Numerical Methods in Chemical Engineering

> Z

Z " Z 0 @

Z

and write the system of equations as

f (x) = 0
We use a Taylor series expansion to obtain Newtons method, representing the ith function in
the vicinity of the current estimate xn as
HK  Z 

P
P
K
K
  ZHO  ZO  ZO     ZO  ZO  ZO HZ R  Z R  Z PR  "
O
O R

HK Z P 

ZP

ZP

Assuming that xn is sufficiently close to the true solution xS, we can drop the quadratic and
higher order terms
0

P
K
  ZHO  Z5 O  ZO 
O

 HK Z P 

ZP

For convenience we collect the first partial derivatives into the N N Jacobian matrix

H
Z

KO

(2.20)

The truncated Taylor series expansion then becomes

0

P
P
  ,KO  ZO
O

 | HK Z P 

or
0

P
P
,KO 'ZO
O

P
 ZO

 HK Z P

(2.21)

where the update vector is given by

(2.22)
'Z P  Z P   Z P
The terms on the left hand side of Eq. (2.21) are the ith component of a matrixvector
product. The linear system is
, P 'Z P 

H ZP

(2.23)

Iterations are performed till there is no change in x1 , x 2 , x3 ,..., x N , that is

P
P
P
P
'Z   F CDU  'Z   F CDU  'Z   F CDU ! 'Z 0  F CDU

(2.24)

Let us consider two nonlinear equations f1(x1, x2) and f2(x1, x2). To start the iteration, some
initial values of x1 and x2 have to be assumed. The change in the values of x1 and x2 are
determined using Eq. (2.23).





Z
H

H
Z

'Z
 'Z


H

H
 
H

(2.25)

Nonlinear Algebraic Equations

27

Now we have to find the inverse of the Jacobian matrix. The inverse of a nonsingular
2 2 matrix #

C
C


C
is given by #
C

 C

FGV #  C

 C
. Thus Eq. (2.25) can be
C

written as
'Z
'Z


where

H 
 Z

& H 
 Z

&

Thus
'Z

H
Z H

H H

Z

(2.26)

H H
H H
  
Z Z Z Z

(2.27)

H
H
 H 
Z
Z
&

(2.28)

H

and

H 
H
 H 
Z
Z
(2.29)
'Z
&
The algorithm for solution of two simultaneous nonlinear algebraic equations is given below:
H

(i) Assume x1 and x2,

(ii) Calculate f1, f2,

H H H
H
,
,
, and
,
Z Z Z
Z

(iii) Calculate Dx1 and Dx2, and

(iv) Calculate new values of x1 and x2.
P 
P
P
P
Go to (ii) till Z  Z  F and Z   Z  F .

EXAMPLE 2.5
equations:

Obtain the values of x and y that satisfy the following two nonlinear algebraic
H  Z [  G Z  Z[   

I  Z [  UKP Z[  Z  [   

Solution

The partial derivatives of function f are given by

H
Z
H
[

GZ  [
Z

28

Introduction to Numerical Methods in Chemical Engineering

The partial derivatives of function g are given by

I
Z
I
[

[ EQU Z[  
Z EQU Z[  

Let us assume x = 0.1 and y = 0.5.

H  Z [ 

I  Z [ 
H
Z
H
[
I
Z
I
[

G Z  Z[   
UKP Z[  Z  [  

 

G Z  [ 
Z



[ EQU Z[   
Z EQU Z[   

&

'Z

'[

H I H I


Z [ [ Z
H
I
I  H
[
[     
 
&

I
H
H
I
Z      
Z
&


New x = 0.1 0.13036 = 0.03036

New y = 0.5 + 0.5406 = 1.0406
The iterations are summarized in Table 2.4.
Table 2.4
x
0.1

y
0.5

Summary of iterations in Example 2.5

H

0.1552 0.3991 1.6052

0.1

0.0097 2.0107 0.03036

1.5

0.03036 1.0406

0.0615

0.00086 0.9685

0.0017 0.0324 1.9676 0.00086 1.9685

2.0406

Dx

Dy

1.1

1.6157 0.13036 0.5406

0.9696

2.0115

0.0295 0.0721

0.99914 1.9676

0.00088 0.0307

0.9992

0.0000 0.0008 1.9992

1.9992

1.9992

0.0008

Nonlinear Algebraic Equations

29

The solution of the given nonlinear algebraic equations is x = 0 and y = 1. Note that when
f = 0 and g = 0 the solution is obtained.
Program 2.4 for the solution of the above two simultaneous nonlinear equations is given in the
Appendix.
EXAMPLE 2.6
equations:

Modify Program 2.4 to solve the following system of two nonlinear algebraic


H  Z  Z   Z   Z   

H  Z  Z 
Solution



 Z  Z   

For the given nonlinear equations

H
Z

H
Z 


 Z

 Z

H 
Z

 Z CPF

H
Z 


 Z 

Program 2.4 can be modified to obtain the following solution: x1 = 3 and x2 = 4.

Exercises
2.1

Determine the root of the equation

 Z    Z    Z   
which is close to 2.5.
(Ans: 2.5034)

2.2

Air at 25C and 1 atm flows through a 4 mm diameter tube with an average velocity
of 25 m/s. The roughness is e = 0.0015 mm. The friction factor is given by

H

F &

  NQI

 4G H

Determine the pressure drop in a 1 m section of the tube using the relation
'2

H.8  S
&

The density of air at 25C and 1 atm is 1.23 kg/m3 and the viscosity is
1.79 105 kg/m-s.
(Ans: f = 0.03467, DP = 3.33 kPa)
2.3

Solid particles having a diameter of 0.05 mm, shape factor fs = 0.88, and density
of 1000 kg/m3 are to be fluidized using air at 2.0 atm and 25C. The voidage
at minimum fluidization is 0.39. The viscosity of air under these conditions is
1.845 10-5 kg/m-s. The molecular weight of air is 28.97.
(Ans: 0.000611 m/s)

30

Introduction to Numerical Methods in Chemical Engineering

2.4

Solve Exercise 2.3 for solid particles having a diameter of 0.25 mm. The voidage
at minimum fluidization is 0.48.
(Ans: 0.0327 m/s)

2.5

Oil droplets of diameter 0.2 mm are to be settled from air at 25C and 1 atm. The
density of oil is 900 kg/m3. Calculate the terminal settling velocity of the particles.
Viscosity of air under these conditions is 1.85 105 kg/m-s. CD is given by

  4G 
%&
R
4G R
(Ans: 0.6462 m/s)

2.6

Solve Exercise 2.5 for oil droplets of diameter 0.02 mm.

(Ans: 0.0105 m/s)

Chapter 3

Chemical Engineering
Thermodynamics
The calculation of molar volume using the van der Waals, RedlichKwong, and Peng
Robinson cubic equations of state at the given temperature and pressure is discussed first in
this chapter. After this, bubble point, dew point, and flash calculations using Raoults and
modified Raoults law are discussed. The determination of vapour pressure at the given
temperature for a pure substance following a cubic equation of state is thereafter discussed.
The determination of system pressure and vapour phase composition at the given temperature
and liquid phase composition is discussed using the gammaphi [ 2G Z H H and phiphi
[K 2GK8 ZK 2GK. approaches. The solution of two simultaneous chemical reactions in
equilibrium in the homogeneous phase and the calculation of adiabatic flame temperature are
also discussed in this chapter.

3.1 Solution of Cubic Equations of State

The molar volume of both the saturated vapour and saturated liquid can be calculated using
cubic equations of state. The cubic equations of state can have three real roots or one real root
and two complex roots. When there is only one real root, then only one phase existsliquid
or vapourand when three real roots exist, then there are two phases. The smallest root is the
molar volume of saturated liquid and the largest root is the molar volume of saturated vapour.
The intermediate root is of the no physical significance. To determine the molar volume of the
liquid phase, the starting value taken is V = b, and to determine the molar volume of the vapour
46
phase, the starting value taken is 8
.
2
The van der Waals equation of state is
46
C
2
 
(3.1)
8 D 8
The cubic form of the van der Waals cubic equation of state is given by
46  C
CD

8  D 

(3.2)
8  8 
2
2
2

where

 4 6E
and D
 2E
31

46E
2E

32

Introduction to Numerical Methods in Chemical Engineering

46  C
CD

8  D 
. At the given temperature and
8  8 
2
2
2

pressure and given critical properties of the substance, the only unknown in this equation is
the molar volume V. The derivative of the function f with respect to the molar volume is given
by

Let us define the function as H

46
C

H c 8    D 
(3.3)
8 
2
2

A value of molar volume is assumed. At the assumed molar volume the value of the
function f and its derivative f are determined and the new molar volume is determined using
Newtons method [see Eq. (2.1)]

8 P 

8P 

H
Hc

(2.1)

Thereafter, the new molar volume becomes the old molar volume, and f and f are determined
again at this molar volume. The procedure is repeated till there is a very meagre change
between the new and old molar volumes, that is, 8 P   8 P    .
The Redlich-Kwong equation of state is

46
C
  
8  D 6 8 8  D 

(3.4)

The cubic form of the Redlich-Kwong cubic equation of state is given by

8 
where

46   D46
C
CD
8  D 

8 
2
2
62
62

4 6E
2E



and

(3.5)

 46E
.
2E

46   D46
C
CD
. At the given
8  D 

8 
2
2
62
62

temperature and pressure and given the critical properties of the substance, the only unknown
in this equation is the molar volume, V. The derivative of the function f with respect to the
molar volume is given by
8 

Let us define the function as H

46
D46
C

8  D 


2
2
62
The PengRobinson equation of state is
H

8   

(3.6)

46
C
 
8  D 8  D8  D 

(3.7)

The cubic form of the PengRobinson cubic equation of state is given by

46    46D C
46  CD

8  D 
 8  D 
D 
8  D 
2
2
2
2
2

(3.8)

Chemical Engineering Thermodynamics

  46E 
2E

33

6
  O  

6E

  X  X 

 46E
2E

Let us define the function as

46    46D C
46  CD

8  D 
 8  D 
D 
8  D 
2
2
2
2
2

At the given temperature and pressure and given critical properties of the substance the only
unknown in this equation is the molar volume V. The derivative of the function f with respect
to the molar volume is given by
H

46

  46D C
H c 8    D 

8  D 
2
2
2

(3.9)

EXAMPLE 3.1 Calculate the molar volume of saturated liquid water and saturated water
vapor at 100C and 101.325 kPa using van der Waals, RedlichKwong and PengRobinson
cubic equations of state. For water: TC = 647.1 K, PC = 220.55 bar, and w = 0.345.
Solution Program 3.1 for calculating the molar volume at the given temperature and pressure
using various cubic equations of state is given in the Appendix. The result obtained from the
program is given below.
Saturated liquid volume using PengRobinson equation of state = 2.25 105 m3/mol
Saturated vapour volume using PengRobinson equation of state = 0.030352 m3/mol
Saturated liquid volume using RedlichKwong equation of state = 2.64 105 m3/mol
Saturated vapour volume using RedlichKwong equation of state = 0.030400 m3/mol
Saturated liquid volume using van der Waals equation of state = 3.90 105 m3/mol
Saturated vapour volume using van der Waals equation of state = 0.030469 m3/mol.

3.2 Bubble Point and Dew Point Temperature Calculations

Using Raoult's Law
3.2.1 Bubble Point Temperature Calculation
When the liquid phase composition is given, the governing equation is 2 Z 2UCV  Z 2UCV . In
this problem, along with the liquid phase composition the system pressure is given and the
bubble point temperature and the vapour composition have to be determined. Newtons method

34

Introduction to Numerical Methods in Chemical Engineering

is used to determine the temperature which satisfies the equation 2

formulate a function f.
H

Z 2UCV  Z 2UCV . Let us

(3.10)

2  Z 2UCV  Z 2UCV

Using Antoine equation

NP 2 UCV

#

we get

$
6 %

(3.11)

$
$
2  Z GZR # 
 Z GZR # 

(3.12)
6  %
6  %

In the above equation the Antoine parameters, system pressure and liquid composition are
given. The only unknown is the temperature. The derivative of the function f with respect to
temperature is given by
H

Hc 

Z 2UCV $

6  % 

Z 2UCV $

6  % 

(3.13)

A value of temperature is assumed. At the assumed temperature the value of function f and its
derivative f are determined and the new temperature is determined using [see Eq. (2.1)]
H
6 P  6 P 
(2.1)
Hc
Thereafter the new temperature becomes the old temperature and again at this temperature, f
and f are determined. The procedure is repeated till there is a very meagre change between
the new and old temperatures, that is, 6 P   6 P    . This equation can also be written as

6 P   6 P
   .
P 
6

ZK 6KUCV . The saturation

The assumed temperature is calculated from the relation 6 P
temperatures 6UCV and 6UCV are calculated for the given pressure using the Antoine equation
6 UCV

$
%
#  NP 2

Once the temperature that satisfies the equation 2

phase composition can be determined using [

(3.14)

Z 2UCV  Z 2UCV is determined, the vapour

Z 2UCV
and [
2

Z 2UCV
.
2

3.2.2 Dew Point Temperature Calculation

[
[

 UCV . In this problem
UCV
2 2
2
system pressure is given along with vapour phase composition and dew point temperature and
liquid phase composition have to be determined. Newtons method is used to determine the
[
[

  . Let us formulate a function f .
temperature which satisfies the equation
2 2UCV 2UCV

When the vapour phase composition is given, use is made of

35

Chemical Engineering Thermodynamics

Using the Antoine equation NP 2 UCV


[
[
 UCV  UCV
2 2
2

#

$
, we get
6 %

(3.15)

$
$

 [ GZR  # 
 [ GZR  # 

(3.16)
2
6  %
6  %

Here in this equation the Antoine parameters, system pressure and vapour composition are
given. The only unknown is the temperature. The derivative of the function f with respect to
temperature is given by
H

Hc

[ $

2UCV

6  % 

[ $

2UCV

(3.17)

 6  % 

A value of temperature is assumed. At the assumed temperature the value of the function f and
its derivative H c are determined and the new temperature is determined using
6 P 

6P 

H
Hc

Thereafter, the new temperature becomes the old temperature and f and H c are determined
again at this temperature. The procedure is repeated till there is a very meagre change between
the new and old temperatures, that is, 6 P   6 P    . This equation can also be written as
6 P  6 P
[ 6 UCV .
   . The assumed temperature is calculated from the relation 6 P
P 
6
[
[

Once the temperature that satisfies the equation
 UCV is determined, the liquid
UCV
2 2
2
[ 2
[ 2
and Z
.
phase composition can be determined using Z
UCV
2
2UCV

EXAMPLE 3.2 Calculate the bubble point and dew point temperatures for the acetone (1)
water (2) system at 101.325 kPa for feed composition z1 = 0.5. Assume the system to follow
Raoults law.
Solution Program 3.2 for calculating the bubble and dew point temperatures for a system
following Raoults law is given in the Appendix. The result obtained from the program is
bubble point temperature = 71.81C, dew point temperature = 87.08C.

3.3 Flash Calculations Using Raoult's Law

The aim here is to calculate the compositions of the vapour and liquid phases at the given
temperature and pressure under flash conditions, assuming Raoults law to be true. For a
mixture at the given pressure, if the temperature lies between the bubble point and dew point

36

Introduction to Numerical Methods in Chemical Engineering

temperatures or at the given temperature, if the pressure lies between the dew point and bubble
point pressure, both liquid and vapour exist. In this section we shall determine the equilibrium
liquid and vapour phase compositions if the temperature, system pressure and feed composition
are given. The overall composition is denoted by zi and L and V denote the amount of moles
in the liquid and vapour phases respectively. Let the initial total number of moles before
flashing be 1. The distribution coefficient (Ki) for a species is defined as its composition in the
vapour phase divided by its composition in the liquid phase. We can write for a particular
species that
-

[
Z

(3.18)

2 UCV
; therefore, if the temperature and the pressure
2
of the system are given, then the K values of all the components can be calculated. The
composition of the vapour in terms of Ki and feed composition is given by
For a system following Raoults law, -

-\
  8  8K

(3.19)
K

and the composition of the liquid phase is given by

Z

\
  8  8K

(3.20)
K

Finally we should have

-\

[   8  8K

(3.21)

where the summation is over all the components, and also

\

Z   8  8-

3.22)

Therefore let us define a function

  \

[  Z   8  8K

(3.23)

The function has to be formulated in such a way that its required value is zero. In this equation
the only unknown is V, which is the number of moles in the vapour phase per unit mol fed
to the system. The derivative of the function with respect to V is given by
Hc 

  \

  8  8- 
K

(3.24)

A value of V is assumed. At the assumed V the value of the function f and its derivative f
are determined and the new V is determined using
8 P 

8P 

H
Hc

Chemical Engineering Thermodynamics

37

Thereafter, the new V becomes the old V and again at this V the function f and its derivative
f are determined. The procedure is repeated till there is a very meagre change between the
new and old values of V, that is, 8 P   8 P    . Once V is determined, the vapour and
liquid phase composition can be determined.
EXAMPLE 3.3 Calculate the compositions of the liquid and vapour phases for the acetone
(1)acetonitrile (2)nitromethane (3) system. The feed composition is z1 = 0.3, z2 = 0.3 and z3
= 0.4. At the given temperature, 2UCV 195.75 kPa, 2UCV 97.84 kPa, and 2UCV 50.32 kPa.
The pressure of the system is 100 kPa. Assume the system to follow Raoults law.
Solution Program 3.3 for calculating the composition of the liquid and vapour phases under
flash conditions for a system following Raoults law is given in the Appendix. The result
obtained from the program is given below: x1 = 0.25057, y1 = 0.490491, x2 = 0.301341,
y2 = 0.294832, x3 = 0.44561, y3 = 0.224231. The number of moles in vapour phase is 0.206026.

3.4 Bubble Point and Dew Point Temperature Calculations

Using Modified Raoult's Law
The modified Raoults law is given by
[ 2

ZH  2UCV

(3.25)

[ 2

Z H  2

(3.26)

UCV


The activity coefficients can be determined using various models. In the present case the
Wilson model is used, because for a given system the activity coefficients can be determined
as a function of the temperature and the liquid composition. The Wilson parameters are given
by
/

8
C
GZR  
46
8

(3.27)

/ 

8
C
GZR  
46
8

(3.28)

NP H 

/
/ 
 NP
Z  Z /   Z


Z  Z / Z  Z / 

(3.29)

NP H 

/
/ 
 NP
Z  Z /    Z


Z  Z / Z  Z / 

(3.30)

The activity coefficients are given by

Calculation of bubble point pressure

(i) Enter the temperature and the liquid composition.

38

Introduction to Numerical Methods in Chemical Engineering

(ii) Calculate the vapour pressure of the components at the given temperature.
(iii) Calculate the activity coefficients at the given temperature and liquid composition.
(iv) Calculate the bubble point pressure using the relation 2 ZH  2UCV  ZH  2UCV
Calculation of bubble point temperature
(i) Enter the pressure and the liquid composition
(ii) At the given pressure, calculate the saturation temperature of the components and the
assumed temperature using 6 P

6Z 6 UCV .
K

(iii) At the assumed temperature, calculate the vapour pressure of the components and the
activity coefficients.
(iv) Update the vapour pressure of Component 1 using the relation
2

2UCV

ZH   ZH 

2UCV
2UCV

(v) From the updated value of 2UCV , calculate the temperature using

$

#  NP 2UCV

 %

(vi) Go to Step (iii) and repeat the procedure till convergence in temperature is obtained.
Calculation of dew point pressure
(i) Enter the temperature and the vapour composition.
(ii) Calculate the vapour pressure of the components at the given temperature.
(iii) Initially assume the activity coefficients to be one and calculate the system pressure
using

2
[
[

UCV
UCV
H 2
H  2

(iv) Calculate the liquid composition using Z
(v) Update the liquid composition using x1

[ 2

UCV
H 2


and Z

x1
and x 2
x1  x 2

[ 2
UCV

H  2

1  x1 .

(vi) At the liquid composition, calculate the activity coefficients.

(vii) Go to Step (iv) and repeat the procedure till convergence in activity coefficients is
obtained.
(viii) Calculate the system pressure using

Chemical Engineering Thermodynamics

39

[
[

UCV
UCV
H 2
H  2


(ix) Go to Step (iv) and repeat the procedure till convergence in the pressure is obtained.
Calculation of dew point temperature
(i) Enter the pressure and the vapour composition.
(ii) At the given pressure, calculate the saturation temperature of the components and the
assumed temperature using 6 P

6[ 6 UCV . Initially take

K

g1 = g2 = 1.

(iii) At the assumed temperature, calculate the vapour pressure of the components.
(iv) Calculate the liquid composition using Z
(v) Update the liquid composition using Z

[ 2

UCV
H 2


and Z

[ 2
UCV

H  2

Z
and x2 = 1 x1.
Z  Z

(vi) At the liquid composition, calculate the activity coefficients.

(vii) Go to Step (iv) and repeat the procedure till convergence in activity coefficients is
obtained.
[
[ 2 UCV
(viii) Update the vapour pressure of Component 1 using the relation 2 UCV 2    UCV

H  H  2
$
(ix) From the updated value of 2UCV , calculate the temperature using 6
 %
#  NP 2UCV
(x) Go to Step (iii) and repeat the procedure till convergence in temperature is obtained:
EXAMPLE 3.4 Consider a binary vapourliquid equilibrium system. The Antoine equations
of the components are given by
NP 2UCV

 


6  

NP 2UCV

 


6  

where the temperature is in C and the vapour pressure in kPa. The parameters in the Wilson
equation are: a12 = 437.98 cal/mol and a21 = 1238 cal/mol. The molar volume of the
components is V1 = 76.92 cm3/mol and V2 = 18.07 cm3/mol. Assume the system to follow the
modified Raoults law.
(i) Calculate the bubble point pressure at 100C and x1 = 0.5.
(ii) Calculate the bubble point temperature at 101.325 kPa and x1 = 0.5.

40

Introduction to Numerical Methods in Chemical Engineering

(iii) Calculate the the dew point pressure at 100C and y1 = 0.5.
(iv) Calculate the dew point temperature at 101.325 kPa and y1 = 0.5.
Solution Program 3.4 for the bubble point and dew point calculations for a system following
the modified Raoults law is given in the Appendix. The result obtained from the program is
given below: (i) 204.264 kPa, (ii) 80.93C, (iii) 184.10 kPa, and (iv) 83.82C.

3.5 Flash Calculations Using Modified Raoult's Law

In flash the vapour and liquid phases coexist at the given temperature and pressure. The feed
composition is given and the compositions of the liquid and vapour phases are to be
determined using the modified Raoults law. For the given temperature and feed composition,
first the bubble point and dew point pressures are determined. Then a pressure is chosen
between the bubble point and dew point pressures.
(i) Enter the temperature.
(ii) At the given temperature calculate the vapour pressure of components.
(iii) Calculate the activity coefficients by assuming the total feed as liquid.
(iv) Calculate the bubble point pressure using the relation 2

ZH  2UCV  ZH  2UCV

(v) Record the bubble point pressure (Pbubble) and the activity coefficients (g 1b and g 2b).
(vi) For the calculation of the dew point pressure (total feed as vapour), first assume the
activity coefficients to be1.

.
[
[

UCV
UCV
H 2
H  2

(viii) Calculate the liquid phase compositions using Z
(vii) Calculate the pressure using 2

(ix) Update the liquid composition using Z

[ 2
and Z
UCV
H 2


[ 2
.
UCV
H  2

Z
and x2 = 1 x1.
Z  Z

(x) At the liquid composition, calculate the activity coefficients.

(xi) Go to step (viii) and repeat the procedure till convergence in activity coefficients is
obtained.
(xii) Calculate the system pressure using 2


.
[
[

UCV
UCV
H 2
H  2


(xiii) Go to step (viii) and repeat the procedure till convergence in pressure is obtained.
(xiv) Store the dew point pressure (Pdew) and the activity coefficients (g 1d and g 2d).

Chemical Engineering Thermodynamics

41

(xv) Enter the pressure between the bubble point and dew point pressures.
(xvi) The assumed number moles in vapour phase is calculated using 8

2DWDDNG  2
.
2DWDDNG  2FGY

(xvii) The assumed value of

g 1 is calculated using

H

 2  2FGY H D  H F 
 H F .
 2DWDDNG  2FGY 

(xviii) The assumed value of

g 2 is calculated using

H

 2  2FGY H D  H  F 
 H F .
 2DWDDNG  2FGY 

H 2


UCV

(xix) Calculate -

and - 

H  2

(xx) Calculate [

- \
and [
  8  8-

(xxi) Calculate Z

[
and Z
-

(xxii) Define a function H

(xxiii) H c 

UCV

-  \
.
  8  8- 

[
.
-

[  Z  [  Z .

  \

  8  8- 
K

(xxiv) 8 P 

8P 

H
.
Hc

(xxv) Go to Step (xx) and repeat the procedure till convergence in V is obtained.
(xxvi) Calculate g1 and g2.
(xxvii) Go to Step (xix) and repeat the procedure till convergence in activity coefficients is
obtained.
EXAMPLE 3.5 Calculate the composition of the liquid and vapour phases for the system
acetone (1)water (2) at 100oC and 200 kPa. The feed composition is z1 = 0.3. The Antoine
equations of the components are given by
NP 2UCV

 


6  

NP 2UCV

 


6  

where the temperature is in C and the vapour pressure in kPa. The parameters in the Wilson
equation are: a12 = 292.66 cal/mol and a21 = 1445.26 cal/mol. The molar volume of the
components is V1 = 74.05 cm3/mol and V2 = 18.07 cm3/mol. Assume the system to follow the
modified Raoults law.

42

Introduction to Numerical Methods in Chemical Engineering

Solution Program 3.5 for calculating the composition of the liquid and vapour phases under
flash conditions for a system following the modified Raoults law is given in the Appendix.
The result obtained from the program is: bubble point pressure = 310.47 kPa, dew point
pressure = 142.80 kPa. The system pressure chosen is 200 kPa and after convergence the
number of moles in the vapour phase is 0.546235. x1 = 0.045019 and y1 = 0.511817.

3.6 Vapour Pressure Using Cubic Equation of State

The cubic equations of state are applicable for both the liquid and vapour phases. At a given
temperature, a cubic equation of state can be used to determine the vapour pressure of a pure
substance. A pressure is assumed and the fugacities in the liquid and vapour phases are
determined. If at the assumed pressure the fugacities are not identical, then another pressure
is assumed and the pressure at which the fugacities are the same (f L = f V) is the vapour
pressure. The algorithm for calculation of vapour pressure is given below.
(i) Assume a pressure.
(ii) At the given temperature and the assumed pressure, calculate VV and VL as described
in Program 3.1.
(iii) Calculate f L and f V using cubic equation of state.
(iv) If

H.  H8
  , stop.
H8

(v) Calculate the new pressure using, 2PGY

2QNF

H.
, and go back to Step (ii) and repeat
H8

the procedure till Condition (iv) is satisfied.

For the PengRobinson cubic equation of state, the fugacity of a pure substance is given by
NP

H
2

8    D
2D
C

NP
<    NP < 

46  D46 8     D

(3.31)

The fugacity of the liquid phase is given by

H.
NP
2

8.    D
C
. 2D
<    NP < 
NP

46  D46 8 .     D

where
<.

28 .
46

(3.31a)

Chemical Engineering Thermodynamics

and the fugacity of the vapour phase is given by

H8
NP
2

88     D
C
8 2D
<    NP < 
NP

46  D46

88     D
8

where

43

(3.31b)

28 8
46

<8

EXAMPLE 3.6 Calculate the vapour pressure of water at 100C using the PengRobinson
cubic equation of state. For water: TC = 647.1 K, PC = 220.55 bar, and w = 0.345.
Solution Program 3.6 for calculating the vapour pressure using the cubic equation of state
is given in the Appendix. The vapour pressure of water at 100C as obtained from the program
is 96071.375 Pa.

3.7 Pxy Diagram Using GammaPhi Approach

In the GammaPhi approach, the vapourliquid equilibrium is described using the equation
[ 2G8

(3.32)

ZH  H

8
(3.33)
[ 2G ZH  H
At the given temperature and liquid phase composition, the equilibrium pressure and the
vapour composition are determined. Then again at the same temperature and at a different
liquid phase composition, the equilibrium pressure and vapour composition are determined.
This is used to generate the Pxy diagram at the given temperature.
The algorithm is given below.

(i) Read T, x1, Tc1, Pc1, Tc2, Pc2, w1, w2, ZC1, ZC2, 2UCV , 2UCV .
(ii) x2 = 1 x1.
(iii) At the given temperature and liquid phase composition, calculate the activity
coefficients g1 and g2.
(iv) At the given temperature, calculate B11, B22, B12 and d12.
(v) Calculate the initial value of the total pressure using 2 ZH  2UCV  ZH  2UCV (only to
start the solution do we assume the modified Raoults law to be true) and the
ZH  2UCV
ZH  2UCV
and [
.
2
2
(vi) At the total pressure, calculate the fugacity of the pure liquid species 1(f1) and 2(f2)
at the given temperature and calculated pressure, using the relation
composition in vapour phase using the relation [

$ 2 UCV
2 UCV GZR
46

KK

8 . 2  2 UCV

GZR

46

44

Introduction to Numerical Methods in Chemical Engineering

(vii) Calculate the fugacity coefficient of the species 1( G ) and 2( G ) in the vapour phase.
(viii) Calculate -
(ix) Calculate 5

H  H
G 2

and - 

H  H
G 2

- u Z  -  u Z  .

- u Z
- u Z
and [
. Go to Step (vii) and repeat the procedure
5
5
till dS < e. (This is because the composition of the vapour phase has changed and
therefore the fugacity coefficients of the species in the vapour phase get changed.)

(x) Calculate [

ZH  H ZH  H
and calculate the new

G
G
ZH  H
ZH  H
compositions in the vapour phase using [
and [
. Go to Step
G 2
G 2
(vi) and repeat the procedure till dP < e.

(xi) Calculate the new pressure using 2

EXAMPLE 3.7 Consider the methanol (1) water (2) system in vapourliquid equilibrium.
The temperature of the system is 100C and the liquid phase composition is x1 = 0.958.
Determine the system pressure and the vapour phase composition. Use the GammaPhi
approach. The Antoine equations of the components are given by
NP 2UCV

 


6  

NP 2UCV

 


6  

where temperature is in C and vapour pressure in kPa. The parameters in the Wilson equation
are: a12 = 107.38 cal/mol and a21 = 469.55 cal/mol. The molar volume of the components is
V1 = 40.73 cm3/mol and V2 = 18.07 cm3/mol. Tc1 = 512.6 K, Pc1 = 80.97 bar, w1 = 0.564,
Zc1 = 0.224, Tc2 = 647.1 K, Pc2 = 220.55 bar, w2 = 0.345, Zc2 = 0.229.
Solution Program 3.7 for Pxy calculations using the GammaPhi approach is given
in the Appendix. The result obtained from the program is given below: pressure = 344930.59
Pa and y1 = 0.980694.

3.8 P-x-y Diagram Using Cubic Equation of State

For the PengRobinson equation of state the fugacity coefficient of component 1 in the liquid
phase is given by

NP G.

D
 < .   D.  NP < .  2D

46


Chemical Engineering Thermodynamics

  Z C  Z C

C.
 D 46
C


 2D
 D
46
 . NP
D
2D .
< .     
46
<.    

45

(3.34)

and the fugacity coefficient of component 1 in the vapour phase is given by

  [ C  [ C

C8
 D 46
8

D
 < 8   D8  NP < 8  2D

46

NP G8


 2D
 D
46
 8 NP
D
2D8
8
<     
46
<8    

(3.35)

The fugacity coefficient of component 2 in the liquid phase is given by

NP G.

  Z C  Z C

C.
 D 46
C

D
 < .   D.  NP < .  2D

46


 2D
 D
46
 . NP
D
2D .
.
<     
46
<.    

(3.36)

and the fugacity coefficient of component 2 in the vapour phase is given by

  [ C  [ C

C8
 D 46
8

D
 < 8   D8  NP < 8  2D

46

8
NP G

where


 2D
 D
46
 8 NP
D
2D8
< 8     
46


<8    

(3.37)

C.



Z C  Z C   Z Z C

(3.38)

D.

ZD  Z D

(3.39)

C8



[ C  [ C   [ [ C

(3.40)

D8

[D  [ D

(3.41)

<.

28 .
46

(3.42)

46

Introduction to Numerical Methods in Chemical Engineering

28 8
46
For a binary VLE mixture the phase equilibrium equations are
<8

[ 2 G8

Z 2 G.

(3.43)
(3.44)

8
(3.45)
[ 2 G Z 2 G.
and variables are T, P, x1, and y1. Thus, if any two variables (T or P, x1 or y1) are specified
the other two can be determined.
Since the compositions of the liquid and vapour phases are different, a and b for each
phase are different. Calculate a and b for the liquid phase and then ZL and VL (the smallest
root), and a and b for the vapour phase and then ZV and VV (the largest root). The molar volume
is calculated by solving the cubic form of the PengRobinson equation of state. The algorithm
for the calculation of the bubble point pressure and the vapour phase composition at the given
temperature and the liquid phase composition for a binary mixture using the cubic equations
of state is given below.

(i) Read T, x1, Tc1, Pc1, Tc2, Pc2, w1, w 2

(ii) Calculate x2 = 1 x1
(iii) Calculate a11, a22, a12
a11 a 22 , b1, b2
.
(iv) Calculate for liquid phase: C



Z C  Z C   Z Z C and D . ZD  Z D .
(v) Assume some pressure (P) and composition in the vapour phase y1 (assume y1 greater
than x1 if component 1 is the more volatile component).

(vi) Using Newtons technique, calculate VL using aL, bL, x1, x2. Take Vold = bL because
28 .
the liquid phase molar volume is to be calculated. From VL, calculate < .
46
(compressibility factor in the liquid phase).
(vii) Calculate the fugacity coefficient of the components G. and G. in the liquid
mixture.
8
(viii) Calculate for the vapour phase: C



[ C  [ C   [ [ C and D8

[D  [ D .

46
because
2
28 8
the vapour phase molar volume is to be calculated. From VV, calculate < 8
46
(compressibility factor in the vapour phase).

(ix) Using Newtons technique, calculate VV using aV, bV, y1, y2. Take 8QNF

8
(x) Calculate the fugacity coefficient of the components G8 and G in the vapour phase
mixture.

(xi) Calculate -
(xii) Calculate 5WO

G.
and - 
G8

G.
.
8
G
- u Z  -  u Z  

Chemical Engineering Thermodynamics

47

- u Z
- u Z
and [
. Go to Step (viii) and repeat the procedure
5WO
5WO
till E
5WO  F . This is because the composition of the vapour phase has changed;
therefore aV and bV get changed.
(xiv) Calculate the new pressure using 2PGY 2QNF u 5WO . Go to Step (vi) and repeat the
procedure till E 2  F .

(xiii) Calculate [

EXAMPLE 3.8 Consider the CO2 (1) n-pentane (2) system in vapourliquid equilibrium.
The temperature of the system is 377.65 K and the liquid phase composition is x1 = 0.5.
Determine the system pressure and the vapour phase composition using the PengRobinson
cubic equation of state. Tc1 = 304.2 K, Pc1 = 73.83 bar, w1 = 0.224, Tc2 = 469.7 K, Pc2 = 33.70
bar, and w2 = 0.252.
Solution Program 3.8 for Pxy calculations using the PengRobinson cubic equation of
state is given in the Appendix. The result obtained from the program is given below: Pressure
= 6524432 Pa and y1 = 0.81127.

3.9

Chemical Reaction EquilibriumTwo Simultaneous

Reactions

The solution of two simultaneous nonlinear algebraic equations is described in Section 2.5. The
application in chemical reaction equilibrium in the homogeneous phase is described in the
example below.
EXAMPLE 3.9
take place

In the production of synthesis gas the following two independent reactions

CH4 + H2O CO + 3H2
CO + H2O CO2 + H2

Starting with 5 moles of steam and 1 mole of methane, calculate the equilibrium composition
of the resulting mixture at 600C and 1 atm. At this temperature the equilibrium constants for
the first and second reaction are 0.574 and 2.21 respectively. Assume the gas mixture to follow
ideal gas behaviour.
Solution Let X1 be the reaction coordinate for the first reaction and X2 for the second. The
number of moles of components at equilibrium is as follows:
CH4: 1 X1
H2O: 5 X1 X2
CO: X1 X2
H2: 3X1 + X2
CO2: X2
Total: 6 + 2X1

48

Introduction to Numerical Methods in Chemical Engineering

Since the pressure is 1 atm, therefore K = KPKy = Ky.

 :  :   :  : 



  : 
  :  :  
   : 

:   :  : 

:  :  
  :  : 



The two nonlinear algebraic equations are

H

H

 :  :   :  : 
  :    :  :     : 
:    :  :  

 :  :     :  : 

 

 

and their derivatives are

H
:

 :  : :  :  
  :   :  :    : 
 :  :   :  :  :   : :   :   :   
  :     :  :      : 


H
: 

  :  :  :  :     :  :  


H
:

  :   :  :    : 
 :  :  :  : 
  :   :  :     : 
:  :  :    : 
 :

 :  :   :  :   :  :    :  : 

H
:

:  :  :  :  
 :   :

 :  :   :  :   :  :    :  : 

The algorithm is described in Section 2.5. Program 3.9 for solution of two chemical reaction
equilibrium equations is given in the Appendix. The solution is X1 = 0.912 and
X2 = 0.633. Thus at equilibrium: moles of CH4 = 0.09 mol, moles of H2O = 3.465 mol, moles
of CO = 0.285 mol, moles of H2 = 3.355 mol, moles of CO2 = 0.625 mol, and total number
of moles = 7.82 mol.

Chemical Engineering Thermodynamics

49

3.10 Adiabatic Flame Temperature

First the inlet species are laised from inlet temperature (T1) to adiabatic flame temperature (T)
and then the reaction at temperature T is carried out. The total enthalpy change is zero as there
is no heat and work exchange with the surroundings. The algorithm for the calculation of
adiabatic flame temperature is described below.
(i) Read the various constants of molar heat capacity at constant pressure for various species.
(ii) Read the various stoichiometric coefficients (ni) and moles of each species (ni) entering.
(iii) Read the standard enthalpy of formation for various species and calculate the
standard enthalpy change of reaction. Read the standard temperature (T0) and inlet
temperature (T1).
(iv) Calculate sa, sb, sc, sd using the relations
UC P C  P C  P C  P C
UD PD  P D  P D  P D
UE PE  P E  P E  P E
UF PF  P F  P F  P F 
(v) Calculate the heat required to raise the inlet species from the inlet temperature (T1)
to the adiabatic flame temperature (T) using
UD 
UE 
UF 
UC  6  6  
6  6 
6  6 
6  6



Note that this formula is valid for the molar heat capacity given by the equation

%2

(vi) Calculate

C  D6  E6   F6 

'C O  C  O  C  O  C  O  C

'D O  D  O  D  O  D  O D

'E O  E  O  E  O  E  O E

'F O  F   O  F  O  F  O F

(vii) Calculate the standard enthalpy change of reaction at the adiabatic flame temperature
(T) with respect to the standard enthalpy change of reaction at temperature (T0)
'D 
'E 
'F 
6  6 
6  6 
6  6



(viii) Assume an adiabatic flame temperature and at that temperature calculate the value of
the function
UD 
UE 
UF 
H UC  6  6  
6  6 
6  6 
6  6



'D 
'E 
'F 

+ '*6  'C  6  6  
6  6 
6  6 
6  6



and its derivative

'*6  'C  6  6  

H c UC  UD u 6  UE u 6   UF u 6   'C  'D u 6  'E u 6   'F u 6 

H
, take this as the
Hc
old temperature and go to Step (n) and repeat the procedure till there is no significant
change in temperature (dT < e).

(ix) Calculate new temperature using Newtons formula 6 P 

6P 

50

Introduction to Numerical Methods in Chemical Engineering

EXAMPLE 3.10 Calculate the adiabatic flame temperature of a gas initially at 25oC
containing 1 mol C2H6 (1), 4 mol O2 (2), 10 mol CO2 (3) and 0 mol of H2O (4). The ethane

is completely burned. The standard heat capacity is given by % 2 C  D6  E6   F6  , where

T is in K and % 2 in cal/mol-K.
Species
C2H6
O2
CO2
H2O(g)

b 102
4.124
0.3631
1.4285
0.04594

a
1.648
6.085
5.316
7.700

c 105
1.530
0.1709
0.8362
0.2521

The standard enthalpy of formation at 298.15 K is: '*  7I

'*  BIs
 kcal/mol, '*  % *
 kcal/mol.
H

d 109
1.740
0.3133
1.784
0.8587

 kcal/mol,

Solution

The reaction with stoichiometric amount of oxygen is


1 o %1  *  1

and the reaction with 4 mol of O2 and 10 mol CO2 is
% *  

%  *   1   %1  o %1   *  1  1

Program 3.10 for the calculation of adiabatic flame temperature (AFT) is given in the
Appendix. The result obtained from the computer program is AFT = 2090.39 K.

Exercises
3.1

Calculate the molar volume of saturated liquid water and saturated water vapour at
180C and 1.0 MPa using the van der Waals, RedlichKwong and PengRobinson
cubic equations of state. For water: TC = 647.1 K, PC = 220.55 bar, and w = 0.345.
(Ans: VL using the PengRobinson equation of state = 2.47 105 m3/mol, VV using
the PengRobinson equation of state = 0.003570 m3/mol, VL using the Redlich
Kwong equation of state = 2.95 105 m3/mol, VV using the RedlichKwong
equation of state = 0.003605 m3/mol, VL using the van der Waals equation of state
= 4.31 105 m3/mol, VV using the van der Waals equation of state = 0.003647 m3/mol)

3.2

Calculate the bubble point and dew point temperatures for the acetone (1)water
(2) system at 101.325 kPa for feed composition z1 = 0.9. Assume the system to
follow Raoults law.
(Ans: Bubble point temperature = 58.58C, dew point temperature = 66.93C)

3.3

Calculate the composition of the liquid and vapour phases for the acetone
(1) acetonitrile (2)nitromethane (3)system. The feed composition is z1 = 0.25,
z2 = 0.5 and z3 = 0.25. At the given temperature: 2UCV 195.75 kPa, 2UCV 97.84
50.32 kPa. The pressure of the system is 100 kPa. Assume the
kPa, and 2UCV
system to follow Raoults law.
(Ans: x1 = 0.175384, y1 = 0.343313, x2 = 0.504845, y2 = 0.493941, x3 =
0.320819, y3 = 0.161436. The number of moles in the vapour phase is 0.444331.)

Chemical Engineering Thermodynamics

3.4

51

Consider a binary vapourliquid equilibrium system. The Antoine equations of the

components are given by

NP 2UCV  
6  
NP 2UCV

 


6  

where the temperature is in C and the vapour pressure in kPa. The parameters in
the Wilson equation are: a12 = 437.98 cal/mol and a21 = 1238 cal/mol. The molar
volumes of the components are V1 = 76.92 cm3/mol and V2 = 18.07 cm3/mol.
Assume the system to follow the modified Raoults law.
(i) Calculate the bubble point pressure at 100C and x1 = 0.3.
(ii) Calculate the bubble point temperature at 101.325 kPa and x1 = 0.3.
(iii) Calculate the dew point pressure at 100C and y1 = 0.3.
(iv) Calculate the dew point temperature at 101.325 kPa and y1 = 0.3.
[Ans:
3.5

(i) 193.78 kPa, (ii) 82.18C, (iii) 140.78 kPa, and (iv) 91.00C]

Calculate the composition of the liquid and vapour phases for the acetone (1)
water (2) system at 100C and 200 kPa. The feed composition is z1 = 0.5. The
Antoine equations of the components are given by

NP 2UCV  
6  
NP 2UCV

 


6  

where the temperature is in C and the vapour pressure in kPa. The parameters in
the Wilson equation are: a12 = 292.66 cal/mol and a21 = 1445.26 cal/mol. The molar
volume of the components is V1 = 74.05 cm3/mol and V2 = 18.07 cm3/mol. Assume
the system to follow the modified Raoults law.
[Ans: Bubble point pressure = 334.97 kPa, dew point pressure = 195.68 kPa,
number of moles in vapour phase = 0.974685, x1 = 0.045018, y1 = 0.511817]
3.6

Calculate the vapour pressure of water at 120C using the PengRobinson cubic
equation of state. For water: TC = 647.1 K, PC = 220.55 bar, and w = 0.345.
(Ans: 191689.125 Pa)

3.7

Consider the methanol (1) water (2) system in vapourliquid equilibrium. The
temperature of the system is 100C and the liquid phase composition is x1 = 0.5.
Determine the system pressure and the vapour phase composition. Use the GammaPhi approach. The Antoine equations of the components are given by
NP 2UCV

 


6  

52

Introduction to Numerical Methods in Chemical Engineering

NP 2UCV

 


6  

where the temperature is in C and the vapour pressure in kPa. The parameters in
the Wilson equation are: a12 = 107.38 cal/mol and a21 = 469.55 cal/mol. The molar
volumes of the components are V1 = 40.73 cm3/mol and V2 = 18.07 cm3/mol.
TC1 = 512.6 K, PC1 = 80.97 bar, w1 = 0.564, ZC1 = 0.224, TC2 = 647.1 K,
PC2 = 220.55 bar, w2 = 0.345, ZC2 = 0.229.
(Ans:
3.8

Consider the CO2 (1) n-pentane (2) system in vapourliquid equilibrium. The
temperature of the system is 377.65 K and the liquid phase composition is x1 = 0.35.
Determine the system pressure and the vapour phase composition using the Peng
Robinson cubic equation of state. TC1 = 304.2 K, PC1 = 73.83 bar, w1 = 0.224,
TC2 = 469.7 K, PC2 = 33.70 bar, w2 = 0.252.
(Ans:

3.9

0.757692)

Pressure = 253786 Pa, y1

Pressure = 4572206 Pa, y1

0.782462)

Calculate the adiabatic flame temperature of a gas initially at 25C containing 1 mol
C2H6 (1), 5 mol O2 (2), 10 mol CO2 (3) and 0 mol of H2O (4). The ethane is
completely burned. The standard heat capacity is given by C0 = a + bT + cT2
P
+ dT3 where T is in K and C 0 in cal/mol-K.
P
Species
C2H6
O2
CO2
H2O(g)

a
1.648
6.085
5.316
7.700

b 102
4.124
0.3631
1.4285
0.04594

c 105
1.530
0.1709
0.8362
0.2521

d 109
1.740
0.3133
1.784
0.8587

The standard enthalpy of formation at 298.15 K is: '*  7I a  kcal/mol,
'*  BIs
 kcal/mol, and '*  % *
 kcal/mol.
H

(Ans: AFT = 2024.45 K)

Chapter 4

Initial Value Problems

F[
\ and F\  [ . The analytical solution
FZ
FZ
of the differential equations is y = A sin(x + a) and z = A cos(x + a). There are two constants
of integration A and a. In general, a system of N first order equations has N constants of
integration. If the values of the dependent variables y and z are specified for a value of x, then
the problem of determining the values of y and z at some future x is called an initial value
problem. Alternatively, the values of some of the dependent variables may be specified at a
number of different values of x, then the problem is called a boundary value problem. The
most common form is a two-point boundary value problem where the function values are given
for two values of x. Boundary value problems are discussed in Chapters 510.
The examples discussed here include the calculation of temperature profile in a double
pipe heat exchanger, of a single stirred tank with coil heater and also of a series of stirred tanks
with coil heater. The velocity profile of a solid particle in a pneumatic conveyor, and the
calculation of the concentration profile in the batch, stirred and plug flow reactors is also
discussed in this chapter.

Consider two simultaneous differential equations

4.1 Solution of Single Ordinary Differential Equation

Consider an ordinary differential equation
F[
H  Z [ 
(4.1)
FZ
with the initial condition: at x = x0, y = y0. The ordinary differential equation has to be
integrated to determine the value of y at some x. A step size, h, is chosen in the independent
variable. At the initial condition both x and y are known and after a step size in independent
variable, i.e. at x = x0 + h the value of y is computed. Then this becomes the starting point
for the next value of independent variable, x = x0 + 2h at which the value of dependent variable
is determined. This procedure is repeated till the value of x at which the y-value is to be
determined is reached. For each problem there exists an optimum step size. The step size
should not be high, otherwise the truncation errors will be high, and if the step size is very
small, then round-off errors are high. At the optimum step size the total error (truncation error
+ round-off error) is the least, and thus the numerical results are accurate.
53

54

Introduction to Numerical Methods in Chemical Engineering

In the numerical formulation of the problem some terms are left out; those errors are
called truncation errors. When the step size is small, these errors are less. If the step size is
very low, then the truncation errors are less but the round-off errors are high. Consider a step
size of 106 m; then to go from 1 to 10 m, the number of iterations required is 107, which is
huge. Whenever the new concentration is computed, the number is not completely stored, it
is stored up to some decimal places only, depending on the compiler used. So to avoid roundoff errors the step size should not be very small and to avoid truncation errors it should not
be very large. So there is an optimum step size and it varies with the problem. To determine
the optimum step size, at a particular value of independent variable x the value of the
dependent variable y is determined using various step sizes. When for two consecutive step
sizes the value of y is the same, then the higher of the two is the optimum step size.
In the RungeKutta fourth order method the following are computed:

M

J u H  Z  [ 

(4.2)

M




J u H Z  J [  M



(4.3)

M




J u H Z  J [  M



(4.4)

M

J u H  Z  J [  M 

(4.5)


 M   M   M  M 
(4.6)

From the initial condition (x0, y0) we have determined the value of y at x0 + h. Now again the
above calculations are carried out to determine the value of y at x0 + 2h. But before carrying
out the next calculation the following statements, due to which the value of y1 becomes y0 and
x0 + h becomes x0, are executed:
x0 = x0 + h
(4.7)
(4.8)
y0 = y1
[

EXAMPLE 4.1

[ 

Integrate the ordinary differential equation

F[
Z[
FZ
using the RungeKutta fourth order method. The initial condition is: at x = 0, y = 0. Determine
the value of y at x = 0.2. The analytical solution is given by y = ex x 1.
F[
Solution Let us take step size of h = Dx = 0.1. The function is H
Z  [ . To compute
FZ
y at x = 0.1 the starting point is x0 = 0 and y0 = 0. The calculations are given below.

f (0,0) = 0; therefore k1 = 0.1 f(0,0) = 0;

f (0.05,0) = 0.05; therefore k2 = 0.1 0.05 = 0.005;
f (0.05,0.0025) = 0.0525; therefore k3 = 0.00525;
f (0.1,0.00525) = 0.10525; therefore k4 = 0.010525.

Initial Value Problems

55

Thus

at x = 0.1
 M   M  M  M  

Now let us compute the value of y at x = 0.2. For this computation the starting point is
x0 = 0.1 and y0 = 0.0051708. The calculations are given below.
[

[ 

f(0.1, 0.0051708) = 0.1051708; therefore k1 = 0.01051708;

f(0.15, 0.01042934) = 0.16042934; therefore k2 = 0.0160429;
f(0.15, 0.01319225) = 0.16319225; therefore k3 = 0.016319225;
Thus

f(0.2, 0.02149) = 0.22149; therefore k4 = 0.022149.


    u    u     

Thus the value of y (at x = 0.2) = 0.0214025.
The analytical solution at x = 0.2 is y = e0.2 0.2 1 = 0.0214028, which is close to the
numerical solution.
[

 

EXAMPLE 4.2

Solve the following ordinary differential equation:

dy
dx

y
1 x

with the initial condition y(0) = 2. Determine y at x = 2.5 using the fourth-order RungeKutta
method.
Solution The initial condition is: at x = 0: y = 2. We have to determine y at x = 2.5. The result
from Program 4.1 (given in the Appendix) at step size of 0.01 is: at x = 2.5, y = 0.57.

4.2 Double Pipe Heat Exchanger

The schematic diagram of the inner pipe of the double pipe heat exchanger is shown in Fig. 4.1.
The outer pipe contains steam at temperature TS and the fluid in the inner pipe is heated.

O%2
6\  6TGH 

O%2
6\  '\  6TGH 

Heat entering through whole

circumference = U(2pRDz)(TS T)
Fig. 4.1

Schematic diagram of double pipe heat exchanger.

56

Introduction to Numerical Methods in Chemical Engineering

Consider a differential section of the inner pipe. Through the circumference of the inner pipe
heat enters from steam in the outer pipe. Under steady conditions (Input Output = 0)
O% 2 6\  6TGH   O% 2 6\  '\  6TGH   7Q & '\  65  6  
Dividing by Dz, we get

 6\
6
 O%2 \  '\
'\

 7Q &  65  6  

As Dz 0, we get
 O% 2

F6
 7Q &  65  6 
F\

(4.9)

where T is the temperature of the fluid in the inner pipe and is a function of length, TS is the
temperature of steam in the outer pipe and is constant, and O is the mass flow rate of fluid in
inner pipe. The analysis of the double pipe heat exchanger is described in the example below.
EXAMPLE 4.3 On one side of a double pipe heat exchanger is saturated steam and water
is flowing in the inner tube. The temperature of entering water is 20C and the velocity of
water is 1 m/s. The inner diameter of the inner pipe is 2.4 cm. Under steady conditions,
determine the temperature of water at the length of 5 and 10 m from the inlet. The total length
of the heat exchanger is 10 m. Assume that the temperature does not change along the radius
of the pipe. The density of water is 1000 kg/m3 and the specific heat capacity is 4184 J/kgK. The overall heat transfer coefficient based on the inside area of the inner pipe is 200 W/
m2-K and the temperature of saturated steam is 250C.
Solution

The mass flow rate of water is

O





S X#  u  u Q

 kg/s

Eq. (4.9) becomes

 u 

F6
  u  u  u    6  
F\
F6
F\

 u      6 

The initial condition is: at z = 0, T = 20. The temperature is to be determined at z = 5 and

z = 10. The differential equation is integrated using the RungeKutta fourth order method.
Program 4.1 can be modified, and with step size of 0.01 m, we get at z = 5 m, T = 28.97C
and at z = 10 m, T = 37.60C.
Let us now check the answer. The exit temperature of water at z = 10 m is 37.60C. The
heat taken up by water is equal to UADTlmtd, and from the energy balance equation we get
7 Q &. '6

NOVF

O% 2
6  6 


Initial Value Problems

57

where T1 is the temperature of the inlet water, T2 is the temperature of the exit water, and
L = 10 m. The temperatures in the double pipe heat exchanger are shown in Fig. 4.2.
250C

250C

20C

Steam temperature

37.60C
Fig. 4.2

Water temperature

Diagram for Example 4.3.

The log mean temperature difference is given by

'6

NOVF

  

NP





Substituting the values in the energy balance equation, we get

7

O% 2
6  6 
Q &. '6NOVF

 u  u 

Q u  u  u 

 W/m2-K

which is close to the given value. In this problem the overall heat transfer coefficient is given
and temperature of water is determined. Usually in heat transfer laboratory experiments, the
exit temperature of water is known and the overall heat transfer coefficient is determined.

4.3 Stirred Tank with Coil Heater

The schematic diagram of a stirred tank with coil heater is shown in Fig. 4.3.

O
M = Mass
of fluid
in tank
T
TS

Fig. 4.3

Schematic diagram of stirred tank with coil heater.

58

Introduction to Numerical Methods in Chemical Engineering

The energy balance equation is given by Accumulation = Input Output. The input is due to
energy input by the entering stream and the heat input from the steam, and the output is energy
carried away by the exit stream. From the energy balance equation, we get
F6
O% 2  6  6   3
(4.10)
FV
where T1 is the temperature of the entering stream and T is the temperature of exit stream and
is equal to temperature of water in the stirred tank. The heat transfer between the steam in the
coil and the fluid is given by Q = UADTlmtd = UA(TS T). The temperature throughout the coil
is TS as the steam is saturated, and outside the whole coil, that is inside the tank uniform
temperature, T exists as the vessel is stirred; therefore DTlmtd = TS T. Note that though the
temperature in the tank is uniform, it varies with time.
/% 2

EXAMPLE 4.4 Consider a stirred tank heater. It is a square tank 0.5 m on its sides and 2
m high and is filled with water at 20C. Water is fed to the tank at a flow rate of 1L/s and
exits out at the same flow rate from the top of the tank. The temperature of inlet water is 20C.
At time t = 0 s, water in the tank is heated by a coil containing steam whose overall heat
transfer coefficient based on the outside area of the coil is 200 W/m2-K. The outside area of
the coil through which heat exchange takes place is 1 m2. The temperature of the steam is
250C. The specific heat capacity of water is 4184 J/kg-K. After how much time is the
temperature of exit water 28C? What is the maximum temperature that can be reached in the
tank?
Solution Volume of tank = 0.5 0.5 2 = 0.5 m3. Since the density of water is 1000 kg/m3,
therefore the mass of water in the tank is 500 kg. Thus M = 500 kg, CP = 4184 J/kg-K,
3 = UA(TS T) = 200(TS T), and m = 1 kg/s, and Eq. (4.10) becomes
 u 

F6
FV

 u  u    6    u    6 

Simplifying, we get
F6
  6
FV
The initial condition is: at t = 0, T = 20C. We have to determine t at T = 28C. Program 4.1 can
be modified, and with step size of 0.1 we get T = 28C at t = 700 s. The variation of
temperature of the fluid in the tank with time is shown in Table 4.1.
Table 4.1

Variation of fluid temperature in tank with time in Example 4.4

Time (s)

Temperature (C)

500

26.81

750

28.31

1000

29.19

3000

30.46

5000

30.48

Initial Value Problems

59

F6
 ; thus
FV
the steady state temperature is given by 0.064 0.0021 T = 0 or T = 30.48C. The same is
also obtained from the numerical solution. Note the temperature at 5000 s in Table 4.1.

The steady state temperature is obtained when in the differential equation

EXAMPLE 4.5 Consider a stirred vessel which initially contains 760 kg of solvent at 25C.
12 kg/min of solvent flows into the stirred vessel at 25C and exits out also at the same rate.
At t = 0 the flow of steam is started in a coil in the stirred vessel. The heat supplied by steam
to the solvent is given by 3 = UA(TS T), where UA is the overall heat transfer coefficient
multiplied by coil area through which heat exchange takes place and TS is the temperature of
steam and is 150C. UA = 11.5 kJ/min-K. The specific heat of the solvent is Cp = 2.3 kJ/kgK. Show that
F6 Q

%U   6

FV
Determine the solvent temperature after 50 min. Also determine the maximum temperature that
can be reached in the tank.

Solution From the energy balance equation we know: Accumulation = Input Output. Here
input energy is due to incoming fluid and steam and output is due to outgoing fluid.
Substituting the values in Eq. (4.10), we get
F6 

u     6  
  6 
FV 

Note that DTlmtd = TS T, where T is the temperature of the fluid in the stirred tank. In the
coil throughout the temperature is TS and the fluid temperature is T. Simplifying the above
equation, we get
 u 

F6
   6
FV
The initial condition is: at t = 0, T = 25C. We have to determine T at t = 3000 s.
Program 4.1 can be modified, and with step size of 0.01 we get: at t = 3000 s, T = 49.69C.
The variation of temperature of the fluid in the tank with time is shown in Table 4.2.
Table 4.2

Variation of fluid temperature in tank with time in Example 4.5

Time (s)

Temperature (oC)

1000
2000
3000
5000
7500
10000
15000
20000
25000

36.41
44.27
49.69
55.98
59.43
60.78
61.53
61.64
61.66

60

Introduction to Numerical Methods in Chemical Engineering

F6
 , thus the
FV
steady state temperature is given by 0.023 0.000373T = 0 or T = 61.66C. The same is also
obtained from the numerical solution. Note the temperature at 25000 s in Table 4.2.

The steady state temperature is obtained when in the differential equation,

4.4 Pneumatic Conveying

Consider a pneumatic conveyor in which solids are inserted from the bottom along with the
flowing gas. The forces acting on the particle are: drag force acting upwards, buoyancy force
acting upwards and gravitational force acting downwards. The momentum balance equation
becomes [see Eq. (2.15)]

SR

FX R

(&  (D  (I

FV

8R

where rp is the density of the particle, vp is the upward velocity of the particle, FD is the drag
force acting on the particle, Fb is the buoyancy force acting on the particle, Fg is the
gravitational force acting on the particle, and Vp is the volume of the particle. The drag force
is given by
(& #R

%&



(4.11)
SI  XI  X R 

where rg is the density of the gas, Ap is the projected area of the particle on a plane at right
angles to the direction of motion, and vg vp is the relative velocity. The gravitational force
minus the buoyancy force on the particle is given by [see Eq. (2.17)]

(I  (D

8R  S R  S I  I

The various forces acting are shown in Figure 4.4.




S I%&

#R
X  X
X  X 
8R I R I R

(rp rg)g

vg
Fig. 4.4

Various forces (divided by volume of particle) acting on particle during pneumatic

conveying.

Initial Value Problems

61

Thus the momentum balance equation becomes

SR

FX R
FV

#R


%& SI
 XI  X R    S I  S R  I

8R

(4.12)

Note that the terms have units of force acting on the particle divided by the volume of the
particle. Dividing both sides of the equation by rp, we get
FX R
FV

SI #R


%&
 XI  X R   S I   I
R

S R 8R


The derivative
FX R

XR

FX R

FV
F\
where z is the direction along the length of the pneumatic conveyor. Thus the momentum
balance equation can be written as
XR

FX R
F\

SI #R


%&
 XI  X R   S I   I
R

S R 8R


(4.13)

Program 4.2 uses the RungeKutta fourth order method for integrating the above ordinary
differential equation and is given in the Appendix.
EXAMPLE 4.6 Determine the velocity of the solid particles of diameter 3 104 m along
the length of the pneumatic conveyor. The initial velocity of the particle is zero and superficial
velocity of air is 12 m/s. The density of the particle is 900 kg/m3. Air is fed at 25C and 1
atm and the viscosity of air under these conditions is 1.8 105 kg/m-s. Neglect wall effects.
Use the following relation to determine CD:

%&


  4G 
R
4G R

where Rep is the particle Reynolds number based on relative velocity and is given by

4G R
Solution

SI  XI  X R  F R
N

The following data are given:

dp = 3 104 m
vg = 12 m/s

= 1.8 105 kg/m-s.

The density of air under the given conditions is given by

SI

2/
46

 u  u  
 u 

 kg/m3

62

Introduction to Numerical Methods in Chemical Engineering

The projected area of the particle divided by the volume of the particle is given by

Q TR

#R


TR

 
Q TR

The particle Reynolds number is
8R

4G R

SI  XI  X R  F R
N


FR


 u  

 m

 u   X R  u  u  

   X R 

 u  

The momentum balance equation is

XR

XR

SI #R


%&
 XI  X R   S I   I


S R 8R
R

FX R

FX R
F\

F\




%&
  X R      





 FX R
 F\
Let [

%&   X R   


X  ; thus
R
F[
F\

where 4G R

   [

%&   [

and %&

 


  4G  . The initial condition is at
R
4G R

z = 0, y = 0. The problem can be solved using the RungeKutta fourth order method. The
velocity of the particle along the length of the pneumatic conveyor as obtained from
Program 4.2 is presented in Table 4.3. The step size of 0.01 m is taken.
Table 4.3

Velocity of particle as obtained from Program 4.2

z (m)

vp (m/s)

0.0
0.1
0.2
0.3
0.5
1.0
2.0
3.0
5.0
10.0

0.00
5.84
7.24
8.06
9.01
10.06
10.67
10.83
10.90
10.90

63

Initial Value Problems

4.5

Solution of Simultaneous Ordinary Differential Equations

Consider a system of two ordinary differential equations

F[
FZ

H  Z [ \ 

(4.14)

F\
H   Z  [ \ 
(4.15)
FZ
with the initial condition: at x = x0, y = y0 and z = z0. The ordinary differential equations have
to be integrated to determine the value of y and z at some x. A step size, h, is chosen in the
independent variable and after a step size in independent variable, i.e., at x = x0 + h the value
of y and z are to be computed. In the RungeKutta fourth order method the following are
computed:

M

J u H  Z  [  \ 

(4.16)

N

J u H  Z  [  \ 

(4.17)

M





J u H Z  J [  M  \  N




(4.18)

N





J u H Z  J [  M  \  N




(4.19)

M





J u H Z  J [  M  \  N




(4.20)

N





J u H Z  J [  M  \  N




(4.21)

M

J u H  Z  J [  M  \  N 

(4.22)

N

J u H  Z  J [  M  \  N 

(4.23)


 M   M   M  M 
(4.24)


\ \   N  N  N  N 
(4.25)

From the initial condition (x0, y0, z0), we have determined the value of y and z at x0 + h. Now
again, the above calculations are carried out to determine the value of y and z at x0 + 2h. But
before carrying out the next calculation the following statements are executed, due to which
the value of y1 becomes y0, z1 becomes z0 and x0 + h becomes x0:
[

[ 

x0 = x0 + h
y0 = y1
z0 = z1

64

Introduction to Numerical Methods in Chemical Engineering

EXAMPLE 4.7

Integrate the ordinary differential equations

dx
dt

x  2y

dy
dt

3x  2 y

using the RungeKutta fourth order method. The initial condition is: at t = 0, x = 6, y = 4.
Determine the values of x and y at t = 0.2. The analytical solution is given by x = 4e4t + 2et
and y = 6e4t 2et.
FZ
Z   [ and
Solution Take step size of h = Dt = 0.1. The functions are H
FV
F[
H
 Z   [ . To compute the value at t = 0.1 the starting point is t0 = 0, x0 = 6 and y0
FV
= 4. The calculations are given below.
f1(0, 6, 4) = 14; therefore k1 = 1.4;
f2(0, 6, 4) = 26; therefore l1 = 2.6;
f1(0.05, 6.7, 5.3) = 17.3; therefore k2 = 1.73;
f2(0.05, 6.7, 5.3) = 30.7; therefore l1 = 3.07;
f1(0.05, 6.865, 5.535) = 17.935; therefore k3 = 1.7935;
f2(0.05, 6.865, 5.535) = 31.665; therefore l3 = 3.1665;
f1(0.1, 7.7935, 7.1665) = 22.1265; therefore k4 = 2.21265;
Thus

f2(0.1, 7.7935, 7.1665) = 37.7135; therefore l4 = 3.77135.

Z

Z 


 M   M  M  M 




(at t = 0.1)


(at t = 0.1)
 N  N  N  N  

Now let us compute the value of y and z at t = 0.2. For this computation the starting point is
t0 = 0.1, x0 = 7.7766, and y0 = 7.140725. The calculations are given below.
[

[ 

f1(0.1, 7.7766, 7.140725) = 22.05805; therefore k1 = 2.205805;

f2(0.1, 7.7766, 7.140725) = 37.61125; therefore l1 = 3.761125;
f1(0.15, 8.8795, 9.0212875) = 26.922075; therefore k2 = 2.6922075;
f2(0.15, 8.8795, 9.0212875) = 44.681075; therefore l2 = 4.4681075;
f1(0.15, 9.12270375, 9.37477875) = 27.87226; therefore k3 = 2.787226;
f2(0.15, 9.12270375, 9.37477875) = 46.1176687; therefore l3 = 4.61176687;
f1(0.2, 10.563826, 11.75249187) = 34.06881; therefore k4 = 3.406881;
f2(0.2, 10.563826, 11.75249187) = 55.19646; therefore l4 = 5.519646.

Initial Value Problems

65

Thus at t = 0.2

    u    u    


[       u    u     

From the analytical solution at t = 0.2: x = 10.5396, y = 11.7158, which is close to the
numerical solution.
Z

 

EXAMPLE 4.8

Solve the following ordinary differential equations:

F[
FZ

F\
[
FZ
with the initial condition y(0) = 2, z(0) = 1. Determine the value of y and z at x = 3. Compare
the numerical solution with the analytical solution. The analytical solution of the given
differential equations is y = Asin(x + a) and z = Acos(x + a).

Solution

The two simultaneous ordinary differential equations can be written as

F[
\
FZ
F\
[
H
FZ
The initial condition is: at x = 0, y = 2, z = 1. We have to determine y and z at x = 3. The
result from Program 4.3 at step size of 0.01 is: at x = 3: y = 1.84, z = 1.27. Now let us check
the numerical result with the analytical solution. First let us determine the constants A and a.
At x = 0: y = 2, z = 1, and thus
H

2 = A sin(0 + a)
1 = A cos(0 + a)
Thus tan a = 2 or a = 63.435 and thus A = 2.236. From the conversion of radians to degrees
we know that 3.1416 radians = 180. Thus x = 3 = 171.887. At x = 3 the following is obtained:
y = 2.236 sin(171.887 + 63.435) = 1.84
z = 2.236 cos(171.887 + 63.435) = 1.27
which is the same as numerical solution.
EXAMPLE 4.9

Solve the following ordinary differential equation:

F [
 [Z
FZ 
with the initial conditions y(0) = 2, y(0) = 1. Determine the value of y at x = 3.

66

Introduction to Numerical Methods in Chemical Engineering

Solution

Let us take
F[
FZ

Then the given differential equation can be written as

F\
FZ

 [Z

The two simultaneous differential equations can be written as

H

H

F[
FZ

F\
FZ

 [Z

The initial condition is at x = 0, y = 2, z = 1. We have to determine y at x = 3. Program 4.3

can be modified (only the functions func1 and func2 have to be changed) and with step size
of 0.01 we get at x = 3: y = 1.90, z = 1.15.

4.6 Series of Stirred Tanks with Coil Heater

The schematic diagram of a series of stirred tanks with coil heater is shown in Fig. 4.5. The mass
in each tank shall be assumed constant as the tank volume and density of oil are assumed
constant. The energy balance of tank 1 (accumulation = Input Output) gives
F6
O% 2  6  6   7#  65  6 
FV
where M is the mass of oil in the tank and O is the flow rate of oil. T0 is the inlet temperature
/% 2

O kg/s
T0

T1

T1

Fig. 4.5

T2

T2

T3

T3

Schematic diagram of series of stirred tanks with coil heater.

Initial Value Problems

67

of the oil. T1, T2, and T3 are the temperatures of the first, second and third tank respectively.
TS is the temperature of steam. The energy balance of tank 2 gives
F6
FV
The energy balance of tank 3 gives
/%2

O%2  6  6   7#  65  6 

F6
O%2  6  6   7#  65  6 
FV
The analysis is described in the example below.
/%2

EXAMPLE 4.10 Three tanks in series are used to heat oil (see Fig. 4.5). Each tank is initially
filled with 1000 kg of oil at 20C. Saturated steam at 250C condenses within the coils
immersed in each tank. Oil is fed into the first tank at a rate of 2 kg/s and overflows into the
second and third tanks at the same flow rate. The temperature of the oil fed to the first tank
is 20C. The tanks are well mixed so that the temperature inside the tanks is uniform and the
outlet stream temperature is the temperature within the tank. Cp of oil = 2000 J/kg-K. The rate
of heat transferred to the oil from the steam is given by 3 = UA(TS T), where A is the outside
area of the coil in one tank, A = 1 m2 and the overall heat transfer coefficient is based on the
outside area of the coil, U = 200 W/m2-K. Determine the steady state temperature in all the
three tanks. What time interval is required for T3 to reach 99% of this steady state value?
Solution

UA = 200 W/K. From the first differential equation we get

 u 

F6
FV
F6
FV

 u     6       6 

  6

From the second differential equation we get

 u 

F6
FV
F6
FV

 u   6  6       6 

  6  6

From the third differential equation we get

 u 

F6
FV
F6
FV

 u   6  6       6 

  6  6

The initial condition is: at t = 0: T1 = T2 = T3 = 20C. Program 4.4 for the solution of above

68

Introduction to Numerical Methods in Chemical Engineering

three ordinary differential equations by the RungeKutta fourth order method is given in the
Appendix. The results at step size of 0.1 is shown in Table 4.4.
Table 4.4

Results in Example 4.10.

Time (s)

T1 (oC)

T2 (oC)

T3 (oC)

1000
2500
7500
15000

29.61
30.89
30.95
30.95

36.08
40.98
41.38
41.38

39.56
49.87
51.31
51.31

The steady state temperature is obtained when in the differential equation

steady state temperatures are given by
6




6

 u   



F6
FV

 ; thus the

 C

 C

 u   

 C

The same steady state temperatures are also obtained from the numerical solution. Note
the temperature at 7500 s in Table 4.4. We are required to determine the time required
for temperature in tank 3 to reach 0.99 51.31 = 50.80C. From Program 4.4 this time
is 3150 s.
6

4.7 Initial Value Problems in Chemical Reaction Engineering

Batch and plug flow reactors are initial value problems. The initial conditions and ordinary
differential equations for batch and plug flow reactors are shown in Table 4.5.
Table 4.5
Initial
Condition for
Batch Reactor

Initial conditions and ODEs for batch and plug flow reactors

ODEs for Batch Reactor

Initial
Condition for
Plug Flow
Reactor

ODEs for Plug Flow

Reactor

#V Z

# o $

#V V



%#

%$

F% #
FV
F%$
FV

 M% #



%#

M% #

%$

F% #
FZ
F% $
W
FZ

 M% #
M% #

Initial Value Problems

Table 4.5

69

(Cont.)

M
M
#  $  %
o
o

#V V



%#

%$

%%

M
#  $  %
o
M
o
$  %  &

F% #
FV
F%$
FV
F%%
FV

#V Z

M% #



%#

%$

M% #  M%$

%%

F% #
FZ
F%$
W
FZ
F%%
W
FZ
W

M%$

 M% #
M% #  M% $
M% $

#V V



%#

%$

%%

%&

F% #
FV
F%$
FV
F%%
FV
F%&
FV

#V Z

M% #% $
M% #% $  M% $%%

F% #
FZ
F% $
W
FZ
F%%
W
FZ
F% &
W
FZ
W



%#

%$

%%

%&

M% #%$  M%$%%

M%$%%

 M% #%$
 M% #%$  M%$%%
M% #% $  M% $%%
M% $%%

4.8 Batch and Stirred Tank Reactors

The solution of initial value problems in batch and stirred tank reactors is described with the
examples given below.
EXAMPLE 4.11 Consider a reaction A B carried out in a batch reactor. The differential
equation for species A is
F% #
 M% #
FV
The initial condition is: at t = 0, CA = 1 mol/m3. The rate constant of the reaction is 1 s1. Using
the RungeKutta fourth order method, determine the concentration of A at 3 s.
Solution The differential equation is written in the form f = kCA. Thereafter the following
are computed:
M J u H  V  % 
M




J u H V  J %  M



M




J u H V   J %   M 



70

Introduction to Numerical Methods in Chemical Engineering

M

J u H  V  J %  M 

%

% 

V

V  J


 M  M  M  M 


%  %
Program 4.1 can be modified and the results for step size of 0.01 s are presented in Table 4.6.
Table 4.6

Results in Example 4.11

t (s)

CA (mol/m3)
Numerical solution

CA (mol/m3) = et
Analytical solution

0.0
1.0
2.0
3.0
5.0
10.0

1.000000
0.367880
0.135335
0.049787
0.006738
0.000045

1.000000
0.367879
0.135335
0.049787
0.006738
0.000045

EXAMPLE 4.12 A liquid phase reaction A B is carried out in a stirred vessel reactor. Feed
enters the reactor at a rate of F = 1 L/s and exits out also at the same flow rate. Both the
reactant and product have the same density. The concentration of reactant in the feed is CA0
= 1 mol/m3. The volume of the tank is V = 10 L and the concentration of A of the solution
in the tank is 1 mol/m3. The vessel may be considered perfectly mixed, so that the
concentration of A in the product stream equals that inside the tank. The rate of consumption
of A equals kCA, where k = 1 s1. Determine the concentration of A at various time periods from
0 to 10 s.
Solution

Mole balance on component A is given by

Accumulation = Input Output Consumption
Moles of A in the reactor = VCA
F 8% # 
Accumulation =
FV
Input = FCA0
Output = FCA
Thus from the mole balance of component A, we get
F 8% # 
(% #   (% #  M% #8
FV
Substituting the values we get
F % # 

  % #  % #
FV
F% #
  % #
FV

Initial Value Problems

71

The initial condition is: at t = 0, CA = 1 mol/m3. Program 4.1 can be modified and at step size
of 0.01 the concentration of component A in the tank with time is shown in Table 4.7.
Table 4.7

Results in Example 4.12

CA (mol/m3)

Time (s)
0.10
0.25
0.50
1.0
2.0
3.0
5.0
10.0

0.9053
0.7891
0.6212
0.3969
0.1927
0.1248
0.0947
0.0909

F% #

 ; thus % #
 mol/m3. The same is also obtained from
FV

numerical solution. Note the concentration at 10 s in the Table 4.7.

At steady state,

M
M
EXAMPLE 4.13 Consider reaction #  $  % carried out in a batch reactor. The
o
o
differential equation for component A is

F% #
FV

for component B
for component C

F% $
FV

 M% #

M% #  M %$

F%%
FV

M % $

The initial condition is: at t = 0, CA = 1 mol/m3, CB = 0 mol/m3, and CC = 0 mol/m3. The rate
constants are k1 = 1 s1 and k2 = 1 s1. Using the RungeKutta fourth order method, determine
the concentration of A, B, and C up to 10 s.
Solution

The differential equations are written in the form of functions

H

 M #

H

M #  M $

H

M $

where A, B and C are the concentrations of the components A, B, and C, respectively. The
initial condition is at time t = t0, A = A0, B = B0, C = C0. Thereafter the concentrations are
computed at time t = t0 + h.

72

Introduction to Numerical Methods in Chemical Engineering

M
N
O
M
N
O
M
N
O

J u H  V  #  $  % 
J u H   V  #  $  % 
J u H  V  #  $  % 






J u H V  J #  M  $  N  %  O










J u H  V  J #  M  $  N  %  O










J u H V  J #  M  $  N  %  O










J u H V  J #  M  $  N  %  O










J u H  V  J #  M  $  N  %  O










J u H V  J #  M  $  N  %  O





M
N
O

J u H  V  J #  M  $  N  %  O 

J u H  V  J #  M  $  N  %  O 
J u H  V  J #  M  $  N  %  O 
#

# 


 M  M  M  M 


$

$ 


 N  N  N  N 


%

% 


 O  O  O  O 


t 0 = t0 + h
A0 = A1
B0 = B1
C0 = C1
Program 4.5 for the solution of the above three simultaneous ordinary differential equations by
the RungeKutta fourth order method is given in the Appendix. The results for step size of 0.01
s are presented in Table 4.8.

Initial Value Problems

Table 4.8

73

Results in Example 4.13

t (s)

CA (mol/m3)

CB (mol/m3)

CC (mol/m3)

0.0
1.0
2.0
3.0
4.0
5.0
10.0

1.000000
0.367880
0.135335
0.049787
0.018316
0.006738
0.000045

0.000000
0.367879
0.270671
0.149361
0.073263
0.033690
0.000454

0.000000
0.264241
0.593994
0.800852
0.908422
0.959573
0.999503

EXAMPLE 4.14

Consider the following two reactions taking place in a batch reactor:

M
#  $  %
o
M
$  %  &
o

The concentration of various species with time are given by the following differential
equations:
for component A

for component C
for component D

 M% #%$

F% $
FV

 M% #% $  M% $%%

F%%
FV

M% #%$  M%$%%

F% &
FV

for component B

F% #
FV

M% $%%

The initial conditions are: at t = 0, CA = 1 mol/m3, CB = 1 mol/m3, CC = 0 mol/m3, and CD

= 0 mol/m3. The rate constant of the reactions are k1 = k2 = 1 m3/mol-s. Using the RungeKutta
fourth order method determine the concentration of species A, B, C, and D up to 10 s.
Solution Program 4.6 for solution of the above four simultaneous ordinary differential
equations by the RungeKutta fourth order method is given in the Appendix. The results for
step size of 0.01 s are presented in Table 4.9.

74

Introduction to Numerical Methods in Chemical Engineering

Table 4.9

Results in Example 4.14

t (s)

CA (mol/m3)

CB (mol/m3)

CC (mol/m3)

CD (mol/m3)

0.0
1.0
2.0
3.0
4.0
5.0
10.0

1.000000
0.528875
0.404510
0.357692
0.337090
0.327357
0.318152

1.000000
0.394646
0.175134
0.083121
0.040733
0.020275
0.000659

0.000000
0.336895
0.366113
0.367737
0.366553
0.365561
0.364356

0.000000
0.134230
0.229376
0.274571
0.296357
0.307082
0.317492

4.9 Plug Flow Reactor

The solution of initial value problems in plug flow reactor is described with examples given
below.
EXAMPLE 4.15 Consider a reaction A B carried out in a plug flow reactor. The
differential equation for species A along the length of the plug flow reactor of length 10 m is
F% #
 M% #
FZ
The initial condition is: at x = 0 (inlet), CA = 1 mol/m3.
A fluid medium comprising initially only A flows through the reactor with a mean axial
velocity u = 1 m/s. The rate constant of the reaction is 1 s1. Using the RungeKutta fourth
order method, determine the concentration of A along the length of the plug flow reactor up
to 10 m.
W

Solution Program 4.1 can be modified and the results for step size of 0.01 m are presented
in Table 4.10.
Table 4.10

Results in Example 4.15

x (m)

CA (mol/m3)

0.0
1.0
2.0
3.0
5.0
10.0

1.000000
0.367880
0.135335
0.049787
0.006738
0.000045

M
M
EXAMPLE 4.16 Consider a reaction #  $  % carried out in a plug flow reactor.
o
o
The differential equation for component A is

F% #
FZ

 M% #

Initial Value Problems

75

for component B
W

F%$
FZ

M% #  M% $

F%%
FZ

M% $

for component C

The initial condition is: at x = 0 (inlet), CA = 1 mol/m3, CB = 0 mol/m3, and CC = 0 mol/m3.

A fluid medium comprising initially only A flows through the reactor with a mean axial
velocity u = 1 m/s. The rate constants are: k1 = 1 s1 and k2 = 1 s1. Using the RungeKutta
fourth order method, determine the concentration of A, B, and C along the length of the plug
flow reactor up to 10 m.
Solution Program 4.5 can be modified (time replaced by distance along the length of the
tubular reactor) and the results for step size of 0.01 m are presented in Table 4.11.
Table 4.11

Results in Example 4.16

x (m)

CA (mol/m3)

CB (mol/m3)

CC (mol/m3)

0.0
1.0
2.0
3.0
4.0
5.0
10.0

1.000000
0.371577
0.136695
0.050287
0.018500
0.006806
0.000046

0.000000
0.367861
0.272024
0.150359
0.073814
0.033960
0.000458

0.000000
0.260562
0.591281
0.799353
0.907686
0.959234
0.999496

EXAMPLE 4.17

Consider the following two reactions taking place in a plug flow reactor:
M
#  $  %
o

M
$  %  &
o
The concentration of various species with the length of the reactor are given by the following
differential equations:
for component A
F%
W #  M% #% $
FZ
for component B
F%
W $  M% #%$  M%$%%
FZ
for component C
F%
W % M% #%$  M%$%%
FZ
for component D
F%
W & M  % $ %%
FZ

76

Introduction to Numerical Methods in Chemical Engineering

The initial conditions are: at x = 0 (inlet), CA = 1 mol/m3, CB = 1 mol/m3, CC = 0 mol/m3, and

CD = 0 mol/m3.
The length of the plug flow reactor is 10 m. A fluid medium comprising initially only
A and B flows through the reactor with a mean axial velocity u = 1 m/s. The rate constant of
the reactions are k1 = k2 = 1 m3/mol-s. Using the RungeKutta fourth order method, determine
the concentration of species A, B, C, and D along the length of the plug flow reactor up to 10
m.
Solution Substituting k1 = k2 = 1 m3/mol-s and u = 1 m/s in the above ordinary differential
equations, we get
F% #
FZ

 % #% $

F% $
FZ

 % #% $  % $%%

F%%
FZ

% #%$  %$%%

F% &
FZ

% $ %%

Program 4.6 can be modified (time replaced by distance along the length of the tubular reactor)
and the results for step size of 0.01 m are presented in Table 4.12.
Table 4.12
x (m)
0.0
1.0
2.0
3.0
4.0
5.0
10.0

Results in Example 4.17

CA (mol/m3)

CB (mol/m3)

CC (mol/m3)

CD (mol/m3)

1.000000
0.528875
0.404510
0.357692
0.337090
0.327357
0.318152

1.000000
0.394646
0.175134
0.083121
0.040733
0.020275
0.000659

0.000000
0.336895
0.366113
0.367737
0.366553
0.365561
0.364356

0.000000
0.134230
0.229376
0.274571
0.296357
0.307082
0.317492

4.10 Nonisothermal Plug Flow Reactor

EXAMPLE 4.18 Consider the reaction A B carried out in a steam heated heat exchanger
reactor. Reactant A is fed at the rate of 1.26 kg/s per tube. The feed consisting of pure A enters
the reactor at a temperature of 21C. It is desired to determine the height of reactor required
for 90% conversion of A. The internal diameter of the reactor tubes may be taken as 2.54 cm.
Steam at 388.71 K is available for heating purposes. The rate constant of the first order

Initial Value Problems

77


 Z GZR 
, where T is in Kelvin. Take the following
46

parameters: R = 8.314 J/mol-K, r = 980.9 kg/m3, molecular weight of reacting stream,

M = 200 g/mol, heat transfer coefficient based on inside area of reactor tube, U = 1900 W/

m2-K, Cp = 15.7 J/kg-K, '* TZP = 92.9 kJ/mol. Assume the heat of reaction to be independent
of temperature.

MP# MP#
Solution Since the reaction is first order, M% #
  :  , where F is the volumetric
(
(

flow rate of reactant A and P# is the inlet molar flow rate of A. The rate constant of the reaction
can be written as

reaction is given by M


M GZR D  
G

M
where D

'
, G
46

6
and M
6

 u  GZR  D  .

T1 is a reference temperature and is taken to be the temperature of steam.



T#

FP#
F8

F:
F8


P# F:
# F\


M GZR D     : 
G

(

T#
P
#

F:
F8


P#

From energy balance on reactants we get

O% 2

F6
 T# #'*   S
F\
TZP

where q = Ua(TS T) and a is the total area of heat transfer per unit length; thus a = pD (for
one tube). A is the cross-sectional area of the tube based on inside diameter. Thus the above
equation becomes
 O% 2

F6 7

65  6   T# '* 
F8
&

TZP

( 

D
M

'
46

MI  O 
U  MI

 u  


 u 

O
U



 u  GZR  D   u  GZR     S1

78

Introduction to Numerical Methods in Chemical Engineering

F:
F\


#M   :  GZR   
G

#M
(



Q


  u 

 m1

Thus

   :  GZR    

6

F:
F\
O% 2



MI
,

U
MI  -



9
-

a, A and U are all based on the internal diameter of tubes. The inlet molar flow rate of A is
given by
P
#



MI OQN
U MI

 O% 2

T#

T#



OQN
U

F6
7

65  6   T# '* 
#F\
&

TZP



Q   


M P GZR D     : 
#
G

(

F6  u 

65  6   T# '* 
F\


TZP

 u GZR       : 

6


 u 

   :  GZR    

6


T# '* TZP

 u    :  GZR    

6

 u     :  GZR    

6

Thus the energy balance equation becomes


T# '* TZP



6
F6

   65  6    u     :  GZR    

F\
6

Initial Value Problems

79

Thus the two simultaneous ordinary differential equations are

F:
F\



   :  GZR   



    6      :  GZR   

The initial condition is: at z = 0, X = 0 and T = 294.15 K.

F6
F\

Program 4.7 for the solution of the above two simultaneous ordinary differential equations by
Runge-Kutta fourth order method is given in the Appendix. The results for step size of 0.1 m
are presented in Table 4.13.
Table 4.13
z (m)
0.1
0.2
0.3
0.4
0.5
1.0
2.0
3.0
5.0
10
15
20
25
30
35
40
45
50
100
150
200
250
300
350

Results in Example 4.18

X

0.000026
0.000363
0.00094
0.0015
0.0015
0.005
0.011
0.017
0.029
0.059
0.088
0.118
0.147
0.176
0.204
0.232
0.260
0.287
0.542
0.752
0.903
0.980
0.998
0.999

343.87
359.29
361.51
362.69
362.69
364.87
365.35
365.40
365.49
365.71
365.93
366.16
366.40
366.64
366.89
367.14
367.39
367.66
370.65
374.56
379.76
385.59
388.33
388.68

Thus 90% conversion is achieved at a height of 200 m.

80

Introduction to Numerical Methods in Chemical Engineering

Exercises
4.1

Integrate the following ODEs using the RungeKutta fourth order method:
FZ
FV

  Z   [

F[
FV

 Z  [  Z\

F\
 \  Z[
FV
Initial condition at t = 0: x = y = z = 5. Determine x(20),

(Ans: x(20) = 6.76,

4.2

y(20) = 12.61,

y(20),

z(20).

z(20) = 10.96)

Consider the second order ordinary differential equation

F Z
FZ

 Z 

FV
FV
FZ
with the initial conditions x(0) = 3 and
     . Compute x(5).
FV
F[
FZ
  Z   [ . The two
[ and thus the given ODE becomes
Hint: Take
FV
FV
simultaneous differential equations can be solved using the Runge-Kutta fourth
order method by taking the following functions.
H

FZ
FV

F[
 Z   [
FV
Initial condition at t = 0: x = 3 and y = 5. Note that since the ordinary differential
equation is second order, therefore two conditions have to be given to completely
define the problem.
H

(Ans: x(5) = 4.9 106)

4.3

Consider the second order ordinary differential equation

F[
F[
 Z
  [ 

FZ
FZ
F[
with the initial conditions y(0) = 1 and
    . Compute y(1).
FZ
F[
F\ Z  \   [ 
Hint: Take
. The two
\ and thus the given ODE becomes
FZ
FZ

simultaneous differential equations can be solved using the RungeKutta fourth
order method by taking the following functions:


Initial Value Problems

81

F[
\
FZ
F\ Z  \   [ 
H

FZ
Initial condition at x = 0: y = 1 and z = 0.
( Ans: y(1) = 0.8785)
H

4.4

Determine the velocity of the solid particles of diameter 0.0003 m in a pneumatic

conveyor at length of 10 m. The initial velocity of the particle is zero and
superficial velocity of air is 10 m/s. The density of the particle is 900 kg/m3. Air
is fed at 25C and 1 atm and the viscosity of air under these conditions is 1.8 105 kg/
m-s. Neglect the wall effects. Use the following relation to determine CD:

   4G 
%&
R
4G R
where Re p is the particle Reynolds number based on relative velocity and is given

by 4G R
(Ans:
4.5

S I  XI  X R  F R
.
N

8.9044 m/s)

Consider a reaction A B carried out in a batch reactor. The differential equation

for species A is
F% #
 M% #
FV
The initial condition is: at t = 0, CA = 1 mol/m3. The rate constant of the reaction
is 0.1 s1. Using the RungeKutta fourth order method, determine the concentration
of A at 10 s.

(Ans:

0.36788 mol/m3)

4.6

Solve Exercise 4.5 for rate constant of the reaction of 0.01 s1.
(Ans: 0.904838 mol/m3)

4.7

Consider a reaction A B carried out in a plug flow reactor. The differential

equation for species A is

F% #
F\

 M% #

The initial condition is: at z = 0, CA = 1 mol/m3. The rate constant of the reaction
is 0.1 s1. Using RungeKutta fourth order method, determine the concentration of
A at 5 m from entrance. Take u = 1 m/s.
(Ans:
4.8

0.606531 mol/m3)

Solve Exercise 4.7 for rate constant of the reaction of 0.01 s1.
(Ans:

0.95123 mol/m3)

82

Introduction to Numerical Methods in Chemical Engineering

4.9

M
M
Consider reaction #  $  % carried out in a batch reactor. The differential
o
o
equation for component A is
F% #
 M% #
FV
for component B
F% $
M% #  M %$
FV
for component C
F%%
M % $
FV

The initial condition is: at t = 0, CA = 1 mol/m3, CB = 0 mol/m3, and CC = 0 mol/m3. The

rate constants are: k1 = 1 s1 and k2 = 0.1 s1. Using the RungeKutta fourth order
method, determine the concentration of A, B, and C at 10 s.
(Ans: CA = 4.54 105 mol/m3, CB = 0.408704 mol/m3, CC = 0.59125 mol/m3)
4.10 Solve Exercise 4.9 for the following rate constants: k1 = 0.1 s1 and k2 = 1 s1.
(Ans: CA = 0.3679 mol/m3, CB = 0.0409 mol/m3, CC = 0.5912 mol/m3)
M
M
4.11 Consider reaction #  $  % carried out in a plug flow reactor. The
o
o
differential equation for component A is

F% #
FZ

 M% #

F%$
FZ

M% #  M% $

for component B

for component C

F%%
M % $
FZ
The initial condition is: at x = 0, CA = 1 mol/m3, CB = 0 mol/m3, and CC = 0 mol/
m3. The rate constants are: k1 = 1 s1 and k2 = 0.1 s1. Using the RungeKutta fourth
order method, determine the concentration of A, B, and C at 5 m from entrance.
W

(Ans: CA = 0.006738 mol/m3, CB = 0.6664 mol/m3, CC = 0.3268 mol/m3)

4.12 Solve Exercise 4.11 for the following rate constants: k1 = 0.1 s1 and k2 = 1 s1.
(Ans: CA = 0.6065 mol/m3, CB = 0.0666 mol/m3, CC = 0.3268 mol/m3)
4.13 Consider the following two reactions taking place in a batch reactor:
M
#  $  %
o
M
$  %  &
o

Initial Value Problems

83

The concentration of various species with time are given by the following
differential equations:
for component A
F% #
FV
F% $
FV

for component D

M% #%$  M%$ %%

F% &
FV

for component C

 M% #% $  M% $%%

F%%
FV

for component B

 M% #%$

M  % $ %%

The initial conditions are: at t = 0, CA = 1 mol/m3, CB = 1 mol/m3, CC = 0 mol/m3,

and CD = 0 mol/m3. The rate constant of the reactions are k1 = 1 m3/mol-s and
k2 = 0.1 m3/mol-s. Using the RungeKutta fourth order method, determine the
concentration of species A, B, C, and D at 10 s.
(Ans: CA = 0.1392 mol/m3, CB = 0.0361 mol/m3, CC = 0.7576 mol/m3,
CD = 0.1032 mol/m3)
4.14 Solve Exercise 4.13 for the following rate constants: k1 = 0.1 m3/mol-s and
k2 = 1 m3/mol-s.
(Ans: CA = 0.5899 mol/m3, CB = 0.2447 mol/m3, CC = 0.0650 mol/m3,
CD = 0.3452 mol/m3)
4.15 Consider the following two reactions taking place in a plug flow reactor:
M
#  $  %
o
M
$  %  &
o
The concentration of various species are given by the following differential
equations:

for component A
W

F% #
FZ

 M% #% $

F% $
FZ

 M% #%$  M%$%%

F%%
FZ

M% #%$  M%$%%

for component B

for component C

84

Introduction to Numerical Methods in Chemical Engineering

for component D
W

F%&
FZ

M  % $ %%

The initial conditions are: at x = 0 (inlet), CA = 1 mol/m3, CB = 1 mol/m3,

CC = 0 mol/m3, and CD = 0 mol/m3. The rate constant of the reactions are
k1 = 1 m3/mol-s and k2 = 0.1 m3/mol-s. Using the RungeKutta fourth order method,
determine the concentration of species A, B, C, and D at 5 m from the entrance.
(Ans: CA = 0.1949 mol/m3, CB = 0.1168 mol/m3, CC = 0.7269 mol/m3,
CD = 0.0781 mol/m3)
4.16 Solve Exercise 4.15 for the following rate constants: k1 = 0.1 m3/mol-s and
k2 = 1 m3/mol-s.
(Ans: CA = 0.7009 mol/m3, CB = 0.4764 mol/m3, CC = 0.0747 mol/m3,
CD = 0.2244 mol/m3)

Chapter 5

Boundary Value Problems

The application of finite difference method for the numerical solution of boundary value
problems in ordinary differential equations is discussed in this chapter with various examples.
One-dimensional steady heat conduction, steady heat conduction in a fin, and chemical
reaction and diffusion in a pore are also discussed in this chapter. The discretization of the
convection term is discussed in the next chapter.

5.1 Discretization in One-Dimensional Space

The basic idea of finite difference methods is that the derivatives in differential equations are
written in terms of discrete quantities of dependent and independent variables, resulting in
simultaneous algebraic equations with all unknowns prescribed at discrete nodal points.
Consider a function y(x) and its derivatives at point x. y(x + Dx) can be expanded in Taylor
series about y(x) as follows:
[  Z  'Z 

[  Z   'Z

F[
'Z  F  [
'Z  F  [


"

 FZ Z
 FZ  Z
FZ Z

(5.1)

Simplifying, we get
[  Z  'Z   [  Z 

'Z F  [
F[

"
FZ Z  FZ  Z

'Z

Thus

F[
FZ

[  Z  'Z   [  Z 
'Z

 1  'Z 

F[
is of first order in Dx, indicating that the truncation error O(Dx) goes to
FZ Z
zero like the first power in Dx. That is why we write the derivative at point x as

The derivative

F[
FZ

NKO

[  Z  'Z   [  Z 
'Z

'Z 

Consider a one-dimensional body as shown in Fig. 5.1.

85

86

Introduction to Numerical Methods in Chemical Engineering

i 2

i 1

i
Fig. 5.1

i+1

i+2

One-dimensional body.

We may write y in Taylor series at i + 1 and i 1 as

[ 
K

[  'Z
K

F[
'Z  F  [
'Z  F  [
'Z  F  [



"
 FZ 
 FZ 
 FZ 
FZ

(5.2a)

F[
'Z  F  [
'Z  F  [
'Z  F  [



"
 FZ 
 FZ 
 FZ 
FZ

(5.2b)

[ 
K

[  'Z
K

From Eq. (5.2a), we get the forward difference approximation of

F[
FZ

F[
at node i as
FZ

[   [
 1  'Z 
'Z
K

(5.3)

and from Eq. (5.2b) we get the backward difference approximation of

F[
FZ

[  [ 
 1  'Z 
'Z
K

F[
at node i as
FZ

(5.4)

F[
at
Subtracting Eq. (5.2b) from Eq. (5.2a), we get the central difference approximation of
FZ
node i as

F[
FZ

[   [ 
 1 'Z 
 'Z
K

(5.5)

It is seen that the truncation errors for the forward difference and backward differences are first
order, whereas the central difference yields a second order truncation error. Adding the two
F[
at node i
equations, we get the central difference approximation of
FZ 
F[
FZ 

[    [  [ 
 1 'Z 

'Z
K

(5.6)

It should be noted that these finite difference approximations are only valid to some order of
Dx. The error in the approximations is called the truncation error. It is possible to get
approximations which are valid to higher order by using more grid points in the
approximations. But for our purposes the approximations given above will be sufficient.
A numerical scheme is called consistent if the finite difference approximations have a
truncation error that approaches zero in the limit that Dx 0, Dt 0.
Even if the numerical scheme is consistent, we are still not guaranteed that iterating the
numerical scheme will give a good approximation to the true solution of the differential
equation. A numerical scheme is called convergent if the solution of the discretized equations
approaches the exact solution of the differential equation in the limit that Dx 0, Dt 0.

Boundary Value Problems

87

For linear equations the issue of convergence is intimately related to the issue of stability
of the numerical scheme. A scheme is called stable if it does not magnify errors that arise in
the course of the calculation.
As Dx and Dt are made smaller, the truncation error of approximating the derivatives by
finite differences decreases. However, for smaller sizes, more computations need to be done
to get solutions for the same domain and total time, which leads to increased round-off errors.
The total error as a function of these sizes is shown in Fig. 5.2. Here it is assumed that the
solution is calculated on the same domain and for the same total time.
Error

Total error
Truncation
error

Round-off
error

Grid size
Fig. 5.2

Errors as function of grid size for finite difference calculation.

For a second order differential equation, two boundary conditions have to be specified and thus
the problem is called the two-point boundary value problem. There are three types of boundary
conditions: Dirichlet, Neumann and mixed. Dirichlet boundary condition is the one in which
the variable is defined such as y = 0 and Neumann boundary condition is the one in which the
F[
 . Mixed
gradient of the variable is defined perpendicular to the surface such as
FP
boundary condition is the one which is a combination of Dirichlet and Neumann, such as
F6
M
J  6  6f  . A well-posed problem is the one which has a unique solution.
FZ
EXAMPLE 5.1 Using finite difference method, solve the second order one dimensional
linear differential equation
F[

FZ 
with the Dirichlet boundary conditions

(0 < x < 1)

at x = 0: y

at x = 1: y

88

Introduction to Numerical Methods in Chemical Engineering

Compute the value of y at x = 0.5. Make two parts (see Fig. 5.3). The exact solution is
y = x2 x.

Fig. 5.3

Solution

Example 5.1.

The central difference in space gives

[    [  [ 
'Z 
K

Substituting i = 2, we get

[   [  [

'Z 
Since two parts are made, therefore Dx = 0.5. It is given that y1 = 0 and y3 = 0 and we get
[


, which is the same as the exact solution.


EXAMPLE 5.2 Using the finite difference method, solve the second order one dimensional
linear differential equation
F[
 
FZ 
with the following boundary conditions:
At x = 0: y

(0 < x < 1)

Dirichlet boundary condition

F[
Neumann boundary condition

FZ
Compute the value of y at x = 0.5. Make two parts (see Fig. 5.4).

At x = 1:

Solution

2
Fig. 5.4

The central difference in space gives

[    [  [ 
'Z 
K

At node 2

3
Example 5.2.

[   [  [
'Z 




Boundary Value Problems

Since y1 = 0, we get

 'Z 

[   [

At node 3

89

[   [  [

'Z 
where node 4 is a hypothetical node. From the boundary condition at node 3, we get
[  [

 'Z
thus y4 = y2 + 2Dx. Therefore
 'Z   [   [

'Z 
Thus
'Z  [  [

'Z 

Solving the equations for nodes 2 and 3, we get [  and y3 = 0.

EXAMPLE 5.3 Using finite difference method, solve the differential equation with the
source term f(x)
F[
(0 < x < 1)
 [ H  Z 
FZ 
f(x) = 4x2 2x 4
with the Dirichlet boundary conditions
At x = 0: y

At x = 1: y 1
The total length is 1 m. Make 3 parts (see Fig. 5.5). The exact solution is y = 2x2 + x.

Solution

2
Fig. 5.5

3
Example 5.3.

The central difference in space gives

[    [  [ 
 [
'Z 
K

At node 2

[   [  [
  [
'Z 

H

90

Introduction to Numerical Methods in Chemical Engineering

[   [  

  [




  [   [    [







At node 3
[   [  [






    


  [

     [  [    [







Solving the equations for nodes 2 and 3, we get y2 = 0.111 and y3 = 0.222.
EXAMPLE 5.4 Using finite difference method, solve the differential equation with the
source term f(x)
F[
 [
FZ 

H Z

H Z
subject to the boundary conditions

(0 < x < 1)

Z  Z  

At x = 0: y = 0

F[

FZ
The total length is 1 m. Make 3 parts (see Fig. 5.6). The exact solution is y = 2x2 + x.

At x = 1:

3
Fig. 5.6

Solution

Example 5.4.

The central difference in space gives

[    [  [ 
 [
'Z 
K

At node 2

[   [  [
  [
'Z 

[   [  



  [

H




Boundary Value Problems

  [   [    [




At node 3
[   [  [






    


  [

  [   [  [    [

At node 4

[   [  [



  [

91









  [   [  [    [



where node 5 is a hypothetical node. From the boundary condition at node 4, we get
[  [
  , therefore y 5 y 3  2 and the equation for node 4 becomes
 'Z
   [   [      [  
Thus the equation of node 2 is
 [   [

Thus the equation of node 3 is

 [   [   [





Thus the equation of node 4 is

 [   [






The equation can be written as


 [

 
 [


  [

Solving using TDMA, we get [

EXAMPLE 5.5

F[
 
FZ


, [


  
 




, y4 = 1.


Solve the boundary value problem

F [
[
FZ 
 and y(1) = 1. Take Dx = 0.1 m. Compare the results with the analytical solution
[

EQUJ Z
EQUJ

92

Introduction to Numerical Methods in Chemical Engineering

Solution

The schematic diagram is shown in Fig. 5.7.

F[
FZ

y =1

6
Fig. 5.7

11

Example 5.5.

Discretizing the given differential equation at node i using the central difference scheme,
we get

[    [  [ 
'Z 
K

[     'Z  [  [ 
K

Since Dx = 0.1, therefore Dx2 = 0.01 and the above equation becomes
[   [  [ 
K

At node 1

[  [  [

Also at node 1,

At node 2
At node 10

F[
FZ

 , thus

[  [
 'Z

 , thus y0 = y2 and we get at node 1

2.01y1 + 2y2 = 0
y1 2.01y2 + y3 = 0
y9 2.01y10 + y11 = 0

Since y11 = 1, the above equation becomes

y9 2.01y10 = 1
Thus the unknowns are y1 to y10. The tridiagonal set of 10 equations becomes


[

[
  


 


 
 [

  [










93

Boundary Value Problems

The solution can be obtained by modifying the parameters ai (i = 2 to N), bi (i = 1 to N) and

ci (i = 1 to N 1) in Program 1.1 given in the Appendix. The numerical and analytical solution
at nodes 1 to 10 are shown in Table 5.1.
Table 5.1

Numerical and analytical solutions at nodes 1 to 10 for Example 5.5

Node

x (m)

Numerical y

Analytical y

0.0
0.1
0.2
0.3
0.5
0.8
0.9

1
2
3
4
6
9
10

0.6482
0.6515
0.6612
0.6776
0.7309
0.8668
0.9287

0.6481
0.6513
0.6611
0.6774
0.7308
0.8667
0.9287

5.2 One-Dimensional Steady Heat Conduction

The steady heat conduction in one dimension is described with examples given below.
EXAMPLE 5.6 Consider 1-dimensional steady state conduction without heat generation
taking place in a rectangular slab. The temperature of the left side of the slab is 100C and
of the right side is 200C. The length of the slab is 10 cm and the thermal conductivity of the
F 6
slab is 120 W/cm-K. Make nine uniform divisions. The governing equation is M  
FZ
Solution

Let us make nine uniform divisions as shown in Fig. 5.8.

Fig. 5.8

10

Example 5.6.

Dx = 1.111, T1 = 100C, T10 = 200C. Using the central difference scheme, we get

6   6   6
'Z 

6   6  6 

The equation for node 2 is

2T2 T3 = 100
Similar equations can be written for all the nodes and the following set of eight linear algebraic
equations is obtained. The equations can be written in tridiagonal form as

94

Introduction to Numerical Methods in Chemical Engineering

 
6
  
6

6
  

  

6

6
  


  

6

   6

  6












The solution can be obtained by modifying the parameters ai (i = 2 to N), bi (i = 1 to N) and

ci (i = 1 to N 1) in Program 1.1 given in the Appendix. Using TDMA the following solution
is obtained:
6 
6

 
6 

6 
6 

6 
6 


6 

EXAMPLE 5.7 A fin of diameter 0.02 m and length 0.05 m is attached to a wall. The
temperature of the wall is 320C. Determine the temperature of the fin at x = 0.0125, 0.025,
0.0375 and 0.05 m using the finite difference technique taking four parts. The thermal
conductivity of the rod is 50 W/m-K and the convective heat transfer coefficient from the rod
to the surroundings is 100 W/m2-K. The temperature of the surroundings is 20C. The
F R J2
governing differential equation is   
R  , where q = T Tsurr and the boundary
M#
FZ
FR J
condition at x = 0.05 m is
 R .
FZ M
The schematic diagram of the fin is shown in Fig. 5.9.

Wall at 320C

Solution

x =0

0.0125

0.025

0.0375

q0 = 300
Fig. 5.9

Steady state heat transfer in fin.

x = 0.05 m

Boundary Value Problems

J2
.
M#

Let O

From the discretization of the differential equation 

F R J2

R
FZ  M#

R  R  R 

 
OR
'Z 

95

 , we get

Simplifying, we get

R      O'Z  R  R 

(for i = 1, 2, 3, 4)

Let D = 2 + (mDx)2. Therefore the above equation becomes

qi1 + Dqi qi+1 = 0
Applying the above equation to node 1, we get
q0 + Dq1 q2 = 0
Since q0 = 300 the above equation becomes Dq1 q2 = 300.
Applying the above equation to node 2, we get
q1 + Dq2 q3 = 0
Applying the above equation to node 3, we get
q2 + Dq3 q4 = 0
Applying the above equation to node 4, we get
q3 + Dq4 q5 = 0
where q5 is a hypothetical node to the right of node 4.
FR J
At x = L (node 4), the equation
 R  is applicable and the difference equation
FZ M
becomes

R  R J
 R
 'Z
M

From this expression we can determine T 5 in terms of T 3 and T 4 .

R R 

J
R  'Z
M

Substituting this in the equation for node 4, we get

 J 'Z

R   & 
R 
M

96

Introduction to Numerical Methods in Chemical Engineering

Thus the four difference equations are

Dq1 q2 = 300
q1 + Dq2 q3 = 0
q2 + Dq3 q4 = 0
J 'Z

R   & 
R 
M

O

J Q F 

J2
M#

QF
M




&    O'Z 

J
MF

 u 
 u 



   u  u  

Thus the four difference equations are

2.0625q1 q2 = 300
q1 + 2.0625q2 q3 = 0
q2 + 2.0625q3 q4 = 0
2q3 + 2.1125q4 = 0
The set of simultaneous linear algebraic equations can be written in tridiagonal form as



R

R
 


 
 R 

  R 




The solution can be obtained by modifying the parameters ai (i = 2 to N), bi (i = 1 to N) and

ci (i = 1 to N 1) in Program 1.1 given in the Appendix. The comparison of numerical and
analytical results is presented in Table 5.2.
Table 5.2

Numerical and analytical results for Example 5.7

x (m)

q (numerical solution
for 4 parts)

q (analytical
solution)

0.0125
0.025
0.0375
0.05

248.95
213.47
191.32
181.13

248.75
213.13
190.90
180.66

Even when 4 parts are made the difference between the numerical and analytical solution is
meagre. The numerical solution can exactly match with the analytical solution if a greater
number of parts is made.

Boundary Value Problems

97

5.3 Chemical Reaction and Diffusion in Pore

The differential equation for diffusion and reaction in a pore is given by
F % M
 %
FZ  &

Let us define

O
Thus the differential equation can be written as

(5.7)

M
&

F %
 O%
FZ 
The boundary conditions are
at x = 0

(5.8)

(5.9)

C = CS

and at x = L

(5.10a)

F%

FZ
where CS is the concentration at the surface of the pore.

(5.10b)

EXAMPLE 5.8 Diffusion and reaction take place in a pore of 1mm in length. The rate
constant of the reaction, k = 103s1 and effective diffusivity of species, D = 109 m2/s. Make
100 parts of the pore and determine the concentration at x = 0.5 mm. The concentration at the
surface of the mouth of the pore is 1 mol/m3.
Solution

We have
O

 
M
 m1


&
m and 100 parts are made, thus 'Z

 
  m. The

schematic diagram of the pore is shown in Fig. 5.10. The first node is labelled 0 and therefore
the last node is the 100th node as 100 parts are made.

The pore length is 1 mm = 10-3

F%
FZ

C=1
0
x=0

Fig. 5.10

The boundary conditions are

Diffusion and reaction in pore.

At x = 0:

C=1

At x = 103 m:

F%
FZ

100
x = 1 mm

98

Introduction to Numerical Methods in Chemical Engineering

Discretizing the differential equation at node i, we get

%   %   %
   %
'Z 
K

At node 1

%  %  %
   %
'Z 

It is given that C0 = 1, therefore

%    %
   %
'Z 

Substituting the value of Dx = 105 m, we get

%    %    u   %

Simplifying, we get
%  %

At node 2



%  %  %
   %
'Z 

C3 + C1 2C2 104C2 = 0
C1 2.0001C2 + C3 = 0
At node 99

%  %  %

   %
'Z 

C100 + C98 2C99 104C99 = 0

C98 2.0001C99 + C100 = 0

At node 100

%  %  %

   %

'Z

%  %  %    %

But

F%
FZ

 ; thus

%  %
 'Z

 and therefore C101 = C99.

Substituting C101 = C99 in the previous equation, we get

2C99 2.0001C100 = 0
The 100 equations can be written in tridiagonal form as

Boundary Value Problems



%

%
 


%
  

  




  

 




%
 



 
 %

  %

99
















The solution can be obtained by modifying the parameters ai (i = 2 to N), bi (i = 1 to N) and

ci (i = 1 to N 1) and di (i = 1 to N) in Program 1.1 given in the Appendix. From the results,
we get C = 0.73 at x = 0.5 mm (50th node).

Exercises
5.1

Consider the two-point boundary value problem

d2y
 y 1 0
dx 2
with the boundary conditions y(0) = y(1) = 0. List the tridiagonal set of equations
and determine y at various values of x. Take Dx = 0.1.
(Ans:

The tridiagonal set of equations are



[

[
  


 


 
 [

  [










y1 = y(0.1) = 0.041253

y3 = y(0.3) = 0.095313

y4 = y(0.4) = 0.108661

y5 = y(0.5) = 0.113096

y6 = y(0.6) = 0.108661

y7 = y(0.7) = 0.095313
5.2

y2 = y(0.2) = 0.072919
y8 = y(0.8) = 0.072919

y9 = y(0.9) = 0.041253

Consider the two-point boundary value problem

F [
F[

[Z 

FZ
FZ
with the boundary conditions y(0) = 5 and y(20) = 8. List the tridiagonal set of
equations and determine y at x = 10. Take Dx = 1.


100

Introduction to Numerical Methods in Chemical Engineering

(Ans:

The tridiagonal set of equations are



[
  
[


 


 
 [

  [










y10 = y(10) = 8.514381.

5.3

Consider the ordinary differential equation

d2y
dx 2

with the boundary conditions y(1) = 1.175 and y(3) = 10.018. Take Dx = 0.5. List
the tridiagonal set of equations and determine y at various x.
(Ans:

The tridiagonal set of equations are



[

 
 [

  [







y1 = y(1.5) = 2.146603 y2 = y(2.0) = 3.654857

5.4

y3 = y(2.5) = 6.076825.

Consider the ordinary differential equation

F [
FZ 

F[
  and F[     . Take Dx = 0.5.
FZ
FZ
List the tridiagonal set of equations and determine y at various x.

with the boundary conditions:

(Ans: The tridiagonal set of equations are



[

[
 


[
 


 
 [

  [





y1 = y(1.0) = 1.552429 y2 = y(1.5) = 2.333983 y3 = y(2.0) = 3.699032

y4 = y(2.5) = 5.988840 y5 = y(3.0) = 9.775857

Boundary Value Problems

5.5

101

Consider 1-D steady state conduction without heat generation taking place in a
rectangular slab. The temperature of the left side of the slab is 100C and of the
right side is 50C. The length of the slab is 1 m and the thermal conductivity of the
slab is 120 W/cm-K. Take Dx = 0.1 m. Determine the temperature distribution in
the slab and list the tridiagonal set of equations. The governing equation is
F 6
.
FZ 
(Ans: The tridiagonal set of equations are


6
  
6


  

 
 6

  6







T1 = T(0.1) = 95.0

T3 = T(0.3) = 85.0

T4 = T(0.4) = 80.0

T5 = T(0.5) = 75.0

T6 = T(0.6) = 70.0

T7 = T(0.7) = 65.0

T8 = T(0.8) = 60.0

T9 = T(0.9) = 55.0

A fin of diameter 0.02 m and length 0.08 m is attached to a wall (see Fig. 5.11).
The temperature of the wall is 200C. List the tridiagonal set of equations and
determine the temperature of the fin at x = 0.02, 0.04, 0.06 and 0.08 m, using the
finite difference technique taking four parts. The thermal conductivity of rod is
25 W/m-K and convective heat transfer coefficient from rod to surroundings is
40 W/m2-K. The temperature of surroundings is 25C. The governing differential
F R J2
equation is   
R  , where q = T Tsurr and boundary condition at
M#
FZ
FR J
x = 0.08 m is
 R .
FZ M

0
Wall at 200C

5.6

T2 = T(0.2) = 90.0

x=0

0.02

Fig. 5.11

0.04

0.06

x = 0.08 m

Exercise 5.6.

102

Introduction to Numerical Methods in Chemical Engineering

(Ans: The tridiagonal set of equations are



R
 
R


 
 R 

  R 

q1 = q (0.02) = 128.49








q2 = q (0.04) = 98.44

q3 = q (0.06) = 80.98

q4 = q (0.08) = 73.88
5.7

Diffusion and reaction take place in a pore of 1mm in length. The rate constant of
the reaction, k = 2.5 104s1 and effective diffusivity of species, D = 109 m2/s. Make
10 parts of the pore. List the tridiagonal set of equations and determine the
concentration along x. The concentration at the surface of the mouth of the pore is
F%
.
1 mol/m3 and at pore end
FZ
(Ans: The tridiagonal set of equations are


%

%
  


 


 
 %

  %

C1 = C(0.1) = 0.978139 C2 = C(0.2) = 0.958723

C4 = C(0.4) = 0.927039 C5 = C(0.5) = 0.914691
C7 = C(0.7) = 0.896832 C8 = C(0.8) = 0.891275
C10 = C(1.0) = 0.886838









C3 = C(0.3) = 0.941703
C6 = C(0.6) = 0.904631
C9 = C(0.9) = 0.887947

Distance (in mm) is measured from the pore mouth.

5.8

Diffusion and reaction take place in a pore of 1 mm in length. The rate constant of
the reaction, k = 0.1 s1 and effective diffusivity of species, D = 109 m2/s. Make
10 parts of the pore. List the tridiagonal set of equations and determine the
concentration along x. The concentration at the surface of the mouth of the pore is
F%
.
1 mol/m3 and at pore end
FZ
(Ans: The tridiagonal set of equations are
 
%
  
%


  

   %

  %










Boundary Value Problems

103

C1 = C(0.1) = 0.381966

C2 = C(0.2) = 0.145898

C3 = C(0.3) = 0.055728

C4 = C(0.4) = 0.021286

C5 = C(0.5) = 0.008131

C6 = C(0.6) = 0.003107

C7 = C(0.7) = 0.001190

C8 = C(0.8) = 0.000463

C9 = C(0.9) = 0.000198

C10 = C(1.0) = 0.000132

Distance (in mm) is measured from the pore mouth.
5.9

Water flows between the two fixed parallel plates as shown in Fig. 5.12. Fluid
moves in the x-direction parallel to the plates and there is no velocity in the y
direction. The spacing between the plates is 0.02 m and pressure gradient is 100
Pa/m. The viscosity of water under the flow conditions is 0.001 kg/m-s. Using the
finite difference method, solve the velocity profile equation

wR
w W
N 
wZ
w[

x
h

Fig. 5.12

Illustration for Exercise 5.9.

Determine the velocity at various nodes between the symmetry line and the wall.
Make 10 parts. Compare the numerical solution with the analytical solution
W

(Ans:

 R 

[ J .
 N Z

The tridiagonal set of equations are

 
W
  
W


  

 
 W

  W

and the results are presented in Table 5.3.









104

Introduction to Numerical Methods in Chemical Engineering

Table 5.3

Results in Exercise 5.9

x (m)

Node

u, Numerical (m/s)

0.000
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0.009

1
2
3
4
5
6
7
8
9
10

5.00
4.95
4.80
4.55
4.20
3.75
3.20
2.55
1.80
0.95

Distance (in m) is measured from the symmetry line.

u, Analytical (m/s)
5.00
4.95
4.80
4.55
4.20
3.75
3.20
2.55
1.80
0.95

Chapter 6

ConvectionDiffusion Problems
The convection-diffusion equation for the transport of a component of concentration C is
given by
W

F%
F %
& 
FZ
FZ

F%
F %
is the convection term and &  is the diffusion term. The
FZ
FZ
central difference scheme (CDS) or the upwind difference scheme (UDS) can be used for the
discretization of the convection term, whereas CDS is used for the discretization of the
diffusion term. The comparison of the central difference and upwind difference schemes for
the discretization of convection term is also discussed here.

In the above equation, W

6.1 Upwind Schemes

The upwind scheme is used for the discretization of the convection term. The first order and
second order upwind schemes are described below.

6.1.1 First Order Upwind Scheme

When the fluid is flowing from left to right properties at grid point i depend only on the
properties at grid point i 1 and when the fluid is flowing from right to left properties at grid
point i depend only on the properties at grid point i + 1. This is nothing more than obeying
the physics of the flow. For information propagated from left to right discretization of
convection term at node i is given by

F%
FZ

%  % 
'Z
K

( x, u)

(6.1)

and for information propagated from right to left discretization of convection term at node i
is given by
F% %   %
( x, u)
(6.2)
FZ
'Z
This is shown in Fig. 6.1.
K

105

106

Introduction to Numerical Methods in Chemical Engineering

6.1.2 Second Order Upwind Scheme

For information propagated from left to right, discretization of convection term at node i is
given by

%  %   %  
 'Z

F%
FZ

( x, u)

(6.3)

and for information propagated from right to left, discretization of convection term at node i
is given by

F%
FZ

%  %   %  
 'Z
K

Direction of flow

i2

i1

( x, u)

(6.4)

The information has

passed through node i 1
and then comes to node i

i+1

i+2

i+3

F%
FZ

%  % 
'Z
K

(a)

The information has

passed through node i + 1
and then comes to node i

i2
Fig. 6.1

i1

Direction of flow

(b)

i +1

i+2

i+3

F%
FZ

%  % 
'Z
K

Discretization of convection term using first order upwind method: (a) Direction of flow
and space identical; (b) Direction of flow opposite to direction of space.

Let us now derive the formula for second order upwind scheme. Since upwind scheme is onesided, we shall consider nodes near to a boundary (see Fig. 6.2). Assume that C can be
expressed near the boundary by the polynomial
C = a + bx + cx2

ConvectionDiffusion Problems

107

3
u

Dx
2
Dx

Boundary

1
Fig. 6.2

Nodes near boundary.

At point 1 (x = 0)
At point 2 (x = Dx)
At point 3 (x = 2Dx)

C1 = a
C2 = a + bDx + cDx2
C3 = a + 2bDx + 4cDx2

Solving the above equations for b, we get

%  %  %
 'Z

D
We find b because it is equal to
and at x = 0,

F%
F%
at the wall (at node 1). This is because
FZ
FZ

D  EZ

F%
= b. Therefore at point 1
FZ

%  %  %
 'Z

F%
FZ

This is a one-sided finite difference expression for the derivative at the boundary. This
becomes the basis for second order upwind scheme
%

Z

%  %   %  
 'Z
K

Here information is propagated in the opposite direction as compared to the direction of x. If

information is propagated in the direction of x, then
%

Z

%  %   %  
 'Z
K

Oscillations do not take place when first order upwind scheme is used for discretization of
convection term.

108

Introduction to Numerical Methods in Chemical Engineering

EXAMPLE 6.1 A component C is transported by means of convection and diffusion through

a one-dimensional space shown in Fig. 6.3.
u
x =1

x=0
Fig. 6.3

One-dimensional space.

Discretize the convectiondiffusion equation

W

F%
F %
& 
FZ
FZ

The boundary conditions are: at x = 0 m, C = 0 and at x = 1 m, C = 1. Discretize the equation

using (i) central difference scheme for both diffusion and convection terms and (ii) central
difference scheme for diffusion term and first order upwind scheme for convection term. Make
50 parts between x = 0 and x = 1 m. Calculate the distribution of C as a function of x for
x = 0.84 to 1.0. Compare the numerical results with the analytical solution. For the boundary
conditions, at x = 0: C = C0 and at x = L: C = CL, the analytical solution for 0 x L is
% Z % 

Z  2G   .


%.  %


2G

where Pe is the Peclet number, the ratio of strength of convection by strength of diffusion, and
W.
. Take Pe 50 .
is given by 2G
&
Solution

We have

(i) Central difference scheme for both diffusion and convection terms
Using central difference scheme (CDS) at node i, we get
%  % 
%  %   %
W 
 & 

 'Z
'Z 

Multiplying by 

'Z 
, we get
&

W'Z
%   %    %   %   %
&
The local Peclet number is given by
K

2G

NQE

W 'Z
&

ConvectionDiffusion Problems

109

Thus the discretized equation at node i becomes

  2G

NQE

Let B
Thus

2G

NQE

  and C

2G

NQE

   %   %   2G
K

NQE

 % 
K


 C %   %  B % 
K

Let the total length be 1 m and let us make 50 parts of the length; therefore 'x
schematic diagram is shown in Fig. 6.4.

0
x=0
C = C0

10

20

Fig. 6.4

At node 0,
At node 1

30

40

0.02 m. The

50
x = 1
C = C50

Schematic diagram.

C = C0.
 C %  %  B %

Since the value of C0 is known; therefore the equation at node 1 becomes

%  B %

C %

At node 2
 C %  %  B %

 C %  %  B % 

At node 3
At node 48
 C %   %   B % 

 C %   %   B %

At node 49

At node 50 the value of C50 is known; therefore the equation for node 49 becomes
 C %   % 

 B % 

Thus the set of equations for value of C at node 1 to 49 using central difference scheme for
both the diffusion and convection terms becomes

110

Introduction to Numerical Methods in Chemical Engineering

 B
%
 C
%
 B

%
C
 B

C
 B

%

%
C
 B

C  B

%


  

  



 









C
 B %

 C  %

C %














B %



W
W 'Z
 and the local Peclet number becomes 2G
 u   . Thus
&
&
a = Peloc 2 = 1 and b = Peloc + 2 = 3. The solution can be obtained by modifying the
parameters ai (i = 2 to N), bi (i = 1 to N) and ci (i = 1 to N 1) in Program 1.1 given in the
Appendix. The numerical and analytical results are shown in Table 6.1.

For Pe = 50,

NQE

(ii) Central difference scheme for diffusion term and upwind difference scheme for convection term
Using the upwind difference scheme (UDS) for the convection term and the central difference
scheme for the diffusion term at node i, we get
%  % 
%   %   %
W
 &

'Z 
'Z

On multiplying by 

'Z 
, the discretized equation at node i becomes
&
  2G   %    2G    %  %  
NQE

Let b = Peloc + 2 and

Thus

NQE

= Peloc + 1
H %   C %  % 
K

Let the total length be 1 m and let us make 50 parts of the length; therefore Dx = 0.02 m. At
node 0, C = C0.
At node 1
H %   C %  %  
Since the value of C0 is known, therefore the equation at node 1 becomes
At node 2

C %  %

H %

H %  C %  %

ConvectionDiffusion Problems

At node 3

H %  C %  %

At node 48

H %  C %   % 

H %  C %  %

At node 49

111

At node 50 the value of C50 is known; therefore the equation for node 49 becomes
H %   C % 

%

Thus the set of equations for value of C at node 1 to 49 using the central difference scheme
for the diffusion term and the first order upwind scheme for the convection term becomes

C
H


C

H

%
%


%
C


C
H

%
%
C 
H

H C 
%

  

  


  


  

H
C  %

H C %

H %














%


W
W 'Z
 and the local Peclet number becomes 2G
 u   . Thus
&
&
b = Peloc + 2 = 3 and g = Peloc + 1 = 2. The solution can be obtained by modifying the
parameters ai (i = 2 to N), bi (i = 1 to N) and ci (i = 1 to N 1) in Program 1.1 given in the
Appendix. The numerical and analytical results are shown in Table 6.1.

For Pe = 50,

NQE

Table 6.1
Node number
42
43
44
45
46
47
48
49

Numerical and analytical results for Example 6.1

x (m)

C (CDS)

0.84
0.86
0.88
0.90
0.92
0.94
0.96
0.98

0.000152
0.000457
0.001372
0.004115
0.012346
0.037037
0.111111
0.333333

C (CDS/UDS)
0.003906
0.007813
0.015625
0.031250
0.062500
0.125000
0.250000
0.500000

G Z  
(Analytical)
G  
0.000335
0.000912
0.002479
0.006738
0.018316
0.049787
0.135335
0.367879

112

Introduction to Numerical Methods in Chemical Engineering

The central difference scheme is a second order scheme and is therefore more accurate,
whereas upwind scheme used is first order and is therefore less accurate. But if more parts are
made, then more accurate results are obtained. The importance of first order upwind scheme
is shown in the next example.
EXAMPLE 6.2
Solution

Solve the previous problem for Pe = 500.

We have

(i) Central difference scheme for both diffusion and convection terms
W
W 'Z
 and the local Peclet number becomes 2G
 u   .
&
&
Thus a = Peloc 2 = 8 and b = Peloc + 2 = 12. The solution can be obtained by modifying
the parameters ai (i = 2 to N), bi (i = 1 to N) and ci (i =1 to N 1) in Program 1.1 given in
the Appendix. The numerical results are shown in Table 6.2.

For Pe = 500,

NQE

(ii) Central difference scheme for diffusion term and upwind difference scheme for convection term
W
W 'Z
 and the local Peclet number becomes 2G
 u  .
&
&
Thus b = Peloc + 2 = 12 and g = Peloc + 1 = 11. The solution can be obtained by modifying
the parameters ai (i = 2 to N), bi (i = 1 to N) and ci (i = 1 to N 1) in Program 1.1 given in
the Appendix. The numerical results are shown in Table 6.2.

For Pe = 500,

NQE

Table 6.2

Numerical results for Example 6.2

Node number

x (m)

C (CDS)

C (CDS/UDS)

42
43
44
45
46
47
48
49

0.84
0.86
0.88
0.90
0.92
0.94
0.96
0.98

0.039018
0.058528
0.087791
0.131687
0.197531
0.296296
0.444444
0.666667

0.000000
0.000000
0.000000
0.000006
0.000060
0.000751
0.008264
0.090909

When the local Peclet number is much below 1, then diffusion is dominant and when the local
Peclet number is much above 1, then convection is dominant. When the central difference
scheme is used for the discretization of both the diffusion and convection terms, then for all
local Peclet number greater than zero, b > 0 but a changes sign at Peloc = 2. The subdiagonal
elements are negative, diagonals are positive and superdiagonals are negative for Peloc < 2,
whereas for Peloc > 2 the subdiagonals elements are negative, diagonals are positive and
superdiagonals are positive. It is seen that when Peloc > 2, oscillations occur in the solution of
CDS, whereas, when UDS is used for discretization of the convection term, then for all values

ConvectionDiffusion Problems

113

of Peloc the subdiagonal elements are negative, diagonals are positive and superdiagonals are
negative. When first order method (UDS) is used, oscillations do not occur. Note that the sign
of subdiagonal, diagonal and superdiagonal elements in UDS match that of CDS for Peloc < 2.
Thus if oscillations occur when CDS is used, then a larger number of parts can be made so that
Dx becomes less and thus Peloc becomes less than 2, or UDS can be used to avoid oscillations.

6.2 Comparison of CDS and UDS

The upwind difference scheme at node i is given by [see Eq. (6.1)]
F%
FZ

7&5

%  % 
'Z
K

(6.1)

The right hand side can be written as

%  % 
'Z
K

%   %  %  %  %   % 


 'Z
 'Z
'Z

(6.5)

Thus
F%
FZ
F%
FZ
F%
FZ
F%
FZ
F%
FZ
F%
FZ

7&5

7&5

7&5

7&5

7&5

7&5

F%
FZ
F%
FZ
F%
FZ
F%
FZ
F%
FZ
F%
FZ

%&5

%  %  %   % 


 'Z
'Z

(6.6)

%  %  %   % 


 'Z
 'Z

(6.7)

%  %   %   % 


 'Z

(6.8)

%  %   % 


 'Z

(6.9)

%&5

%&5

%&5

%&5

'Z %  %   % 


'Z 

(6.10)

'Z F  %
 FZ 

(6.11)

%&5

Now consider the discretization of the convectiondiffusion equation

F%
F %
&  
FZ
FZ
Using the UDS for the discretization of the convection term, we get
W

W

F%
FZ

7&5

&

F %
FZ 

(6.12)

114

Introduction to Numerical Methods in Chemical Engineering

Substituting Eq. (6.11) in Eq. (6.12), we get

%&5

F%
W
FZ

F%
W
FZ

'Z F  %
F %
& 
 FZ 
FZ

W'Z F  %
F %
& 
 FZ 
FZ

%&5

(6.13)

Thus UDS is equivalent to adding the additional numerical diffusion (or artificial diffusion)
term to the CDS. The effective diffusion coefficient is
&GHH

&

W 'Z


(6.14)

and the effective local Peclet number is

2G

NQEGHH

W'Z
&
GHH

W'Z
W'Z
&



&

W'Z





2G

(6.15)

NQE

Thus due to the addition of the numerical diffusion term, the effective local Peclet number is
always less than 2, whatever the value of the local Peclet number and thus oscillations do not
occur when first order UDS is used.

Exercises
6.1

A component of concentration C is transported by means of convection and

diffusion through a one-dimensional space
F%
F %
&  
FZ
FZ
The boundary conditions are: at at x = 0 m, C = 1 and at x = 1 m, C = 0. Discretize
the convection-diffusion equation using the central difference scheme for both
diffusion and convection terms. Calculate the distribution of C as a function of x.
W
Make 10 parts between x = 0 and x = 1 m. Take
 m1. Compare the
&
G Z  
numerical result with the analytical solution %  Z    
.
G 
(Ans: The tridiagonal set of equations are
W



%
 
%



 


 
 %

  %






ConvectionDiffusion Problems

115

and the results are shown in Table 6.3.

Table 6.3

Results of Exercise 6.1

x (m)

C (analytical)

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9

6.2

C (numerical CDS)
0.999966
0.999865
0.999560
0.998645
0.995902
0.987671
0.962979
0.888904
0.666678

0.999922
0.999710
0.999133
0.997567
0.993307
0.981729
0.950256
0.864704
0.632149

A component of concentration C is transported by means of convection and

diffusion through a one-dimensional space
F%
F %
&  
FZ
FZ
The boundary conditions are: At x = 0 m, C = 1 and at x = 1 m, C = 0. Discretize
the convection-diffusion equation using the central difference scheme for the
diffusion term and the first order upwind difference scheme for the convection term.
Calculate the distribution of C as a function of x. Make 10 parts between
W
x = 0 and x = 1 m. Take
 m1. Compare the numerical result with the
&
G Z  
analytical solution %  Z    
.
G 
(Ans: The tridiagonal set of equations are
 
% 
  
% 

 
  

   % 

  % 

and the results are shown in Table 6.4.
W

Table 6.4

Results of Exercise 6.2

x (m)

C (numerical CDS/UDS)

C (analytical)

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9

0.999023
0.997068
0.993157
0.985337
0.969697
0.938417
0.875855
0.750733
0.500489

0.999922
0.999710
0.999133
0.997567
0.993307
0.981729
0.950256
0.864704
0.632149

116

Introduction to Numerical Methods in Chemical Engineering

6.3

Since the first order upwind is used for the discretization of the convection term,
therefore more parts are a must for a better answer as the first order method is
O(Dx).
W
Solve Exercise 6.1 for
 m1. Compare the numerical result with the
&
G Z  
analytical solution %  Z    
.
G 
(Ans:

The tridiagonal set of equations are

 
%
  
%


  

   %

  %

and the results are shown in Table 6.5.
Table 6.5









Results of Exercise 6.3

x (m)

C (analytical)

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9

6.4

C (numerical CDS)
1.000000
1.000000
1.000000
1.000000
1.000000
1.000000
1.000000
1.000000
1.000000

0.999999
0.999999
0.999999
0.999994
0.999955
0.999665
0.997521
0.981684
0.864665

In this problem the local Peclet number is 2.0; therefore central difference gives a
wrong answer.
W
Solve Exercise 6.2 for
 m1. Compare the numerical result with the
&
G Z  
analytical solution %  Z    
.
G 
(Ans: The tridiagonal set of equations are


%
 
%



 


 
 %

  %






ConvectionDiffusion Problems

117

and the results are shown in Table 6.6.

Table 6.6

Results of Exercise 6.4

x (m)

C (analytical)

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9

6.5

C (numerical CDS/UDS)
0.999966
0.999865
0.999560
0.998645
0.995902
0.987671
0.962979
0.888904
0.666678

0.999999
0.999999
0.999999
0.999994
0.999955
0.999665
0.997521
0.981684
0.864665

Since the first order upwind method is used for the discretization of the convection
term, therefore more parts are a must for a better answer as the first order method
is O(Dx).
W
Solve Exercise 6.1 for
 m1. Compare the numerical result with the
&
G Z  
analytical solution %  Z    
.
G 
(Ans:

The tridiagonal set of equations are

 
%
  
%






   %

  %









and the results are shown in Table 6.7.

Table 6.7

Results of Exercise 6.5

x (m)

C (numerical CDS)

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9

1.000697
0.999071
1.002865
0.994011
1.014670
0.966466
1.078942
0.816497
1.428870

C (analytical)
1.000000
1.000000
1.000000
1.000000
1.000000
0.999999
0.999999
0.999955
0.993262

118

Introduction to Numerical Methods in Chemical Engineering

In this problem the local Peclet number is greater than 2.0; therefore central
difference gives oscillations.
6.6

Solve Exercise 6.2 for

W
&

 m1. Compare the numerical result with the

G Z  
analytical solution %  Z    
.
G 
(Ans: The tridiagonal set of equations are
 
%
  
%


 


   %

  %









and the results are shown in Table 6.8.

Table 6.8
x (m)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9

Results of Exercise 6.6

C (numerical CDS/UDS)
1.000000
1.000000
0.999997
0.999979
0.999872
0.999229
0.995371
0.972223
0.833334

C (analytical)
1.000000
1.000000
1.000000
1.000000
1.000000
0.999999
0.999999
0.999955
0.993262

Since the first order upwind method is used for the discretization of convection
term, therefore more parts are a must for a better answer as the first order method
is O(Dx)).

Chapter 7

Tubular Reactor with Axial

Dispersion
Plug flow reactors were discussed in Chapter 4. When axial dispersion takes place in a tubular
reactor, then the problem becomes a boundary value problem and the differential equation
becomes second order due to the addition of a diffusion term. Thus two conditions are required
to completely define the problem. Danckwerts boundary conditions are considered here. One
boundary condition is specified at the inlet and one at the exit of the tubular reactor, for each
species. The solution of various single, series and parallel reactions are discussed using the
finite difference method in this chapter.

7.1 Boundary Value Problems in Chemical Reaction

Engineering
In tubular reactor with axial dispersion the boundary conditions are specified. The boundary
conditions and ordinary differential equations for the tubular reactor with axial dispersion are
shown in Table 7.1.
Table 7.1

Boundary conditions and ODEs for tubular reactor with axial dispersion

Boundary condition
at x = 0

Boundary condition
at x = L

M
#  $
o

W% # KP


W%$ KP


F% #
FZ
F%$
W% $  &
FZ
W% #  &

F% #
FZ
F%$
FZ

ODEs for plug

flow reactor
F % #
F%
 W #  M% #
FZ 
FZ
F %$
F%$
&
W
 M% #
FZ 
FZ
&







M
M
#  $  %
o
o

W% # KP


W%$ KP


W%% KP


F% #
FZ
F%$
W% $  &
FZ
F%%
W%%  &
FZ
W% #  &

o
#  $  %
M
$  %  &
o

F% #
FZ
F%$
FZ
F%%
FZ

F % #
F%
 W #  M% # 
FZ 
FZ
F %$
F%$
&
W
 M% #  M%$
FZ 
FZ
F %%
F%
&
 W %  M%$ 

FZ
FZ
&





M

119

120

Introduction to Numerical Methods in Chemical Engineering

Table 7.1

W% #
W%$
W%%

 KP

 KP

 KP

W%&

 KP

F% #
FZ
F%$
FZ
F%%
FZ
F%&
FZ

F% #
FZ
F%$
W% $  &
FZ
F%%
W%%  &
FZ
F%&
W%&  &
FZ
W% #  &

(Cont.)

&

&

&

&

F % #
FZ

W

F% #
 M% #%$
FZ

F % $
F%
 W $  M% #% $  M%$%%
FZ
FZ 
F %%
FZ 

W

F%%
 M% #%$  M% $%%
FZ

F % &
F%
 W &  M% $%%
FZ
FZ 




7.2 First Order Reaction

Consider a tubular vessel in which axial dispersion occurs along with convection. The velocity
of the fluid is u, the axial dispersion coefficient is D, the concentration of species is C and A
is the cross-sectional area. Consider a differential section in this vessel (see Fig. 7.1).

dx
Fig. 7.1

Tubular reactor and differential section.

In this differential section the material entering through convection

that entering through dispersion

= uCA

(7.1)

F%
#
FZ

(7.2)

F%

FZ #
= W% 
FZ

(7.3)

F% F F%
= &

FZ #
FZ FZ FZ

(7.4)

= &
that leaving through convection

and that leaving through dispersion

Accumulation
=

F%
#FZ
FV

(7.5)

Tubular Reactor with Axial Dispersion

121

We know that Input Output = Accumulation. Thus

F%
#FZ
FV

W%#  &

F% F F%
F%
F%

#  W% 
FZ #  &

FZ #
FZ
FZ

FZ FZ FZ

F%
FZ
FV

W

F%
F F%
FZ  &
FZ
FZ
FZ FZ

F%
FV

F %

&

FZ

W

F%
FZ

(7.6)

(7.7)
(7.8)

At steady state and if reaction also occurs in the tubular vessel, we get

&

F %
FZ

W

F%
  T  
FZ

(7.9)

C now refers to the concentration of the reactant or product. r is a net positive quantity if C
refers to a reactant and negative if C refers to a product.
Use of a dispersion model changes the reactor analysis from an initial value problem to
a boundary value problem. The boundary conditions proposed by Danckwerts are
At inlet:

W%

At exit:

F%
FZ

W%  &

KP

F%
FZ

(7.10)
(7.11)

At the reactor inlet, the flux entering is uCin but once inside the reactor and in the presence
of dispersion, the flux is
W%  &

F%
FZ

Balancing these two fluxes at x = 0 yields the inlet boundary condition

W%

KP

W%  &

F%
FZ

If the reaction stops once the stream leaves the reactor, the concentration profile becomes
F%
uniform, and the outlet boundary condition becomes
.
FZ
EXAMPLE 7.1 Consider a reaction A B carried out in a tubular reactor. The differential
equation for species A along the length of the tubular reactor of length 10 m is

&

F % #
FZ

W

F% #
 M% #
FZ

122

Introduction to Numerical Methods in Chemical Engineering

The boundary conditions are

W% #

At x = 0 (inlet):

KP

W% #  &

F% #
FZ

F% #

FZ
A fluid medium comprising initially only A flows through the reactor with a mean axial
velocity u = 1 m/s. The axial dispersion coefficient, D = 104 m2/s and rate constant of the
reaction is 1 s1. The inlet concentration, CA,in = 1 mol/m3. Make 50, 20, and 10 parts of the
reactor and determine the concentration of A at various nodes along the length of the tubular
reactor.

At x = 10 m (exit):

Solution

We have

Concentration profile for 50 parts

50 parts of the reactor are made as shown in Fig. 7.2.

Z1

Z1

Fig. 7.2

Example 7.1.


 m

We solve the differential equation using upwind difference scheme for convection term.
Discretizing the differential equation at node i, we get
'Z

 %   %
%
& # 
'Z 

#K

#K

%
 W

#K

%
'Z

#K



 M%

#K

At node 1
%  % #   % #
% #  % #
& #
 W

'Z
'Z

 M% #

W
&
W
&

&
% #   
 M   % #   % #  

'Z
'Z
'Z
'Z
'Z

From the boundary condition at node 1, we get

W% #KP

%  % #
W% #  & # 

 'Z




Tubular Reactor with Axial Dispersion

123

Solving for CA0 we get

% #

 W 'Z
% #KP  % #   % #
&

Substituting for CA0 in the equation for node 1, we get

W
&
W  W 'Z
&

&

% #   
 M   % #    
% #KP  % #   % #

'Z
'Z &
'Z
'Z
'Z

 & W
W 
W
&
 M 
% #
  
% #   
'Z

'Z
&
'Z
'Z

 W  W


% #KP
&
'Z

At node 2
W
W
&
&
&

 M % #   % #
 
% #    
'Z
'Z
'Z
'Z
'Z

W
W
&
&
&

 M % #   % # 
 
% #    
'Z
'Z
'Z
'Z
'Z

At node 3

At node 51
W
W
&
&
&

 M % #   % #
 
% #     
'Z
'Z
'Z
'Z
'Z

From the boundary condition at node 51, we get

% #   % # 

 'Z

thus

CA52 = CA50

Substituting for CA52 in the equation for node 51, we get

W
W
&
&

 M % #
 
% #     
'Z
'Z
'Z
'Z

The coefficients of equation 1 (at node 1) are

Coefficient of % #

Coefficient of % #

&
'Z

&
'Z


W
'Z

W
W
 M 
'Z
&
 u  






 u  




   



 



W W
Right hand side of equation 1 = 
&  'Z % #

KP



 
 

 

124

Introduction to Numerical Methods in Chemical Engineering

The coefficients of equation 2 (at node 2) are

Coefficient of % #
Coefficient of % #
Coefficient of % #

&
'Z

&
'Z

 

W
'Z



W
 M
'Z






 u  



   


 

&


'Z  
Right hand side of equation 2 = 0.
The coefficients of equation 3 (at node 3) are
Coefficient of % #
Coefficient of % #
Coefficient of % #

&
'Z

&
'Z

W
'Z

 


W
 M
'Z






 u  



   


 

&


'Z  
Right hand side of equation 3 = 0.
The coefficients of equation 51 (at node 51) are
Coefficient of % #

Coefficient of % #

&
'Z


&
'Z

W
'Z


 u  


W
 M
'Z




 u  





   


Right hand side of equation 51 = 0.

The above equations can be written in tridiagonal form as given below. The solution can be
obtained by modifying the parameters ai (i = 2 to N), bi (i = 1 to N) and ci (i = 1 to N 1) in
Program 1.1 given in the Appendix.


% #

%
  

#






   % # 

  % # 





Tubular Reactor with Axial Dispersion

125

The solution using TDMA is presented in Table 7.2.

Table 7.2

Results for concentration profile for 50 parts

Node number

x (m)

CA

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
51

0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
10.0

0.999908
0.833268
0.694400
0.578675
0.482236
0.401869
0.334895
0.279083
0.232573
0.193813
0.161513
0.134596
0.112165
0.093472
0.077895
0.064913
0.054095
0.045080
0.037567
0.031306
0.026089
0.021741
0.018118
0.000110

More conversion would have occurred if the reactor is assumed to be ideal plug flow.
Concentration profile for 20 parts

If 20 parts of the reactor are made, then 'Z
 m. The coefficients of the 21 equations

at 21 nodes are as given below.
The coefficients of equation 1 (at node 1) are

Coefficient of % #




Coefficient of % #

&
'Z 

W
W
 M 
&
'Z

 u  




&
'Z

W
'Z



   



 u  







 



W W
Right hand side of equation 1 = 
&  'Z % #

KP




  

 

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Introduction to Numerical Methods in Chemical Engineering

The coefficients of equation 2 (at node 2) are

Coefficient of % #
Coefficient of % #
Coefficient of % #

&
'Z


&

'Z

 

W
'Z



W
 M
'Z

&

 

'Z 








 u  




   




Right hand side of equation 2 = 0.

The coefficients of equation 3 (at node 3) are
Coefficient of % #
Coefficient of % #
Coefficient of % # 

&
'Z


&
'Z

W
'Z


 




W
 M
'Z

&

 

'Z 








 u  





  




Right hand side of equation 3 = 0.

The coefficients of equation 21 (at node 21) are
Coefficient of % #

Coefficient of % #

&
'Z


&
'Z

W
'Z


 u  




W
 M
'Z




 u  







   


Right hand side of equation 21 = 0.

The above equations can be written in tridiagonal form as given below:
 
% #

  

% # 






   % # 

  % # 





The solution can be obtained by modifying the parameters ai (i = 2 to N), bi (i = 1 to N)

and ci (i = 1 to N 1) in Program 1.1 given in the Appendix. The results are presented in Table
7.3.

Tubular Reactor with Axial Dispersion

Table 7.3

127

Results for concentration profile for 20 parts

Node number

x (m)

1
3
5
7
9
11
13
15
17
19
21

CA

0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0

0.999917
0.444400
0.197500
0.087800
0.039000
0.017300
0.007700
0.003400
0.001500
0.000677
0.000301

Concentration profile for 10 parts




If 10 parts of the reactor are made, then 'Z

at 11 nodes are as given below.

 m. The coefficients of the 11 equations

The coefficients of equation 1 (at node 1) are

Coefficient of % #
Coefficient of % #

&

'Z

&
'Z

W
W
 M 
'Z
&

W
'Z

 u  


 u  


KP

Coefficient of % #
Coefficient of % #

&
'Z


&
'Z

W
'Z


 


W
 M
'Z

 u  


&
'Z

W
'Z

 




 
 


   



'Z 

Right hand side of equation 2 = 0.
The coefficients of equation 3 (at node 3) are
Coefficient of % #





 

&



   



 





W W
Right hand side of equation 1 = 
&  'Z % #

The coefficients of equation 2 (at node 2) are

Coefficient of % #





 

128

Introduction to Numerical Methods in Chemical Engineering

Coefficient of % #

Coefficient of % #

&

'Z

W
 M
'Z

&

 

'Z 



 u  



   




Right hand side of equation 3 = 0.

The coefficients of equation 11 (at node 11) are
Coefficient of % #

Coefficient of % #

&
'Z


&
'Z

 u  

W
'Z


W
 M
'Z





 u  



    


Right hand side of equation 11 = 0.

The above equations can be written in tridiagonal form as given below.
 
% #

  

% # 






   % #

  % #





The solution can be obtained by modifying the parameters ai (i = 2 to N), bi (i = 1 to N)

and ci (i = 1 to N 1) in Program 1.1 given in the Appendix. The results are presented in
Table 7.4.
Table 7.4

Results for concentration profile for 10 parts

Node number
1
2
3
4
5
6
7
8
9
10
11

x (m)
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0

CA
0.999925
0.499975
0.249994
0.125000
0.062502
0.031252
0.015626
0.007813
0.003907
0.001953
0.000977

Tubular Reactor with Axial Dispersion

129

7.3 Second Order Reaction

Consider a tubular reactor with axial dispersion in which second order reaction takes place.
The analysis is described with an example.
EXAMPLE 7.2 Consider a reaction A B carried out in a tubular reactor. The differential
equation for species A along the length of the tubular reactor of length 10 m is

&

F % #
FZ

W

F% #

 M% #
FZ

The boundary conditions are

W% #

At x = 0 (inlet):

W% #  &

KP

F% #
FZ

F% #

FZ
A fluid medium comprising initially only A flows through the reactor with a mean axial
velocity u = 1 m/s. The axial dispersion coefficient, D = 104 m2/s and rate constant of the
reaction is 1 m3/mol-s. The inlet concentration CA,in =1 mol/m3. Make 20 parts of the reactor
and determine the concentration of A at various nodes along the length of the tubular reactor.

At x = 10 m (exit):

Solution Since 20 parts of the reactor are made, 'Z

equations at 21 nodes are as given below.




 m. The coefficients of the 21

The coefficients of equation 1 (at node 1) are

Coefficient of % #




Coefficient of % #

&
'Z 

W
W
 M% # 
&
'Z

 u  




&
'Z

W
'Z



 % #  



 u  







  % #



W W
Right hand side of equation 1 = 
&  'Z % #

KP

The coefficients of equation 2 (at node 2) are

Coefficient of % #

&
'Z

W
'Z

 











 
 

 

130

Introduction to Numerical Methods in Chemical Engineering

Coefficient of % #
Coefficient of % #

&


'Z

W
 M% #
'Z

 u  





 % #


   % #


 % #


   % #

 

&


'Z  
Right hand side of equation 2 = 0.
The coefficients of equation 3 (at node 3) are
Coefficient of % #
Coefficient of % #
Coefficient of % #

&
'Z


&
'Z

W
'Z


 




W
 M% #
'Z




 u  




 

&


'Z  
Right hand side of equation 3 = 0.
The coefficients of equation 21 (at node 21) are
Coefficient of % #
Coefficient of % #

&
'Z


&
'Z

W
'Z


 u  




W
 M% #
'Z







 u  





 % #


   % #

Right hand side of equation 21 = 0.

The above equations can be written in tridiagonal form as given below.
  % # 


  % # 





   % #



% #
%

#



#
  % # % #





Program 7.1 for the solution of the above problem is given in the Appendix. In the program
the initial values of concentration of A at nodes 1 to 21 is assumed and then the TDMA is used
to determine new values of concentration of A at nodes 1 to 21. Again, these values are used
to determine the coefficients in the matrix, and after the coefficients are determined the TDMA
is used to determine new values of concentration of A at nodes 1 to 21. The procedure is
repeated till there is no change in the concentration at each node. The results are presented in
Table 7.5.

Tubular Reactor with Axial Dispersion

Table 7.5

131

Results in Example 7.2

Node number

x (m)

1
3
5
7
9
11
13
15
17
19
21

CA

0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0

0.999923
0.569732
0.387587
0.290241
0.230588
0.190624
0.162124
0.140841
0.124379
0.111286
0.100638

7.4 Multiple Reactions

Consider a tubular reactor with axial dispersion in which multiple reactions takes place. The
analysis is described with an example.
EXAMPLE 7.3 Consider the following two reactions taking place in a tubular reactor with
axial dispersion:
M
#  $  %
o
M
$  %  &
o

Assuming the axial dispersion coefficient to be the same for all the species, the concentration
of various species along the length of the reactor are given by the following differential
equations:
for component A

F % #

&

FZ

W

F% #
 M% #%$
FZ

for component B

&

F % $

&

F %%

FZ

W

F%$
 M% #%$  M%$%%
FZ

W

F%%
 M% #%$  M%$%%
FZ

for component C

FZ

for component D

&

F % &
FZ

W

F%&
 M%$%%
FZ

132

Introduction to Numerical Methods in Chemical Engineering

The boundary conditions are

W% #

KP

W% $

W%%

At inlet:

W% &

F% #
FZ

At exit:

F%$
FZ

W% #  &

F% #
FZ

W% $  &

F% $
FZ

W%%  &

F%%
FZ

W% &  &

F% &
FZ

KP

KP

KP

F%%
FZ

F%&
FZ

CPF

Make 20 parts of the reactor of length 10 m. A fluid medium comprising initially only A and
B flows through the reactor with a mean axial velocity u = 1 m/s. The axial dispersion
coefficient is the same for all the species, D = 104 m2/s, and the rate constants of the reactions
are k1 = k2 = 1 m3/mol-s. The inlet concentrations of A and B are CA,in = CB,in = 1 mol/m3.
Compute the concentration of various species along the length of the reactor.
Solution

We have



'Z

 m

We solve the differential equation using the upwind difference scheme for the convection term.
Discretizing the differential equation at node i, we get for species A
 %   %
%
& # 
'Z 

#K

#K

%
 W

#K

%
'Z

#K



 M% %

#K

$K

for species B
 %   %
%
%
& $ 
 W

'Z

$K

$K

$K

%
'Z

$K



 M% %  M% %

#K

$K

$K

%K

for species C
 %%K   %%K
%
& %K 
'Z 

%%K  %%K 
 W
 M% #K % $K  M% $K %%K
'Z

for species D
 %   %
%
& & 
'Z 

&K

&K

%
 W

&K

%
'Z

&K



 M% %

$K

%K

133

Tubular Reactor with Axial Dispersion

At node 1 the discretized equation for the component A is

%  % #  % #
% #  % #
& #
 W

'Z
'Z

 M% #% $

W
&
W
&

&
% #   
 M% $   % #   % #   

'Z
'Z
'Z
'Z
'Z
From the boundary condition at node 1, we get
W% #KP




%  % #
W% #  & # 

 'Z

Solving for CA0, we get

 W 'Z
% #KP  % #   % #
&
in the equation for node 1, we get
% #

Substituting for CA0

W
&
W W 'Z
&

&
% #   
 M% $   % #    
% #KP  % #   % #

'Z
'Z &
'Z
'Z
'Z

 & W
W
W
&
 M%$ 
% #
  
% #   
'Z

'Z
&
'Z
'Z

At node 1 the discretized equation for component B is

W W


% #KP
&
'Z

%  % $   %$
% $  %$
& $
 W
 M% #%$  M% $%%

'Z
'Z

W
&
W
&

&
% $   
 M% #  M%%   % $  % $  

'Z
'Z
'Z
'Z
'Z
From the boundary condition at node 1, we get
W%$KP




%  %$
W%$  & $ 

 'Z

Solving for CB0, we get

%$

W 'Z
%$KP  %$   %$
&

Substituting for CB0 in the equation for node 1, we get

W
&
W W 'Z
&

&
% $   
 M% #  M%%    % $    
%$KP  %$   %$

'Z
'Z &
'Z
'Z
'Z

 & W
W
W
&
 M% #  M%% 
%$ 
  
%$   
'Z

'Z
&
'Z
'Z

W W


%$KP
&
'Z

134

Introduction to Numerical Methods in Chemical Engineering

At node 1 the discretized equation for component C is

%  %%   %%
%%  %% 
& %
 W

'Z
'Z

 M% #% $  M% $%%

W
&
W
&

&
%%   
 M % $   %%   %%   

'Z
'Z
'Z
'Z
'Z
From the boundary condition at node 1, we get


 M% #%$

%  %% 
W%%  & % 

 'Z

Solving for CC0, we get

W'Z%%
 %% 
&
Substituting for CC0, in the equation for node 1, we get
%% 

W
&
W W 'Z%%

&

&
%%   
 M% $   %%    
 %% 

&
'Z
'Z
'Z
'Z
'Z

 & W
W 
W
&
 M%$ 
%% 
  
%%   
'Z

'Z
&
'Z
'Z

 M% #% $

 M% #%$

At node 1 the discretized equation for component D is

%  %&   % &
%&  %& 
& &
 W

'Z
'Z

 M %$%%

W
&
W
&
&
% &   
  % &   %&   

' Z 'Z
'Z
'Z
'Z
From the boundary condition at node 1, we get


 M%$%% 

%  %&
W% &  & & 

 'Z

Solving for CD0, we get

W 'Z% &
 %&
&
Substituting for CD0, in the equation for node 1, we get
%&

W
&
W W 'Z% &

&
&
% &   
 %& 
  %&   

'Z 'Z
'Z
&
'Z
'Z

 & W W
W
&



%

% 
'Z  'Z
& 'Z  'Z & 
&

 M%$%%

 M% $%%

Tubular Reactor with Axial Dispersion

At node 2 the discretized equations for various components are

W
W
&
&
&

 M% $ % #    % #
 
% #    
'Z
'Z
'Z
'Z
'Z

W
W
&
&
&

 M% #  M%%  %$   %$

 
% $    
'Z
'Z
'Z
'Z
'Z

W
W
&
&
&

 M %$ %%    %% 
 
%%    
'Z
'Z
'Z
'Z
'Z

W
W
&
&
&
 
% &    
%&    % &
'Z
'Z
'Z
'Z
'Z
At node 21 the discretized equation for component A is

 M% # % $

 M %$ %% 

W
W
&
&
&

 M% $  % #    % #
 
% #     
'Z
'Z
'Z
'Z
'Z

From the boundary condition at node 21, we get

Substituting for CA22

% #   % # 
thus CA22 = CA20


 'Z

in the equation for node 21, we get

W
W
&
&

 M%$  % # 
 
% #     
'Z
'Z
'Z
'Z

At node 21 the discretized equation for component B is

W
W
&
&
&

 M% #  M%%  %$   % $

 
% $     
'Z
'Z
'Z
'Z
'Z

From the boundary condition at node 21, we get

Substituting for CB22

% $   % $ 
thus CB22 = CB20


 'Z

in the equation for node 21, we get

W
W
&
&

 M% #  M%%  % $

 
% $     
'Z
'Z
'Z
'Z

At node 21 the discretized equation for component C is

W
W
&
&
&

 M %$ %%    %% 
 
%%     
'Z
'Z
'Z
'Z
'Z

From the boundary condition at node 21, we get

%%   %% 

 'Z

thus CC22 = CC20

 M% #% $

135

136

Introduction to Numerical Methods in Chemical Engineering

Substituting for CC22 in the equation for node 21, we get

W
W
&
&

 M%$ %% 
 
%%     
'Z
'Z
'Z
'Z

At node 21 the discretized equation for component D is

 M% #% $

W
W
&
&
&
 
% &     
% &    % & 
'Z
'Z
'Z
'Z
'Z
From the boundary condition at node 21, we get
%&   %& 

 'Z

 M% $ %% 

thus CD22 = CD20

Substituting for C D 22 in the equation for node 21, we get

W
W
&
&
 
% &     
% & 
'Z
'Z
'Z
'Z

 M% $%% 

The coefficients of equation 1 (node 1, species A) are

Coefficient of % #

 u  






 %$  



   %$

Coefficient of CB1 = 0
Coefficient of CC1 = 0
Coefficient of CD1 = 0
Coefficient of % #

 u  









Coefficient of CB2 = 0
Coefficient of CC2 = 0
Coefficient of CD2 = 0

W W
Right hand side of equation 1 = 
&  'Z % #

KP



 
 

 

The coefficients of equation 2 (node 1, species B) are

Coefficient of CA1 = 0
Coefficient of CB1 = 
Coefficient of CC1 = 0
Coefficient of CD1 = 0
Coefficient of CA2 = 0

 u  






 % #  %%  



   % #  %%

Tubular Reactor with Axial Dispersion

Coefficient of %$

 u  









Coefficient of CC2 = 0
Coefficient of CD2 = 0

W W
Right hand side of equation 2 = 
&  'Z %$

KP



 
 

 

The coefficients of equation 3 (node 1, species C) are:

Coefficient of CA1 = 0
Coefficient of CB1 = 0
Coefficient of CC1 = 

 u  





 %$  



   %$

Coefficient of CD1 = 0
Coefficient of CA2 = 0
Coefficient of CB2 = 0
Coefficient of CC2 =

 u  









Coefficient of CD2 = 0
Right hand side of equation 3 = CA1CB1.
The coefficients of equation 4 (node 1, species D) are:
Coefficient of CA1 = 0
Coefficient of CB1 = 0
Coefficient of CC1 = 0
Coefficient of %&

 u  






 
 

 

Coefficient of CA2 = 0
Coefficient of CB2 = 0
Coefficient of CC2 = 0

 u  





Right hand side of equation 4 = CB1CC1.
Coefficient of %&

The coefficients of equation 5 (node 2, species A) are:

Coefficient of % #

 









137

138

Introduction to Numerical Methods in Chemical Engineering

Coefficient of CB1 = 0
Coefficient of CC1 = 0
Coefficient of CD1 = 0
Coefficient of % #

 u  





 %$ 


   %$

Coefficient of CB2 = 0
Coefficient of CC2 = 0
Coefficient of CD2 = 0

Coefficient
Coefficient
Coefficient
Right hand

 



of CB3 = 0
of CC3 = 0
of CD3 = 0
side of equation 5 = 0.

Coefficient of % #

The coefficients of equation 6 (node 2, species B) are:

Coefficient of CA1 = 0
Coefficient of %$

 


Coefficient of CC1
Coefficient of CD1
Coefficient of CA2


=0
=0
=0

Coefficient of %$




 u  







 % #  %% 


   % #  %% 

Coefficient of CC2 = 0
Coefficient of CD2 = 0
Coefficient of CA3 = 0
Coefficient of %$

 



Coefficient of CC3 = 0
Coefficient of CD3 = 0
Right hand side of equation 6 = 0.

The coefficients of equation 7 (node 2, species C) are:

Coefficient of CA1 = 0
Coefficient of CB1 = 0
Coefficient of %%

 









Tubular Reactor with Axial Dispersion

Coefficient of CD1 = 0
Coefficient of CA2 = 0
Coefficient of CB2 = 0
Coefficient of %% 

 u  




 %$


   %$ 

Coefficient of CD2 = 0
Coefficient of CA3 = 0
Coefficient of CB3 = 0

 



Coefficient of CD3 = 0
Right hand side of equation 7 = CA2CB2

Coefficient of %% 

The coefficients of equation 8 (node 2, species D) are:

Coefficient of CA1 = 0
Coefficient of CB1 = 0
Coefficient of CC1 = 0
Coefficient of %&

 


Coefficient of CA2
Coefficient of CB2
Coefficient of CC2


=0
=0
=0

Coefficient of %&




 u  









 

Coefficient of CA3 = 0
Coefficient of CB3 = 0
Coefficient of CC3 = 0

 



Right hand side of equation 8 = CB2CC2.
Coefficient of %&

The coefficients of equation 81 (node 21, species A) are:

Coefficient of % #

 u  

Coefficient of CB20 = 0
Coefficient of CC20 = 0
Coefficient of CD20 = 0








139

140

Introduction to Numerical Methods in Chemical Engineering

Coefficient of % #
Coefficient
Coefficient
Coefficient
Right hand

 u  





 %$


   %$

of CB21 = 0
of CC21 = 0
of CD21 = 0
side of equation 81 = 0.

The coefficients of equation 82 (node 21, species B) are:

Coefficient of CA20 = 0
Coefficient of %$

 u  









Coefficient of CC20 = 0
Coefficient of CD20 = 0
Coefficient of CA21 = 0
Coefficient of %$

 u  





 % #  %% 


   % #  %% 

Coefficient of CC21 = 0
Coefficient of CD21 = 0
Right hand side of equation 82 = 0.
The coefficients of equation 83 (node 21, species C) are:
Coefficient of CA20 = 0
Coefficient of CB20 = 0
Coefficient of %% 

 u  









Coefficient of CD20 = 0
Coefficient of CA21 = 0
Coefficient of CB21 = 0
Coefficient of %% 

 u  





 %$


   %$

Coefficient of CD21 = 0
Right hand side of equation 83 = CA21CB21.
The coefficients of equation 84 (node 21, species D) are:
Coefficient of CA20 = 0
Coefficient of CB20 = 0
Coefficient of CC20 = 0

Tubular Reactor with Axial Dispersion

Coefficient of %& 

 u  





141



Coefficient of CA21 = 0
Coefficient of CB21 = 0
Coefficient of CC21 = 0

 u  


 


Right hand side of equation 84 = CB21CC21.
Coefficient of %&

Thus the set of equations for concentration of species A, B, C, and D at nodes 1 to 21 can be
written in the block tridiagonal form as

$
#


%
$ %
# $
#

%
$ %
# $
#

%
$ %
 



 
  
 
#


$
#

:
:

:

:
:

:







% : 

$ : 

&
&

&

&
&

&







&
&


where

:

For node 1
  %$


$

% #
%
$
%%

%&

:

% #
%
$
%% 

%& 


  % #  %%



: 

% #
%
$
%% 

%& 



  % $








142

Introduction to Numerical Methods in Chemical Engineering

%




















&




% #%$

%$%%

For node 2
#

$

%

&
For node 3
#

$





















  % $ 


  % #   %% 









  % $ 


























% #%$

%$%% 





















  % $


  % #  %% 









  % $








Tubular Reactor with Axial Dispersion

%

&
For node 21
#

$

&

143




















% #%$

%$%% 























  %$


  % #  %% 






  %$






% #%$

%$%% 

The 84 linear algebraic equations can be written in the form Ax = d, where A is a 84 84

matrix, x is the vector of size 84 1 containing the variables to be determined, and d is also
a vector of size 84 1. The variables can be written as

>% #

%$ %% %&     % # %$ %%  %&  @

The Gauss elimination method can be used to solve these 84 linear algebraic equations. The
non-zero elements of the matrix A are
A(1,1) = 20005.9992CB1, A(1,5) = 2.0008, A(2,2) = 20005.9992CA1CC1, A(2,6) = 2.0008
A(3,3) = 20005.9992CB1, A(3,7) = 2.0008, A(4,4) = 20005.9992, A(4,8) = 2.0008, A(5,1)
= 2.0004, A(5,5) = 2.0008CB2, A(5,9) = 0.0004, A(6,2) = 2.0004, A(6,6) = 2.0008CA2CC2,
A(6,10) = 0.0004, A(7,3) = 2.0004, A(7,7) = 2.0008CB2, A(7,11) = 0.0004, A(8,4) = 2.0004,
A(8,8) = 2.0008, A(8,12) = 0.0004, A(9,5) = 2.0004, A(9,9) = 2.0008CB3, A(9,13) = 0.0004,
A(10,6) = 2.0004, A(10,10) = 2.0008CA3CC3, A(10,14) = 0.0004, A(11,7) = 2.0004,
A(11,11) = 2.0008CB3, A(11,15) = 0.0004, A(12,8) = 2.0004, A(12,12) = 2.0008, A(12,16)
= 0.0004, A(13,9) = 2.0004, A(13,13) = 2.0008CB4, A(13,17) = 0.0004, A(14,10) = 2.0004,
A(14,14) = 2.0008CA4CC4, A(14,18) = 0.0004, A(15,11) = 2.0004, A(15,15) = 2.0008CB4,
A(15,19) = 0.0004, A(16,12) = 2.0004, A(16,16) = 2.0008, A(16,20) = 0.0004, A(17,13) =

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Introduction to Numerical Methods in Chemical Engineering

2.0004, A(17,17) = 2.0008CB5, A(17,21) = 0.0004, A(18,14) = 2.0004, A(18,18) = 2.0008

CA5CC5, A(18,22) = 0.0004, A(19,15) = 2.0004, A(19,19) = 2.0008CB5, A(19,23) = 0.0004,
A(20,16) = 2.0004, A(20,20) = 2.0008, A(20,24) = 0.0004, A(21,17) = 2.0004, A(21,21) =
2.0008CB6, A(21,25) = 0.0004, A(22,18) = 2.0004, A(22,22) = 2.0008CA6CC6, A(22,26) =
0.0004, A(23,19) = 2.0004, A(23,23) = 2.0008CB6, A(23,27) = 0.0004, A(24,20) = 2.0004,
A(24,24) = 2.0008, A(24,28) = 0.0004, A(25,21) = 2.0004, A(25,25) = 2.0008CB7, A(25,29)
= 0.0004, A(26,22) = 2.0004, A(26,26) = 2.0008CA7CC7, A(26,30) = 0.0004, A(27,23) =
2.0004, A(27,27) = 2.0008CB7, A(27,31) = 0.0004, A(28,24) = 2.0004, A(28,28) = 2.0008,
A(28,32) = 0.0004, A(29,25) = 2.0004, A(29,29) = 2.0008CB8, A(29,33) = 0.0004, A(30,26)
= 2.0004, A(30,30) = 2.0008CA8CC8, A(30,34) = 0.0004, A(31,27) = 2.0004, A(31,31) =
2.0008CB8, A(31,35) = 0.0004, A(32,28) = 2.0004, A(32,32) = 2.0008, A(32,36) = 0.0004,
A(33,29) = 2.0004, A(33,33) = 2.0008CB9, A(33,37) = 0.0004, A(34,30) = 2.0004, A(34,34)
= 2.0008CA9CC9, A(34,38) = 0.0004, A(35,31) = 2.0004, A(35,35) = 2.0008CB9, A(35,39)
= 0.0004, A(36,32) = 2.0004, A(36,36) = 2.0008, A(36,40) = 0.0004, A(37,33) = 2.0004,
A(37,37) = 2.0008CB10, A(37,41) = 0.0004, A(38,34) = 2.0004, A(38,38) = 2.0008CA10
CC10, A(38,42) = 0.0004, A(39,35) = 2.0004, A(39,39) = 2.0008CB10, A(39,43) = 0.0004,
A(40,36) = 2.0004, A(40,40) = 2.0008, A(40,44) = 0.0004, A(41,37) = 2.0004, A(41,41) =
2.0008CB11, A(41,45) = 0.0004, A(42,38) = 2.0004, A(42,42) = 2.0008CA11CC11, A(42,46)
= 0.0004, A(43,39) = 2.0004, A(43,43) = 2.0008CB11, A(43,47) = 0.0004, A(44,40) = 2.0004,
A(44,44) = 2.0008, A(44,48) = 0.0004, A(45,41) = 2.0004, A(45,45) = 2.0008CB12, A(45,49)
= 0.0004, A(46,42) = 2.0004, A(46,46) = 2.0008CA12CC12, A(46,50) = 0.0004, A(47,43) =
2.0004, A(47,47) = 2.0008CB12, A(47,51) = 0.0004, A(48,44) = 2.0004, A(48,48) = 2.0008,
A(48,52) = 0.0004, A(49,45) = 2.0004, A(49,49) = 2.0008CB13, A(49,53) = 0.0004, A(50,46)
= 2.0004, A(50,50) = 2.0008CA13CC13, A(50,54) = 0.0004, A(51,47) = 2.0004, A(51,51) =
2.0008CB13, A(51,55) = 0.0004, A(52,48) = 2.0004, A(52,52) = 2.0008, A(52,56) = 0.0004,
A(53,49) = 2.0004, A(53,53) = 2.0008CB14, A(53,57) = 0.0004, A(54,50) = 2.0004, A(54,54)
= 2.0008CA14CC14, A(54,58) = 0.0004, A(55,51) = 2.0004, A(55,55) = 2.0008CB14,
A(55,59) = 0.0004, A(56,52) = 2.0004, A(56,56) = 2.0008, A(56,60) = 0.0004, A(57,53) =
2.0004, A(57,57) = 2.0008CB15, A(57,61) = 0.0004, A(58,54) = 2.0004, A(58,58) = 2.0008
CA15CC15, A(58,62) = 0.0004, A(59,55) = 2.0004, A(59,59) = 2.0008CB15, A(59,63) =
0.0004, A(60,56) = 2.0004, A(60,60) = 2.0008, A(60,64) = 0.0004, A(61,57) = 2.0004,
A(61,61) = 2.0008CB16, A(61,65) = 0.0004, A(62,58) = 2.0004, A(62,62) = 2.0008CA16
CC16, A(62,66) = 0.0004, A(63,59) = 2.0004, A(63,63) = 2.0008CB16, A(63,67) = 0.0004,
A(64,60) = 2.0004, A(64,64) = 2.0008, A(64,68) = 0.0004, A(65,61) = 2.0004, A(65,65) =
2.0008CB17, A(65,69) = 0.0004, A(66,62) = 2.0004, A(66,66) = 2.0008CA17CC17, A(66,70)
= 0.0004, A(67,63) = 2.0004, A(67,67) = 2.0008CB17, A(67,71) = 0.0004, A(68,64) = 2.0004,
A(68,68) = 2.0008, A(68,72) = 0.0004, A(69,65) = 2.0004, A(69,69) = 2.0008CB18, A(69,73)
= 0.0004, A(70,66) = 2.0004, A(70,70) = 2.0008CA18CC18, A(70,74) = 0.0004, A(71,67) =
2.0004, A(71,71) = 2.0008CB18, A(71,75) = 0.0004, A(72,68) = 2.0004, A(72,72) = 2.0008,
A(72,76) = 0.0004, A(73,69) = 2.0004, A(73,73) = 2.0008CB19, A(73,77) = 0.0004, A(74,70)
= 2.0004, A(74,74) = 2.0008CA19CC19, A(74,78) = 0.0004, A(75,71) = 2.0004, A(75,75) =
2.0008CB19, A(75,79) = 0.0004, A(76,72) = 2.0004, A(76,76) = 2.0008, A(76,80) = 0.0004,
A(77,73) = 2.0004, A(77,77) = 2.0008CB20, A(77,81) = 0.0004, A(78,74) = 2.0004, A(78,78)
= 2.0008CA20CC20, A(78,82) = 0.0004, A(79,75) = 2.0004, A(79,79) = 2.0008CB20,
A(79,83) = 0.0004, A(80,76) = 2.0004, A(80,80) = 2.0008, A(80,84) = 0.0004, A(81,77) =

Tubular Reactor with Axial Dispersion

145

2.0008, A(81,81) = 2.0008CB21, A(82,78) = 2.0008, A(82,82) = 2.0008CA21CC21, A(83,79)

= 2.0008, A(83,83) = 2.0008CB21, A(84,80) = 2.0008, A(84,84) = 2.0008
The nonzero right hand side terms are given in augmented matrix A form as
A(1,85) = 20004, A(2,85) = 20004, A(3,85) = CA1CB1, A(4,85) = CB1CC1, A(7,85) =
CA2CB2, A(8,85) = CB2CC2, A(11,85) = CA3CB3, A(12,85) = CB3CC3, A(15,85) = CA4CB4,
A(16,85) = CB4CC4, A(19,85) = CA5CB5, A(20,85) = CB5CC5, A(23,85) = CA6CB6, A(24,85)
= CB6CC6, A(27,85) = CA7CB7, A(28,85) = CB7CC7, A(31,85) = CA8CB8, A(32,85) =
CB8CC8, A(35,85) = CA9CB9, A(36,85) = CB9CC9, A(39,85) = CA10CB10, A(40,85) =
CB10CC10, A(43,85) = CA11CB11, A(44,85) = CB11CC11, A(47,85) = CA12CB12, A(48,85) =
CB12CC12, A(51,85) = CA13CB13, A(52,85) = CB13CC13, A(55,85) = CA14CB14, A(56,85) =
CB14CC14, A(59,85) = CA15CB15, A(60,85) = CB15CC15, A(63,85) = CA16CB16, A(64,85) =
CB16CC16, A(67,85) = CA17CB17, A(68,85) = CB17CC17, A(71,85) = CA18CB18, A(72,85) =
CB18CC18, A(75,85) = CA19CB19, A(76,85) = CB19CC19, A(79,85) = CA20CB20, A(80,85) =
CB20CC20, A(83,85) = CA21CB21, A(84,85) = CB21CC21
Program 7.2 for the solution of the above problem is given in the Appendix. The concentration
of various species along the length of the reactor is obtained using the Gauss elimination
method. The results are shown in Table 7.6.
Table 7.6

Results in Example 7.3

Node number

x (m)

CA

CB

CC

CD

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21

0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0

0.999925
0.745869
0.602852
0.516040
0.460355
0.423163
0.397574
0.379579
0.366717
0.357413
0.350622
0.345632
0.341947
0.339216
0.337186
0.335674
0.334547
0.333705
0.333075
0.332604
0.332252

0.999918
0.681292
0.474505
0.336482
0.241939
0.175791
0.128732
0.094823
0.070151
0.052067
0.038739
0.028875
0.021552
0.016103
0.012040
0.009008
0.006742
0.005048
0.003780
0.002831
0.002121

0.000060
0.189554
0.268800
0.304402
0.321230
0.329465
0.333583
0.335665
0.336717
0.337242
0.337497
0.337612
0.337659
0.337671
0.337668
0.337659
0.337649
0.337639
0.337630
0.337623
0.337617

0.000006
0.064577
0.129276
0.181438
0.221265
0.251137
0.273464
0.290175
0.302718
0.312168
0.319310
0.324724
0.328835
0.331960
0.334332
0.336124
0.337466
0.338454
0.339160
0.339638
0.339996

EXAMPLE 7.4

Solve Example 7.3 by making 3 parts of the reactor of length 3 m.

Solution Since three parts are made, therefore the total number of nodes is 4.
The coefficients of equation 1 (node 1, species A) are:

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Introduction to Numerical Methods in Chemical Engineering

Coefficient of % #

  




 %$  



   %$

Coefficient of CB1 = 0
Coefficient of CC1 = 0
Coefficient of CD1 = 0
Coefficient of % #

  






Coefficient of CB2 = 0
Coefficient of CC2 = 0
Coefficient of CD2 = 0

W  W
Right hand side of equation 1 = 
&  'Z % #

KP



 
 

 

The coefficients of equation 2 (node 1, species B) are:

Coefficient of CA1 = 0
Coefficient of %$

  




 % #  %%  



   % #  %%

Coefficient of CC1 = 0
Coefficient of CD1 = 0
Coefficient of CA2 = 0
Coefficient of %$

  






Coefficient of CC2 = 0
Coefficient of CD2 = 0

W  W
Right hand side of equation 2 = 
&  'Z %$

KP




  

 

The coefficients of equation 3 (node 1, species C) are:

Coefficient of CA1 = 0
Coefficient of CB1 = 0
Coefficient of %%

Coefficient of CD1 = 0
Coefficient of CA2 = 0
Coefficient of CB2 = 0

  




 %$  



   %$

Tubular Reactor with Axial Dispersion

Coefficient of %% 

  






Coefficient of CD2 = 0
Right hand side of equation 3 = CA1CB1
The coefficients of equation 4 (node 1, species D) are:
Coefficient of CA1 = 0
Coefficient of CB1 = 0
Coefficient of CC1 = 0
Coefficient of %&

  





  

 

Coefficient of CA2 = 0
Coefficient of CB2 = 0
Coefficient of CC2 = 0

  





Right hand side of equation 4 = CB1CC1
Coefficient of %&

The coefficients of equation 5 (node 2, species A) are:

Coefficient of % #
Coefficient of CB1
Coefficient of CC1
Coefficient of CD1
Coefficient of % #

 



=0
=0
=0






  



  %$ 


   %$

Coefficient of CB2 = 0
Coefficient of CC2 = 0
Coefficient of CD2 = 0
Coefficient of % #

 



Coefficient of CB3 = 0
Coefficient of CC3 = 0
Coefficient of CD3 = 0
Right hand side of equation 5 = 0.
The coefficients of equation 6 (node 2, species B) are:
Coefficient of CA1 = 0

147

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Introduction to Numerical Methods in Chemical Engineering

Coefficient of %$

 


Coefficient of CC1
Coefficient of CD1
Coefficient of CA2


=0
=0
=0

Coefficient of %$





  



  % #  %% 


   % #  %% 

Coefficient of CC2 = 0
Coefficient of CD2 = 0
Coefficient of CA3 = 0

 



Coefficient of CC3 = 0
Coefficient of CD3 = 0
Right hand side of equation 6 = 0.

Coefficient of %$

The coefficients of equation 7 (node 2, species C) are:

Coefficient of CA1 = 0
Coefficient of CB1 = 0
Coefficient of %%
Coefficient of CD1
Coefficient of CA2
Coefficient of CB2
Coefficient of %% 

 



=0
=0
=0






  



  % $


   %$

Coefficient of CD2 = 0
Coefficient of CA3 = 0
Coefficient of CB3 = 0

 



Coefficient of CD3 = 0
Right hand side of equation 7 = CA2CB2.

Coefficient of %% 

The coefficients of equation 8 (node 2, species D) are:

Coefficient of CA1 = 0

Tubular Reactor with Axial Dispersion

Coefficient of CB1 = 0
Coefficient of CC1 = 0
Coefficient of %&
Coefficient of CA2
Coefficient of CB2
Coefficient of CC2
Coefficient of %& 

 


=0
=0
=0






  


Coefficient of CA3 = 0
Coefficient of CB3 = 0
Coefficient of CC3 = 0




 

 



Right hand side of equation 8 = CB2CC2
The coefficients of equation 13 (node 4, species A) are:
Coefficient of %&

Coefficient of % #

  






Coefficient of CB3 = 0
Coefficient of CC3 = 0
Coefficient of CD3 = 0
Coefficient of % #
Coefficient
Coefficient
Coefficient
Right hand

  



  %$ 


   %$

of CB4 = 0
of CC4 = 0
of CD4 = 0
side of equation 13 = 0.

The coefficients of equation 14 (node 4, species B) are:

Coefficient of CA3 = 0
Coefficient of %$

  






Coefficient of CC3 = 0
Coefficient of CD3 = 0
Coefficient of CA4 = 0
Coefficient of %$

  



  % #   %% 


   % #  %% 

149

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Introduction to Numerical Methods in Chemical Engineering

Coefficient of CC4 = 0
Coefficient of CD4 = 0
Right hand side of equation 14 = 0
The coefficients of equation 15 (node 4, species C) are:
Coefficient of CA3 = 0
Coefficient of CB3 = 0
Coefficient of %% 

  






Coefficient of CD3 = 0
Coefficient of CA4 = 0
Coefficient of CB4 = 0
Coefficient of %% 

  



  %$


   %$

Coefficient of CD4 = 0
Right hand side of equation 15 = CA4CB4.
The coefficients of equation 16 (node 4, species D) are:
Coefficient of CA3 = 0
Coefficient of CB3 = 0
Coefficient of CC3 = 0
Coefficient of %&

  






Coefficient of CA4 = 0
Coefficient of CB4 = 0
Coefficient of CC4 = 0

  


 


Right hand side of equation 16 = CB4CC4.
Coefficient of %& 

Thus the set of equations for concentration of species A, B, C, and D at nodes 1 to 4 can be
written in the block tridiagonal form as

$

#


%

$
#

%
$

#

 :

 :

% :

$ : 

& 

&
&


&

Tubular Reactor with Axial Dispersion

where

:

% #
%
$
%%

%&

:

% # 
%
$
%% 

%& 

:

% # 
%
$
%% 

%& 

For node 1

$

  %$


  % #  %%



%


























&



  % $




% #%$

%$%%

For node 2

#




















$

  % $ 

%


  % #   %% 




  %$ 

























151

152

Introduction to Numerical Methods in Chemical Engineering

&

% #%$

%$%% 

#




















$

  % $

For node 3

%

&
For node 4


  % #  %% 







  %$ 






















% #%$

%$%% 

#




















$

  % $ 


  % #   %% 




  % $ 






Tubular Reactor with Axial Dispersion

&

153

% # %$ 

%$ %% 

The 16 linear algebraic equations can be written in the form Ax = d, where A is a 16 16

matrix, x is the vector of size 16 1 containing the variables to be determined, and d is also
a vector of size 16 1. The variables can be written as

>% #

%$ %% %&     % # 

%$ 

%% 

%&  @

The Gauss elimination method can be used to solve these 16 linear algebraic equations (see
Program 1.2 given in the Appendix). The results are given in Table 7.7.
Table 7.7

Results in Example 7.4

Node number

x (m)

CA

CB

CC

CD

1
2
3
4

0
1
2
3

0.999933
0.652683
0.503350
0.430048

0.999927
0.532064
0.296694
0.170485

0.000060
0.226697
0.289994
0.310390

0.000006
0.120620
0.206656
0.259562

Exercises
7.1

Consider a reaction A B carried out in a tubular reactor. The differential equation

for species A along the length of the tubular reactor of length 10 m is

&

F % #
FZ

W

F% #
 M% #
FZ

The boundary conditions are

At x = 0 (inlet)
W% #

KP

W% #  &

F% #
FZ

At x = 10 m (exit)
F% #

FZ
A fluid medium comprising initially only A flows through the reactor with a mean
axial velocity u = 1 m/s. The axial dispersion coefficient, D = 104 m2/s and the rate
constant of the reaction is 0.1 s1. The inlet concentration CA,in =1 mol/m3. Make
10 parts of the reactor. List the tridiagonal set of equations and determine the
concentration of A at various positions along the length of the tubular reactor.
(Ans: The tridiagonal set of equations are

154

Introduction to Numerical Methods in Chemical Engineering

 
% #

%
  

#






   % #

  % #

CA1 = CA(0.0) = 0.999991

CA3 = CA(2.0) = 0.826440
CA5 = CA(4.0) = 0.683009
CA7 = CA(6.0) = 0.564471
CA9 = CA(8.0) = 0.466506
CA11 = CA(10.0) = 0.385549
7.2









CA2 = CA(1.0) = 0.909083

CA4 = CA(3.0) = 0.751310
CA6 = CA(5.0) = 0.620918
CA8 = CA(7.0) = 0.513156
CA10 = CA(9.0) = 0.424097

Consider a reaction A B carried out in a tubular reactor. The differential

equation for species A along the length of the tubular reactor of length 10 m is

&

F % #


FZ
The boundary conditions are

W

F% #

 M% #
FZ

At x = 0 (inlet): W% #

KP

W%  &
#

F% #
FZ

F% #

FZ
A fluid medium comprising initially only A flows through the reactor with a mean
axial velocity u = 1 m/s. The axial dispersion coefficient, D = 104 m2/s and rate
constant of the reaction is 0.1 m3/mol-s. The inlet concentration CA,in = 1 mol/m3.
Make 10 parts of the reactor. List the tridiagonal set of equations and determine the
concentration of A at various positions along the length of the tubular reactor.
(Ans: The tridiagonal set of equations are

At x = 10 m (exit):

  



% #



   % #  

CA1 = CA(0.0) =
CA3 = CA(2.0) =
CA5 = CA(4.0) =
CA7 = CA(6.0) =
CA9 = CA(8.0) =
CA11 = CA(10.0)





    % #


0.999991
0.844719
0.730059
0.642133
0.572688
= 0.516529





   % #

CA2 = CA(1.0) = 0.916073

CA4 = CA(3.0) = 0.783356
CA6 = CA(5.0) = 0.683363
CA8 = CA(7.0) = 0.605478
CA10 = CA(9.0) = 0.543192

% #
% #







%#
%#

 



Chapter 8

Chemical Reaction and Diffusion

in Spherical Catalyst Pellet
Chemical reaction and diffusion in a spherical catalyst pellet is a boundary value problem,
because at the surface of the pellet the concentration of the species is known and at the centre
of the pellet the gradient of concentration is zero. The finite difference method is used for the
numerical solution of the first and second order reactions along with the diffusion term in a
spherical catalyst pellet. The numerical solution under nonisothermal conditions is also
discussed in this chapter.

8.1 First Order Reaction

The differential equation for diffusion and reaction in a spherical catalyst pellet is given by

F %  F%
&  
 M% 
(8.1)
FT
T FT

It is assumed that the pellet is isothermal and therefore the rate constant is also fixed. D is the
effective binary diffusivity of A within the catalyst pellet. The boundary conditions are
at r = R
(8.1b)
C = CS
and at r = 0

dC
dr

(8.1b)

where CS is the concentration at the surface of the spherical catalyst pellet.

EXAMPLE 8.1

The chemical reaction and diffusion in a spherical catalyst pellet is given by

&

F % #
FT

 F% #
&
 M% #
T
FT

where D is the effective binary diffusivity of A within the catalyst pellet. The pellet is
isothermal. The concentration at the surface of the spherical catalyst pellet is 1 mol/m3, thus
the boundary conditions are
155

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Introduction to Numerical Methods in Chemical Engineering

at r = R

CA = 1

at r = 0

F% #

FT
The radius of the catalyst pellet is 1.0 cm. Make 100 parts of the radius. Take the rate constant,
k = 10-3 s1 and D = 109 m2/s. Determine the concentration of species A at various nodes along
the radius of the catalyst pellet.

Solution

The differential equation for diffusion and reaction in a spherical catalyst pellet is

F %
FT
It is given that

M
&

 
 

 F% M
 %
T FT &

  m2.

 
  m. The schematic

diagram of the spherical catalyst pellet is shown in Fig. 8.1. The first node is labelled 0 and
therefore the last node is the 100th node as 100 parts are made.

The radius is 1 cm = 102 m and 100 parts are made, thus 'T

100
r= R

C100 = 1
0
r=0
Fig. 8.1

Diffusion and reaction in spherical catalyst pellet.

The boundary conditions are:

at r = 1 cm
r=0

C=1
F%
FT

Chemical Reaction and Diffusion in Spherical Catalyst Pellet

157

Discretizing the differential equation at node i, we get

%   %   %

 %   % 

  %
O 'T
 'T

%   %   % 


%   %      'T %
O

'T
K

%   %   % 
K


%   %    %
O
K




%     %  %    
O
O

At node 0 (centre of spherical catalyst pellet) the differential equation becomes

K

F %
FT 

   %

Discretizing, we get
%  %  %
 
'T 


  %

  %  %  %     'T  %

  %  %  %   %

At node 0,

F%
FT

 ; thus

%  %
 'T

 , and therefore C1 = C1. Therefore the above equation

becomes

  %  %   %

%  %

At node 1 (m = 1)




%     %  %   
O
O

%  %  


At node 2 (m = 2)

At node 3 (m = 3)




%    %  %  






%    %  %  



158

Introduction to Numerical Methods in Chemical Engineering

At node 99 (m = 99)

Since C100 = 1, we get




%    %  %  




%    %


  





%    % 



The 100 equations can be written in tridiagonal form as



%
      




%

      


%

%
      

















      

%



       %

    %












 

The solution can be obtained by modifying the parameters ai (i = 2 to N), bi (i = 1 to N) and

ci (i = 1 to N 1) in Program 1.1 given in the Appendix. The results for nodes 77 to 99 are
presented in Table 8.1 given in the next section.

8.2 Second Order Reaction

The differential equation for diffusion and second order reaction in a spherical catalyst pellet
is given by

F %  F%

&  

 M%
(8.2)
FT

T FT

It is assumed that the pellet is isothermal and therefore the rate constant is also fixed. D is the
effective binary diffusivity of A within the catalyst pellet. The boundary conditions are
At r = R:

C = CS

At r = 0:

F%
FT

where CS is the concentration at the surface of the spherical catalyst pellet.

Chemical Reaction and Diffusion in Spherical Catalyst Pellet

EXAMPLE 8.2

159

The chemical reaction and diffusion in a spherical catalyst pellet is given by

F % #

 F% #

&
 M% # 
T
FT
FT
where D is the effective binary diffusivity of A within the catalyst pellet. The pellet is
isothermal. The concentration at the surface of the spherical catalyst pellet is 1 mol/m3; thus
the boundary conditions are
&

At r = R:

CA = 1
F% #
FT

At r = 0:

The radius of the catalyst pellet is 1.0 cm. Make 100 parts of the radius. Take the rate constant,
k = 103 m3/mol-s and D = 109 m2/s. Determine the concentration of species A at various
nodes along the radius of the catalyst pellet.
Solution

The differential equation for diffusion and reaction in a spherical catalyst pellet is

F %
FT
It is given that

M
&

 




 F% M 
 %
T FT &

  .

 
  m. The schematic

diagram of the spherical catalyst pellet is given in Fig. 8.1. The first node is labelled 0 and
therefore the last node is the 100th node as 100 parts are made. Discretizing the differential
equation at node i, we get

The radius is 1 cm = 102 m and 100 parts are made, thus 'T

%   %   %

 %   % 
 
  %
O 'T
 'T

%   %   % 


%   %     'T % 
O

'T
K

%   %   % 
K


%   %    % 
O
K




%     %    %   %    
O
O

At node 0 (centre of spherical catalyst pellet) the differential equation becomes

K

F %
FT 

   % 

160

Introduction to Numerical Methods in Chemical Engineering

Discretizing, we get
%  %  %
 
'T 

 
  %


  %  %  %     'T %

F%
At node 0,
FT
becomes


  %  %  %   % 
%  %
 , and therefore C1 = C1. Therefore the above equation
 ; thus 
 'T

  %  %   %

%    %   %

At node 1 (m = 1)




%        %  %  %   
O
O

   %  %  %  

At node 2 (m = 2)




%       %  %  %  



At node 3 (m = 3)
At node 99 (m = 99)

Since C100




%       %  %  %  






%       %  %  %  





= 1, we get



%       %  %   




%       %  %



The 100 equations can be written in tridiagonal form as

  %

 



  %

 


     %

 





%

%


 
%

%

  %






 

Chemical Reaction and Diffusion in Spherical Catalyst Pellet

161

It is seen that the coefficient matrix also depends on the concentrations. Therefore, to start the
program the concentrations are assumed, the coefficients are calculated and TDMA is used to
determine the new concentrations. At these concentrations the coefficients are re-calculated
and TDMA is used to determine the new concentrations. The procedure is repeated till there
is no change in the concentration profile. Program 8.1 for the solution of the above problem
is given in the Appendix. The results for nodes 77 to 99 are presented in Table 8.1.
Table 8.1 Concentration of reactants in spherical catalyst pellet for first and second order reactions under
isothermal condition
Node number
99
98
97
96
95
94
93
92
91
90
89
88
87
86
85
84
83
82
81
80
79
78
77

r (cm)

C (first order reaction)

0.99
0.98
0.97
0.96
0.95
0.94
0.93
0.92
0.91
0.90
0.89
0.88
0.87
0.86
0.85
0.84
0.83
0.82
0.81
0.80
0.79
0.78
0.77

0.914015
0.835509
0.763826
0.698366
0.638586
0.583988
0.534119
0.488564
0.446948
0.408925
0.374184
0.342438
0.313425
0.286908
0.262670
0.240513
0.220257
0.201735
0.184799
0.169310
0.155144
0.142186
0.130331

C (second order reaction)

0.930360
0.868043
0.812053
0.761560
0.715865
0.674377
0.636593
0.602084
0.570482
0.541468
0.514766
0.490138
0.467374
0.446290
0.426724
0.408536
0.391599
0.375800
0.361041
0.347233
0.334296
0.322160
0.310759

8.3 Nonisothermal Conditions

The differential equation for diffusion and reaction in a spherical catalyst pellet is given by

F %  F%
&  
 M 6  % 
FT
T FT

where the rate constant is a function of the temperature, or

M 6 

' 65

M  65  GZR 
6  

465

(8.3)

(8.4)

162

Introduction to Numerical Methods in Chemical Engineering

Consider the case of a non-isothermal first order reaction A B occurring in the interior of
a spherical catalyst pellet. We wish to compute the effect of internal heat and mass transfer
resistance upon the reaction rate and the concentration and temperature profiles within the
pellet. The concentration profile CA(r) is governed by the mole balance
F% # 
F 
(8.5)
T &# FT  T M  6  % # 
FT

where DA is the effective binary diffusivity of A within the pellet. If k is the effective thermal
conductivity of the pellet, the temperature profile T(r) is governed by the energy balance
F  F6 


T M
 T  '* TZP M  6  % #
FT
FT

(8.6)

Neglecting external heat and mass transfer resistance, we have known values of the
concentration and temperature at the surface, r = R: CA(R) = CAS and T(R) = TS. Also, at the
centre of the pellet, r = 0:
rate constant is

F% #
FT

 and


F6
FT

 . The temperature dependence of the

T

' 65

M  65  GZR 
(8.7)
6  

465

If we assume constant DA, k and '*TZP the problem reduces to a single ordinary differential

equation. Dividing the energy balance equation by '* TZP and adding to the mole balance
equation, we get
M 6 

Integrating, we get

F% # F 
F 
M
F6
T &#

T


FT
FT FT

 '* TZP FT

F% #
M
F6
T  &#

%


FT
 '* TZP FT

2
where C1 is the constant of integration. Dividing by r gives

%
F
M
&#% # 
6


FT
 '* TZP T

From the symmetry boundary condition C1 = 0 and a second integration

&#% # 

 '* 

TZP

%

(8.8)

(8.9)

(8.10)

(8.11)

where C2 is the constant of integration. At the surface, we get the value of constant C2 as
%

& # % #5 

 '* 

TZP

65

(8.12)

Chemical Reaction and Diffusion in Spherical Catalyst Pellet

163

Comparing Eqs. (8.11) and (8.12), we get

&#% # 


 '* TZP

& # % #5 

 '* 

TZP

65

(8.13)

Thus there exists the following linear relation between CA(r) and T(r):

&# '* TZP
% #  T   % #5
(8.14)

M
Thus only the mole balance equation has to be solved. Thus, if we assume constant DA, k and

'* TZP , we can show that at any point along the radius the temperature and concentration of
the reactant are related by Eq. (8.14). A parameter is defined as

6  T   65


&  '* TZP %5

M65

(8.15)

From Eq. (8.14), we get

6
65




& '* TZP
 %  %5 
M65

Therefore

65
6




&'* TZP
 %  %5 
M65

Subtracting one from both the sides, we get

65

6


& '* TZP
 %  %5 
M65


& '* TZP

 %  %5 
M65

(8.16)

Let us define a parameter as

H

If CS = 1, then C
becomes


&  '* TZP

M65

M 6 

'
465

(8.17)

and the expression for rate constant given in Eq. (8.7)

HC  %  %5 
M 65  GZR 

  C  %  %5 

(8.18)

164

Introduction to Numerical Methods in Chemical Engineering

EXAMPLE 8.3 Diffusion and reaction take place in a non-isothermal spherical catalyst pellet
of radius 1 cm. The rate constant of the reaction k(TS) = 103 s1 and effective diffusivity of
species, D = 109 m2/s. Make 100 parts of the radius and determine the concentration within
the catalyst pellet. The concentration at the surface of the spherical catalyst pellet CS = 1 mol/
m3. Take b = 1 and g = 1.
Solution The differential equation for diffusion and reaction in a non-isothermal spherical
catalyst pellet is

F %
FT

 F% M
 %
T FT &

where
HC  %  %5 
M 65  GZR 

  C  %  %5 

Thus the differential equation becomes

M 6 

F %
FT

It is given that

M  65 

HC  %  %5 
 F% M  65 
%

GZR 
  C %  % 

T FT
&
5

 

&



  m2.



 
  m. The schematic

diagram of the spherical catalyst pellet is given in Fig. 8.1. The boundary conditions are

The radius is 1 cm = 102 m and 100 parts are made; thus 'T
At r = 1 cm:

C =1
F%
FT

At r = 0:

Since b = 1, g = 1, and CS = 1 mol/m3, the differential equation becomes

F %
FT

  %
 F%
   GZR
%
T FT
  %

Discretizing the differential equation at node i, we get

%   %   %
K

'T 

%
 %   % 


  GZR   %
O 'T
 'T

K
K

%   %   % 
K

  %

%   %     GZR
%
O

  %

Chemical Reaction and Diffusion in Spherical Catalyst Pellet

165

  %


  GZR
 %    
O

  %

At node 0 (centre of spherical catalyst pellet), the differential equation becomes



%     %
O

F %

  %
   GZR
%
FT 
  %

Discretizing, we get

%  %  %
 
'T 

  %


  GZR   % %

  %
  %  %  %    GZR

  %

At node 0,
becomes

F%
FT

 ; thus

%  %
 'T

%

 , and therefore C1 = C1. Therefore the above equation

  %
  %  %    GZR
%

  %

  %
  GZR

  %

%  %




At node 1 (m = 1)

%


%       GZR
O

%

%  %    
O

  %

  GZR
%  %   

  %

At node 2 (m = 2)

  %



%      GZR
%  %   



  %
At node 3 (m = 3)

  %



%      GZR
%  %   



  %

At node 99 (m = 99)

  %



%      GZR
%  %   

  %


166

Introduction to Numerical Methods in Chemical Engineering

Since C100 = 1, we get

  %


%      GZR
%


  %




The 100 equations can be written in tridiagonal form as


  GZR




%
%

%
%

 
  GZR

 



%
%





















  GZR




%
%



%
%





  GZR





%
%









It is seen that the coefficient matrix also depends on the concentrations. Therefore, to start the
program the concentrations are assumed, the coefficients are calculated and TDMA is used to
determine the new concentrations. At these concentrations the coefficients are re-calculated
and TDMA is used to determine the new concentrations. The procedure is repeated till there
is no change in the concentration profile. Program 8.2 for the solution of the above problem
is given in the Appendix. The results for nodes 77 to 100 are presented in Table 8.2.
Solve Example 8.3 for b = 10 and g = 1.

EXAMPLE 8.4
Solution

Since b = 10, g = 1, and CS = 1 mol/m3, the differential equation becomes

F %
FT

  %
 F%
   GZR
%
T FT
  %

Discretizing the differential equation at node i, we get

%   %   %
K

'T

  %
 %   % 


  GZR   %
O'T
 'T

%   %   % 
K

  %

%   %     GZR
%
O

  %

  %


  GZR
 %    
O

  %

At node 0 (centre of spherical catalyst pellet), the differential equation becomes



%     %
O

F %

  %
   GZR
%
FT
  %

Chemical Reaction and Diffusion in Spherical Catalyst Pellet

167

Discretizing, we get

  %


  GZR   %

%

  %
  %  %  %    GZR

  %

%

%  %  %
 
'T 

At node 0,
becomes

F%
FT

 ; thus

%  %
 'T

, and therefore C1 = C1. Therefore the above equation

  %
  %  %    GZR

  %

  %
  GZR

  %

%

%  %

At node 1 (m = 1)

  %



%       GZR
%  %    
O
O

  %

  %

  GZR
%  %   

  %

At node 2 (m = 2)

  %



%      GZR
%  %   

  %


At node 3 (m = 3)

  %



%      GZR
%  %   



  %

At node 99 (m = 99)

  %



%      GZR
%  %   



  %

Since C100 = 1, we get

  %


%      GZR
%


  %




168

Introduction to Numerical Methods in Chemical Engineering

The 100 equations can be written in tridiagonal form as

 

%
%

   

   

GZR






 

%
%

   

   

GZR

%
%





















%
%

   
  GZR

   







 

%
%




%
%

  

GZR

  









It is seen that the coefficient matrix also depends on the concentrations. Therefore, to start the
program the concentrations are assumed, the coefficients are calculated and TDMA is used to
determine the new concentrations. At these concentrations the coefficients are re-calculated
and TDMA is used to determine the new concentrations. The procedure is repeated till there
is no change in the concentration profile. Program 8.2 can be modified to solve this problem.
The results for nodes 77 to 100 are presented in Table 8.2.
Table 8.2

Concentration of reactant in spherical catalyst pellet under non-isothermal conditions for first
order reaction for b = 1 and b = 10

Node number
100
99
98
97
96
95
94
93
92
91
90
89
88
87
86
85
84
83
82
81
80
79
78
77

r (cm)

C (b = 1)

C (b = 10)

1.00
0.99
0.98
0.97
0.96
0.95
0.94
0.93
0.92
0.91
0.90
0.89
0.88
0.87
0.86
0.85
0.84
0.83
0.82
0.81
0.80
0.79
0.78
0.77

1.000000
0.901657
0.803074
0.713959
0.633761
0.561849
0.497557
0.440217
0.389179
0.343828
0.303586
0.267922
0.236345
0.208414
0.183724
0.161913
0.142658
0.125665
0.110677
0.097460
0.085810
0.075543
0.066497
0.058529

1.000000
0.873620
0.752422
0.646573
0.554827
0.475639
0.407470
0.348888
0.298610
0.255496
0.218553
0.186914
0.159829
0.136650
0.116820
0.099585
0.085352
0.072949
0.062345
0.053280
0.045531
0.038908
0.033247
0.028409

Chemical Reaction and Diffusion in Spherical Catalyst Pellet

169

Exercises
8.1

The chemical reaction and diffusion in a spherical catalyst pellet is given by

F % #

 F% #
&
 M% # 
T
FT
FT
where D is the effective binary diffusivity of A within the catalyst pellet. The pellet
is isothermal. The concentration at the surface of the spherical catalyst pellet is 1
mol/m3 thus the boundary conditions are:
&

At r = R:

CA = 1
F% #
FT

At r = 0:

The radius of the catalyst pellet is 1.0 cm. Make 10 parts of the radius. Take the
rate constant, k = 0.1 s1 and D = 109 m2/s. Determine the concentration of species
A at various positions along the radius of the catalyst pellet.
(Ans: The tridiagonal set of equations are



      






 

CA0
CA2
CA4
CA6
CA8

=
=
=
=
=

CA(0.0)
CA(0.2)
CA(0.4)
CA(0.6)
CA(0.8)

=
=
=
=
=

% #

% #




    % #

    % #


0.000000
0.000000
0.000000
0.000000
0.000120

CA1
CA3
CA5
CA7
CA9

=
=
=
=
=

CA(0.1)
CA(0.3)
CA(0.5)
CA(0.7)
CA(0.9)








 
=
=
=
=
=

0.000000
0.000000
0.000000
0.000001
0.010894

Distance (in cm) is measured from the centre of the spherical pellet.
8.2

The chemical reaction and diffusion in a spherical catalyst pellet is given by

&

F % #
FT

 F% #

&
 M% #
T
FT

where D is the effective binary diffusivity of A within the catalyst pellet. The pellet
is isothermal. The concentration at the surface of the spherical catalyst pellet is
1 mol/m3, thus the boundary conditions are
At r = R:
At r = 0:

CA = 1
F% #
FT

170

Introduction to Numerical Methods in Chemical Engineering

The radius of the catalyst pellet is 1.0 cm. Make 10 parts of the radius. Take the
rate constant, k = 0.1 m3/mol-s and D = 109 m2/s. Determine the concentration of
species A at various positions along the radius of the catalyst pellet.
(Ans: The tridiagonal set of equations are

  % # 

% 

  % #   

# 



% #




 

     % #
 

% # 





% #   



  % # 

CA0 = CA(0.0) = 0.001837

CA1 = CA(0.1) = 0.001894
CA3 = CA(0.3) = 0.002419
CA2 = CA(0.2) = 0.002073
CA4 = CA(0.4) = 0.003030
CA5 = CA(0.5) = 0.004131
CA6 = CA(0.6) = 0.006286
CA7 = CA(0.7) = 0.011211
CA9 = CA(0.9) = 0.096965
CA8 = CA(0.8) = 0.025902
Distance (in cm) is measured from the centre of the spherical pellet.
8.3

Diffusion and reaction take place in a non-isothermal spherical catalyst pellet of

radius 1 cm. The rate constant of the reaction k(TS) = 0.1 s1 and effective
diffusivity of species, D = 109 m2/s. Make 10 parts of the radius and determine the
concentration within the catalyst pellet. The concentration at the surface of the
spherical catalyst pellet, CS = 1 mol/m3. Take b = 1 and g = 1.
(Ans: The tridiagonal set of equations are


   GZR




%
%

CA0
CA2
CA4
CA6
CA8

%
%

 
   GZR

 



%

%











   GZR




=
=
=
=
=

CA(0.0)
CA(0.2)
CA(0.4)
CA(0.6)
CA(0.8)

=
=
=
=
=

0.000000
0.000000
0.000000
0.000000
0.000045




CA1
CA3
CA5
CA7
CA9

=
=
=
=
=

%
%







   GZR


CA(0.1)
CA(0.3)
CA(0.5)
CA(0.7)
CA(0.9)

=
=
=
=
=

%
%

0.000000
0.000000
0.000000
0.000000
0.006659

Distance (in cm) is measured from the centre of the spherical pellet.



%

%







Chapter 9

One-Dimensional Transient
Heat Conduction
The numerical solution of one-dimensional transient heat conduction in a rectangular slab,
cylinder, and sphere is discussed in this chapter using the finite difference method. The onedimensional transient heat conduction in a rectangular slab is given by

6
V

 6

(9.1)

Z 

In a cylinder it is given by
6

6
V

6
V

 6
T T

(9.2)

 6

T T

(9.3)

and in a sphere it is given by

6

M
. Discretization is carried out using the forward in time and central in space
S%2
(FTCS) difference scheme. The explicit, implicit and CrankNicolson discretizations are
discussed. An example of one-dimensional transient diffusion is also discussed. Von Neumann
stability analysis, which is used to determine the criteria under which the explicit scheme is
stable, is also discussed.

where

9.1

Classification of Partial Differential Equations

Consider the two-dimensional partial differential equation (PDE)

#

When B2 4AC <

When B2 4AC =
When B2 4AC >
A summary of the

 H
Z 

$

 H
 H
H
H
%  &
'
 (H  )
Z [
Z
[
[

0, characteristics do not exist and it is elliptic PDE.

0, one set of characteristics exists and it is parabolic PDE.
0, two sets of characteristics exist and it is hyperbolic PDE.
above result with examples is presented in Table 9.1.
171

(9.4)

172

Introduction to Numerical Methods in Chemical Engineering

Table 9.1

Classification of partial differential equations

PDE

6
Z 

Parameters

6
[

6
6
B 
V
Z

A=1
B=0
C=1

1-D wave equation

W
W
(a > 0)
C

V
Z

(9.5)

B2 4AC = 0
Parabolic

A=1

 (a > 0)

B2 4AC = 4 < 0
Elliptic

A = a
B=0
C=0

Classification of PDE

B2 4AC = 4a2 > 0

B=0
C = a2

Hyperbolic

The coefficients in the 1D wave equation are determined using the following. Differentiating
Eq. (9.5) with respect to x, we get

 W
 W
C 
VZ
Z

Differentiating Eq. (9.5) with respect to t, we get

W
V 

C

 W
V Z

Combining the above two equations, we get

 W
V 

 C

 W
Z 

A linear PDE is one in which A, B, C, D, E, F, and G are functions of x and y only.

9.2 Explicit and Implicit Discretization

Consider conduction in a one-dimensional rectangular slab. The partial differential equation is
[see Eq. (9.1)]

6
V

 6
Z 

Using the forward in time and central in space explicit difference scheme, we get
6KP   6KP
'V

6KP   6KP   6KP




 'Z  

(9.6)

One-Dimensional Transient Heat Conduction

173

If the solution is known at time n, then it is very easy to determine the solution at time
n + 1 using the explicit method.

6KP
where /

B'V

 'Z  

/ 6KP   6KP  6KP  6KP




(9.7)

Thus if the temperature at all the nodes is known at time t, the temperature at time t + Dt can
be computed and from this temperature at time t + Dt, the temperature at time t + 2Dt can be
computed. Thus the temperature at any required time can be computed. Thus the values of all
the nodes can be updated to compute the temperature profile at the required time. But there
is a disadvantage, which is that explicit discretization is not stable for all values of Dt and Dx.
It is stable only when

'V

 'Z 




(9.8)


is not satisfied,
 'Z  
then convergence shall not be obtained and the solution shall start diverging. The implicit
method is an unconditionally stable method and the implicit discretization of Eq. (9.1) is given
by

Thus the choice of Dt and Dx is not independent. If the condition

6KP   6KP
'V

'V



6KP   6KP   6KP 



 'Z 

(9.9)

When the temperature at time t is known, then to calculate the temperature at time t + Dt the
tridiagonal set of linear algebraic equations is solved. Thus 6KP are known and 6KP  are
calculated. Thus marching in time can be carried out to obtain the temperature at various nodes
at the next time step for the parabolic PDE.

9.3 Crank-Nicolson Discretization

Consider conduction in a rectangular slab. The partial differential equation is [see Eq. (9.1)]

6
V
CrankNicolson discretization is given by
6KP   6KP
'V

 6
Z 

B 6KP   6KP   6KP 





 'Z 

6KP   6K P   6KP



'Z 
 

(9.10)

In the CrankNicolson method the discretization of space term is carried out using the central
difference scheme at time n and at time n + 1 and taking the mean of the two. It is an

174

Introduction to Numerical Methods in Chemical Engineering

unconditionally stable method. It is an more accurate than the implicit method. The accuracy
of the implicit method is O(Dt,Dx2), whereas that of CrankNicolson is O(Dt2,Dx2). The central
difference scheme is not used in time because it would require high storage, as there would
be terms of three typesT n+1, T n, T n1.

9.4 Von Neumann Stability Analysis

Von Neumann stability analysis is also called the Fourier method. The method shall be
described for the one-dimensional transient heat conduction [see Eq. (9.1)]

6
 6
B 
V
Z
Discretizing using the FTCS explicit scheme, we get at node i [see Eq. (9.6)]
6KP 

6KP 

B'V

'Z 

6 

P
K 

 6KP   6KP


Let the exact solution of this equation be D. This is the solution that would be obtained using
a computer with infinite accuracy (infinite storage of each variable). Let the numerical solution
on a real machine with finite accuracy be N. Then, round-off error = N D = e. Thus, N =
D + e and the above equation becomes
&KP   F KP   &KP  F KP
'V

&KP  F KP   &KP  F KP    &KP  F KP




'Z 

(9.11)

Since the exact solution D must satisfy the difference equation, the same is true of the error,
that is
P 

FK

 F KP
'V

F P  F KP   F KP

B K 


'Z

(9.12)

Thus the exact solution D and the error e must both satisfy the same difference equation.
Consider a distribution of errors at any time. The error e (x, t) can be written as a series of the
form
F  Z V 

CV

KM

OZ

(9.13)

where
MO

OQ
.

m = 0, 1, 2, , M

(9.14)

M is the number of intervals (Dx units long) contained in length L. Since the difference
equation is linear, superposition may be used and we may examine the behaviour of a single
term of the series. Thus, when the finite difference equation (FDE) is linear, it is sufficient to

One-Dimensional Transient Heat Conduction

175

investigate only one component of the Fourier series. The error is in the form of Fourier series.
Consider the term
F O  Z V 

G G
CV

where km is real but a may be complex. Substituting F

C V  'V
G   GKMO Z  G CV GKMO Z

where /

B'V
'Z

 Z V 

G G
CV

KM O Z

into Eq. (9.12), we get

KM Z  'Z 
KM Z  'Z 
/ G CV G O 
  G CV GKMO Z  G CV G O 

. If we divide by G G
CV

KM O Z

(9.16)

, we get

/ G O'  G O '  

G ' 
C

(9.15)

KM O Z

and if we utilize the relation

KM

KM

G C  G C


(9.17)

   /  EQU C  

(9.18)

EQU C

we get
G C'V

where

MO 'Z

(9.19)

  EQU C


(9.20)

We know
UKP 

Thus
G C'V

   / UKP 

(9.21)

Since F KP  G C'V F KP for each frequency present in the solution for the error, it is clear that if
GC'V is less than or equal to one, a general component of the error will not grow from one
time step to the next. Stability means that error should not grow. This requires that
   / UKP 

The factor    / UKP

P 

C


d

(9.22)

FK

(representing P ) is called the amplification factor. If the sign on


FK
the left hand side of Eq. (9.22) is either positive or negative, two conditions result.
For positive sign
 / UKP 

For negative sign

 / UKP 

C


!

(9.23)

(9.24)
d

Since M is positive, the first condition is always satisfied. The second inequality is satisfied

176

Introduction to Numerical Methods in Chemical Engineering


, which is the stability requirement. Thus for the explicit finite difference

B'V
equation 6KP  6KP   6KP   6KP   6KP to be stable


'Z
B'V d 
(9.25)
'Z  
The two-dimensional transient heat conduction equation is

only if / d

6

6
V

Z 

6

[ 

(9.26)

Discretizing at node (i, j) using the FTCS explicit scheme, we get

6KPL


6KPL 


B'V
'Z

6 

P
K  L

 6KP  L  6KPL 



B'V
'[ 

P
K  L 

 6KPL   6KPL


(9.27)

From the von Neumann stability analysis, we get the explicit FTCS discretization to be stable
when

B'V
'Z

B'V
'[




(9.28)

When Dx = Dy = D, the discretized form of Eq. (9.26) becomes

6KPL


6KPL 


B'V
'

6 
K



 6KP




 6KPL   6KPL   6KPL



(9.29)

and the stability criterion for explicit discretization becomes

B'V
'

9.5




(9.30)

Transient Conduction in Rectangular Slab

One-dimensional transient heat conduction in a rectangular slab using the implicit method is
described in the example below.
EXAMPLE 9.1 Consider transient heat conduction in a rectangular slab. The partial
differential equation is

6
V

 6
Z 

The total width of the rectangular slab is 0.8 cm. Initially the temperature is uniform at 20C.
The temperature of the end faces of the rectangular slab is made 300C at t = 0 s. Use implicit
discretization and take Dx = 0.1 cm, Dt = 0.1 s, and a = 105 m2/s. List the tridiagonal system

One-Dimensional Transient Heat Conduction

177

of equations and determine the temperature at the centre and the intermediate points of the slab
up to 3.1 s.
Solution

The schematic diagram of the rectangular slab is shown in Fig. 9.1.

Symmetry
Fig. 9.1

Wall at 300C
Transient heat conduction in rectangular slab.

Using forward in time and central in space implicit difference scheme, we get
6KP   6KP
'V

6KP  6KP
where /

B'V

 'Z  



6KP   6KP   6KP 



 'Z 


/ 6KP  6KP  6KP



 /  6KP     /   6KP    /  6KP 




 6KP

 /  6P     /   6P    /  6P 

 6P

 /  6P     /   6P    /  6P 

 6P

 /  6P     /   6P    /  6P 

 6P

At node 2
At node 3
At node 4

where T5 = 300C. At node 1 the finite difference equation is

 /  6P     /   6P    /  6P 

 6P

178

Introduction to Numerical Methods in Chemical Engineering

where 0 is a hypothetical node to the left of node 1. Since at x = 0 (node 1) the symmetry
condition is satisfied, we get

6
Z

 ; thus

6P   6P 
 'Z

n 1
 and so T0

T2n 1 .

Thus at i = 1, we get

  /   6P    /  6P 

 6P

The following tridiagonal set of linear algebraic equations is obtained:

 /  
6 P 


/




6P 
/
 /  

/
P 

/
/ 6
 /  


P 


/
 /   6

6P

6P

6P

6   /

where the old values are at time n and the computed values are at time n + 1. Here a = 105 m2/s,
Dt = 0.1 s, Dx = 0.1 cm, 6P 6P 6P 6P  C, T5 = 300C. Thus
/

B'V

 'Z 

  
  

P 
   6

P 
 
  6


 
 6P 

  6 P 
 

6P
P

6

6

6  

At time t = 0, 6P 6P 6P 6P  C and the solution by TDMA is obtained at time
t = 0.1s. These become the old values for solution by TDMA at t = 0.2 s and so on. Note that
in this sort of discretization a tridiagonal matrix is bound to get formed because, for
discretization at node i, use is made of the values at nodes i 1, i + 1, and i. Program 9.1 for
the solution of the above problem is given in the Appendix. The coefficient matrix parameters
are constant, but the right hand side of the linear algebraic equations each time is updated. The
results of Program 9.1 are presented in Table 9.2.

One-Dimensional Transient Heat Conduction

Table 9.2

179

Results of Program 9.1

Time (s)

T1

T2

T3

T4

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3.0
3.1

31.91
53.21
78.59
104.35
128.55
150.45
169.87
186.90
201.78
214.72
225.98
235.75
244.24
251.60
258.00
263.55
268.36
272.54
276.17
279.32
282.05
284.42
286.48
288.27
289.82
291.16
292.33
293.34
294.22
294.99
295.65

37.87
63.86
91.28
117.22
140.66
161.40
179.57
195.42
209.21
221.20
231.60
240.64
248.48
255.29
261.19
266.32
270.77
274.63
277.98
280.89
283.42
285.61
287.51
289.16
290.59
291.84
292.91
293.85
294.66
295.37
295.98

61.70
100.49
131.40
156.04
176.20
193.09
207.45
219.79
230.44
239.65
247.64
254.56
260.57
265.78
270.30
274.22
277.63
280.58
283.15
285.38
287.31
288.99
290.44
291.70
292.80
293.75
294.58
295.29
295.92
296.46
296.92

127.23
175.91
202.44
219.49
231.90
241.66
249.71
256.50
262.31
267.32
271.65
275.40
278.66
281.48
283.93
286.05
287.89
289.49
290.88
292.09
293.13
294.04
294.83
295.51
296.10
296.62
297.07
297.45
297.79
298.08
298.33

EXAMPLE 9.2 A brick wall with a thickness of 0.5 m is initially at a uniform temperature
of 300 K. At time t = 0 the left surface is maintained at 425 K and right at 600 K. Determine
the time required for its centre temperature to reach 425 K. Use implicit discretization and take
Dx = 0.05 m, a = 105m2/s, and Dt = 1.0 s.
Solution

The schematic diagram is shown in Fig. 9.2.

Initial temperature = 300
425

600
1

Fig. 9.2

6
Example 9.2.

11

180

Introduction to Numerical Methods in Chemical Engineering

In a rectangular slab

6
6
B 
V
Z
Discretizing using implicit FTCS at node i, we get
6 P   6 P
'V
K

6 P   6 P   6 P 



'Z 

Dx = 0.05 m and Dt = 1.0 s; thus

6KP   6KP

'V
'Z

 
 

 . Therefore

 6KP   6KP   6KP 





6 P   6 P   6 P 



6P

6P   6P   6P 

6P

At node 2

Since T1 = 425, we get

6P   6P 

6P   

At node 3
6P   6P   6P 

6P

P
6P   6P   6

6P

P
P
6P   6  6

P
6

At node 9
At node 10
Since T11 = 600, we get
P
6P   6

P
6   

Thus the unknowns are T2 to T10. The tridiagonal set of 9 linear algebraic equations is
P 
 
6
P 

6
 






  6P 



 6 P 




6P  
P

6



6 P

P
6  

P
Initially 6P 6P 6P 6P 6P 6P 6P 6P 6  . After every iteration the time
is incremented by 1 s. We have to determine the time when T6 = 425. Program 9.1 can

One-Dimensional Transient Heat Conduction

181

be modified by changing the coefficients and the following solution is obtained at 2865 s:
T2 = 415.87, T3 = 409.24, T4 = 407.40, T5 = 412.24, T6 = 425.06, T7 = 446.44, T8 = 476.11,
T9 = 512.95, and T10 = 555.07.

9.6 Transient Conduction in Cylinder

One-dimensional transient heat conduction in a cylinder using the implicit method is described
in the example below.
EXAMPLE 9.3 Consider a cylinder of radius 0.4 cm. Initially the temperature is uniform at
20C. The temperature of the cylinder surface is made 300C at t = 0 s. Use implicit
discretization and take Dr = 0.1 cm, Dt = 0.1 s, and a = 105m2/s. List the tridiagonal system
of equations and determine the temperature at the centre and the intermediate points of the
cylinder up to 2.1 s.
Solution

The partial differential equation is

6
V

6

 6
T T

Using the forward in time and central in space implicit difference scheme, we get
6KP   6KP
'V
6 P   6 P
K

where /

B'V

 ' T 

6 P   6 P   6 P 
K 
K 
K

 'T  

 6KP   6KP 



O 'T
 'T

/ 6 P   6 P   6 P  
6 P   6 P 




O

.
6 P   6 P
K

/
/


6 P  / 
 6 P  / 
  /6 P 



O
O
K

/ P 
/ P 

P 
 / 
/ 
6     /   6
6 

O
O
K

6P
K

At node 2 (m = 1)
/ P 
/ P 

P 
/  6    /   6  /  6




 6P

/ P 
/ P 

P 
/   6    /   6  /   6

 6P

At node 3 (m = 2)

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Introduction to Numerical Methods in Chemical Engineering

At node 4 (m = 3)
/ P 
/ P 

P 
/   6    /   6  /   6

 6P

6
where T5 = 300C. On using LHospitals rule at node 1, the PDE becomes
V
implicit FTCS to discretize, we get

 6KP   6KP   6KP 




6KP   6KP
'V
6K

 / 

P 

 6K

6KP 


/

 'T 

6KP 


   /   6

P 

6
T 

. Using

 6KP   6KP 

  / 

6KP 


 6P
K

At i = 1, we get

 /  6P     /   6P    /  6P 

 6P

where 0 is a hypothetical node to the left of node 1.

6 P   6P 
6
, 
T
 'T
Thus at i = 1, we get

Since at r = 0,

 ; thus 6P 

6P  .

  /   6P     /  6P 

 6P

The following tridiagonal set of linear algebraic equations is obtained.

/


 /  
P

6P  6
/

P

 /  

6P  6


/
 / 6 P  6P


 /  





P  6 P   / 
6

/



 /    

where the old values are at time n and the computed values are at time n + 1. Here a = 105 m2/s,
Dt = 0.1 s, Dr = 0.1 cm, 6P 6P 6P 6P  C, T5 = 300C. Thus

B'V

 'T 

  

  

 

P 


 6

P 


 6
 


 
 6P 


  6 P 


6P

6

6

6  

One-Dimensional Transient Heat Conduction

183

At time t = 0, 6P 6P 6P 6P  C, and the solution by TDMA is obtained at time
t = 0.1 s. These become the old values for solution by TDMA at t = 0.2 s and so on. Program 9.1
can be modified to solve this problem and the results are given in Table 9.3.
Table 9.3

Results in Example 9.3

Time (s)

T1

T2

T3

T4

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1

48.29
91.65
135.90
174.33
205.21
229.08
247.17
260.72
270.83
278.34
283.92
288.06
291.13
293.40
295.09
296.34
297.26
297.95
298.46
298.83
299.11

55.37
102.48
146.97
183.93
212.93
235.05
251.69
264.11
273.36
280.22
285.32
289.09
291.89
293.97
295.51
296.65
297.49
298.12
298.58
298.93
299.18

81.30
137.51
180.31
211.78
234.84
251.79
264.29
273.53
280.36
285.43
289.18
291.96
294.02
295.54
296.67
297.51
298.13
298.60
298.94
299.19
299.38

145.91
203.48
234.56
253.66
266.43
275.39
281.85
286.56
290.04
292.60
294.49
295.90
296.94
297.71
298.28
298.70
299.02
299.25
299.42
299.55
299.64

The number of parts can be increased to obtain a better solution.

9.7 Transient Conduction in Sphere

One-dimensional transient heat conduction in a sphere using the implicit method is described
in the example below.
EXAMPLE 9.4 Consider a sphere of radius 0.4 cm. Initially the temperature is uniform
at 20C. The temperature of the sphere surface is made 300C at t = 0 s. Use implicit
discretization and take Dr = 0.1 cm, Dt = 0.1 s, and a = 105 m2/s. List the tridiagonal system
of equations and determine the temperature at the centre and the intermediate points of the
sphere up to 1.4 s.
Solution

The partial differential equation is

6
V

6

T 

 6

T T

184

Introduction to Numerical Methods in Chemical Engineering

Using the forward in time and central in space implicit difference scheme, we get
6 P   6 P   6 P 
K 
K 
K

6KP   6KP
'V

 'T  

 6KP   6KP 



O 'T
 'T

6 P   6 P

 P 



/ 6 P   6 P   6 P  
6   6 P 



O

6 P   6 P

/
/


6 P  /   6 P  /    /6 P 



O
O

where /

B'V

 ' T 

.
K

/
/


6 P  /   6 P  /   6 P    /  



O
O
K

6P

At node 2 (m = 1)
6P   /  /   6P      6P    /  

 6P

At node 3 (m = 2)
/
/

6P  /   6P  /   6P    /  




 6P

At node 4 (m = 3)
/
/

6P  /   6P  /   6P    /  




 6P

where T5 = 300C

6
6
  .
V
T
Again, using the implicit FTCS, we get
At node 1 the PDE becomes

6 P   6 P
'V
K

6KP   6KP


 6 P   6 P   6 P 


K

 'T 


 / 6KP   6KP   6KP 



6 P   /   6 P   /   6 P    /  



6P

6P   /   6P   /   6P    /  

 6P

At i =1, we get
where 0 is a hypothetical node to the left of node 1.
At r = 0,

6
T

 ; thus

6P   6P 
 'T

 and so 6P 

6P  .

One-Dimensional Transient Heat Conduction

185

Thus at i = 1, we get
6P    /   6P    /  

 6P

The following tridiagonal set of linear algebraic equations is obtained:

/


 /  
P 

6

 /  
/


6 P 

/ 
/

 /  

6P 



/



 /   6P 

6P

6

6

P /

6   

where the old values are at time n and the computed values are at time n + 1. Here a = 105
m2/s, Dt = 0.1 s, Dr = 0.1 cm, 6P 6P 6P 6P  C, T5 = 300C. Thus






B'V

  

 'T 

  

 

P 
 6
P 

 6

 
 6P 


  6 P 









6P

6

6

6  

At time t = 0, 6P 6P 6P 6P  C and the solution by TDMA is obtained at
time t = 0.1 s. These become the old values for solution by TDMA at t = 0.2 s and so on.
Program 9.1 can be modified to solve this problem and the results are given in Table 9.4.
Table 9.4

Results in Example 9.4

Time (s)

T1

T2

T3

T4

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4

65.71
126.67
180.57
220.93
248.79
267.24
279.18
286.82
291.67
294.74
296.68
297.91
298.68
299.17

73.33
136.83
189.55
227.66
253.44
270.32
281.17
288.09
292.48
295.25
297.00
298.11
298.81
299.25

100.00
168.57
215.92
246.71
266.33
278.75
286.60
291.55
294.67
296.64
297.88
298.66
299.16
299.47

162.22
224.87
256.27
273.58
283.71
289.85
293.64
296.00
297.48
298.41
299.00
299.37
299.60
299.75

186

Introduction to Numerical Methods in Chemical Engineering

9.8 Transient Diffusion in Sphere

One-dimensional transient diffusion in a sphere using the implicit method is described in the
example below.
EXAMPLE 9.5 Consider a 6.52 mm diameter bead which contains 10 mg of a certain drug
in gel matrix. The diffusion coefficient of drug in gel matrix is 3.0 107 cm2/s. The drug is
immediately swept away once it reaches the bulk solution, that is, CS = 0. The transient
diffusion of the drug is given by
%
V

%  %
&  
T T
T

The boundary conditions are

%
T

At r = 0:

t 0

At r = R:

C = CS = 0

At t = 0:

C = C0

t>0

The initial condition is

0rR

Determine the concentration of the drug in the centre of the bead after 3, 12, 24, and 48 h.
Make 10 parts of the radius from r = 0 to r = R. Take Dt = 1.0 s.
Solution

The radius of the bead is 0.326 cm and the initial concentration of the drug in the

 OI
 mg/cm3. The schematic diagram of the bead from r = 0 to r = R with


Q4

10 parts is shown in Fig. 9.3.

bead is =

Initial concentration
= 68.9 mg/cm3
r= R

T 
F%

FT

C =0
0

5
Fig. 9.3

Example 9.5.

In a sphere
%
V

%  %
&  
T T
T

10

One-Dimensional Transient Heat Conduction

187

Discretizing using FTCS at node i, we get

% P   % P
'V
K

% P   % P   % P 
 % P   % P



& 


O 'T
 'T
'T 

& 'V P 
 P 

 % P   % P 
%
%   % P


 
O
'T

Dr = 0.0326 cm and Dt = 1.0 s. Thus

% P   % P
K

&

  
 

'V
'T 

  

Thus at node i
 P 

   % P  % P   % P 

%   % P



O

% P   % P
K




% P    % P   % P  



O
O

Using LHospitals rule, the PDE at node 0 becomes

K

% P
K

%
%
& 
V
T
Discretizing the above equation at node 0, we get
P
P
%   %
'V

&
'T

P
P
 %   %

At node 0,

%
T

 ; thus

%  %
 'T

% 

P 


P
P
 %   % 

  % 

P 


P
P
 %   %  

 , and therefore C1 = C1. Thus the above equation

becomes

  %   %  
%  %  % 

P
P
 %   %

P
 % 

Thus the equation at node 0 is

P 


P


P
P
%   % 

P 


P 


P 


P
%

At node 1


P
P
P
%     %   %   




P
%

188

Introduction to Numerical Methods in Chemical Engineering

At node 2


P
%



P
P
P
%     %   %   




P
%



P
P
P
%     %   %  




P
%

P
%   


P
P
 %   %   

At node 8

At node 9

Since C10 = 0, the equation for node 9 becomes


P
P
%     % 

P
%

The above set of 10 equations (at nodes 0 to 9) can be written in tridiagonal form as



   




    




  





  


% P 

P
% 


P
    % 


% P 
 

P
%

P
%



% P


P
%

P
P
P
P
P
P
P
P
P
P
Initially % % % % % % % % % %  mg/cm3. At the completion of an iteration, time is incremented by 1 s. Program 9.2 for the solution of the above
problem is given in the Appendix. The following concentration of drug at the centre of the
bead is obtained from Program 9.2: after 3 h the concentration is 62.39 mg/cm3; after 12 h the
concentration is 26.36 mg/cm3, after 24 h the concentration is 7.99 mg/cm3; and after 48 h the
concentration is 0.73 mg/cm3.

Exercises
9.1

Consider transient heat conduction in a rectangular slab. The total width of the
rectangular slab is 1 cm. Initially the temperature is uniform at 25C. The
temperature of the end-faces of the rectangular slab is made 300C at t = 0 s. Use
implicit discretization and take Dx = 0.1 cm, Dt = 0.1 s, and a = 105 m2/s. List the
tridiagonal system of equations and determine the temperature at the centre and the
intermediate points of the slab after 5 s.
(Ans: The tridiagonal set of equations is

One-Dimensional Transient Heat Conduction

 











P 
6
6 P 

6P 

 6 P 


 P 
6

189

6P

6

6

6

6  

T1 = T(0.0) = 87.43
T2 = T(0.1) = 96.08
T3 = T(0.2) = 122.44
T4 = T(0.3) = 166.98
T5 = T(0.4) = 228.16.
Distance (in cm) is measured from the centre.
9.2

Consider a cylinder of radius 0.5 cm. Initially the temperature is uniform at 25C.
The temperature of the cylinder surface is made 300C at t = 0 s. Use implicit
discretization and take Dr = 0.1 cm, Dt = 0.1 s, and a = 105 m2/s. List the
tridiagonal system of equations and determine the temperature at the centre and the
intermediate points of the cylinder after 5 s.
(Ans: The tridiagonal set of equations is



6 P 
 



6 P 


 


6 P 
 
 


 6P 

  P 
6

T1 = T(0.0) = 150.81
T2 = T(0.1)
T3 = T(0.2) = 179.46
T4 = T(0.3)
T5 = T(0.4) = 256.06
Distance (in cm) is measured from the centre.
9.3

6P

6

6

6

P 
6  

= 158.06
= 213.45

Consider a sphere of radius 0.5 cm. Initially the temperature is uniform at 25C.
The temperature of the sphere surface is made 300C at t = 0 s. Use implicit
discretization and take Dr = 0.1 cm, Dt = 0.1 s, and a = 105 m2/s. List the
tridiagonal system of equations and determine the temperature at the centre and the
intermediate points of the sphere after 5 s.
(Ans: The tridiagonal set of equations is
P



6P  6
P

  
P 

6 6

P  6 P
  

6 


 P  6 P




 6 

  6P  6P  

190

Introduction to Numerical Methods in Chemical Engineering

T1 = T(0.0) = 200.21
T2 = T(0.1) = 205.72
T3 = T(0.2) = 221.68
T4 = T(0.3) = 245.88
T5 = T(0.4) = 274.07
Distance (in cm) is measured from the centre.
9.4

Consider a concrete wall 0.5 m thick. Initially the temperature is uniform at 20C.
The temperature of one surface of the wall x = 0 is suddenly raised to 80C and
the right surface at x = 0.5 m remains always at 20C. Use implicit discretization
and take Dx = 0.1 m, Dt = 10 s, and a = 1.25 105 m2/s. List the tridiagonal
system of equations and determine the temperature distribution throughout the slab
after 1 h.
(Ans: The tridiagonal set of equations are
P 


6
P 
 
6


 
 6P 

  6 P 

6P  
P

6

6

6  

T2 = T(0.1) = 64.06
T3 = T(0.2) = 49.66
T4 = T(0.3) = 37.70
T5 = T(0.4) = 28.13
Distance (in m) is measured from surface at 80C.
9.5

A large flat slab of clay is to be dried. The slab is dried from both sides, is 4 cm
thick and has an initial uniform water concentration of 0.5 g of water per cm3. The
movement of water within the clay occurs by diffusion. It is known that, with the
proposed drying conditions, the drying will occur in the constant rate period at a
rate of 0.1 g/cm2-h of water as long as the surface moisture concentration remains
above 0.2257 g of water per cm3. Use implicit discretization and take Dx = 0.2 cm,
Dt = 0.01 h, and D = 0.25 cm2/h. List the tridiagonal system of equations and
determine the duration of the constant rate period and the distribution of water
within the clay at the end of the constant rate period. The partial differential
equation is

%
V

&

 %
Z 

and the boundary conditions are: at x = 0 (centre), %  and at x = 2 cm,

Z
%
&

Z
(Ans: The solution of the problem is obtained by calculating the time required for
the surface concentration to fall to 0.2257 g/cm3. This concentration is obtained at
1.5 h. The tridiagonal set of equations is

One-Dimensional Transient Heat Conduction

P 


%
P 

  

%






P
   %

  % P 



At t = 1.5 h:
C1 = C(0.0) = 0.4947
C2 = C(0.2) = 0.4937
C5 = C(0.8) = 0.4738
C4 = C(0.6) = 0.4841
C7 = C(1.2) = 0.4342
C8 = C(1.4) = 0.4011
C10 = C(1.8) = 0.2983
C11 = C(2.0) = 0.2257
Distance (in cm) is measured from the centre.

P
%

 %



% P



P
%  

C3 = C(0.4) = 0.4904
C6 = C(1.0) = 0.4578
C9 = C(1.6) = 0.3563

191

Chapter 10

Two-Dimensional Steady and

Transient Heat Conduction
Two-dimensional steady heat conduction is given by
6
Z 

6

[ 

(10.1)

This is an elliptic partial differential equation and the temperature T(x, y) must satisfy this
equation as well as the boundary conditions along the entire boundary of the plate. Twodimensional transient heat conduction is given by [see Eq. (9.26)]
6
V

6

Z 

6

[ 

This is a parabolic partial differential equation. Relaxation techniques are used for the
numerical solution of elliptic equations, whereas marching in time is used for parabolic
equations. The numerical solution of two-dimensional steady heat conduction is carried out by
the GaussSeidel, RedBlack GaussSeidel, and Alternating Direction Implicit (ADI)
methods. The boundary conditions like convection, exterior corner with convection, interior
corner with convection and insulation are discussed in this chapter. The numerical solution of
two-dimensional transient heat conduction is discussed using ADI method, which is an implicit
method and is therefore unconditionally stable. It is also called line-by-line TDMA.

10.1 Discretization in Two-Dimensional Space

Consider a two-dimensional body as shown in Fig. 10.1. Around each node a control volume
is made. If there is no net accumulation of mass in the body, then the mass balance equation
at a node can be interpreted as indicating that the net mass entering through all the four sides
of the control volume is zero. The depth of the body in the z-direction may be taken to be
unity. The temperature in the control volume is uniform and under steady conditions the heat
input through all the sides of the control volume is zero. The heat inputs are given by terms
6
6
6
6
like  M#
and  M#
. Therefore the derivatives
and
have to be evaluated at the
[
Z
[
Z
control volume boundaries. The temperature gradients around the control volume (i, j) may be
written as
192

Two-Dimensional Steady and Transient Heat Conduction

6
Z
6
Z
6
[
6
[


K  L


K L

(10.2)

'Z
6

6

K L

(10.3)

 L

'Z

K L

6



(10.4)

K L

'[




K L

L

K L

6   6 

193

K L

6

K L



(10.5)

'[




i, j + 1

K L  

Dy
i, j

i 1, j

i + 1, j

K  L


K  L

K L  


i, j 1
Dx
Fig. 10.1

Control volume around node.

The second derivatives may be written as

6
Z


K


6
[

K L


K  L


K L

6
[

6
Z


K L 



L


6
Z

Z




 L

K L

'Z


K


6
[

[

 

K L


L


6   6   6   6 




6

K L



K L

 6  6  6
K L

'[

K L

K L



6   6   6 

6

K L

'Z 

K L



 6

K L

'[




 6 

K L

(10.6)

(10.7)

194

Introduction to Numerical Methods in Chemical Engineering

 6 6
Discretizing the equation

Z  [ 
zero, we get

 for any interior node in which the source term is

6   6   6 
K

'Z

K L

6

K L



 6

K L

'[



 6 

K L

(10.8)

For Dx = Dy, we get

6   6   6   6 
K

K L

K L



 6

K L



 6 

K L

or
6

6   6   6 
K

K L



 6

K L



K L

(10.9)

10.2 Gauss-Seidel Method

In calculating Ti,j the values of the temperatures on the right hand side of Eq. (10.9) consist
initially of estimated values or known boundary values. However, as soon as an appropriate
temperature at a node is calculated, this calculated value supersedes the estimated value and
is used as the temperature at that point until it is, in turn, superseded by a new calculated value.
Thus the latest calculated values of the temperatures are always used in calculating newer and
better values.
Consider nodes in a two-dimensional space, with the bottom left node being (0,0) and the
top right node being (10,10). Suppose that node (0,0) is updated first followed by node (1,0),
(2,0),, (10,0), (0,1), (1,1),, (10,1), (0,2), (1,2),, (10,2),, (0,10), (1,10),, (10,10).
Then, by the time the value of Ti,j is updated, the values Ti1,j and Ti,j1 have already been
updated. On using the GaussSeidel method, Eq. (10.9) becomes

6KPL


6KP  L  6KPL  6KPL   6KPL



 

(10.10)

10.3 Relaxation Parameter

The temperature taken at the beginning of an iteration is Tn and the new temperature computed
during the iteration is T n+1. Now, for the next iteration the temperature can be taken to be either
T n+1, between Tn and T n+1, or more than T n+1, and is given by
The parameter
Table 10.1.

6 P  6 P  X'6 P 
(10.11)
is known as the relaxation parameter. The various cases are described in

Two-Dimensional Steady and Transient Heat Conduction

195

Table 10.1 Relaxation parameter values

Temperature
taken at the
beginning of
iteration
100
100
100

New
temperature
computed
during iteration

Temperature
taken at the
beginning of
next iteration

110
110
110

Relaxation
parameter

110
105
115

1
0.5
1.5

Type of
Relaxation

GaussSeidel
Underrelaxation
Overrelaxation

The method is convergent only for 0 < w < 2. For overrelaxation the relaxation parameter lies
between 1 and 2 and for underrelaxation between 0 and 1. When w = 1, it becomes the Gauss
Seidel method. The optimum value of w is different for each problem. It has to be determined
by hit and trial.

10.4 RedBlack GaussSeidel Method

When the GaussSeidel method is used, the nodes are processed down the rows (or columns)
or the mesh is divided into black and red nodes as shown in Fig. 10.2. This method for solution
of elliptic PDE is RedBlack GaussSeidel. Both GaussSeidel and RedBlack GaussSeidel
are pointwise methods. The Alternating Direction Implicit (ADI) method described in the next
section is a line-by-line method.

RBRBRBRBRBRBRBRB
BRBRBRBRBRBRBRBR
RBRBRBRBRBRBRBRB
BRBRBRBRBRBRBRBR
RBRBRBRBRBRBRBRB
BRBRBRBRBRBRBRBR
RBRBRBRBRBRBRBRB
BRBRBRBRBRBRBRBR
Fig. 10.2

Redblack nodes in two-dimensional space.

The nodes surrounding the black node are all red and the nodes surrounding the red node are
all black. The surrounding nodes are those nodes which are to the east, west, north and south
of a node. The other four nodes are called the corner nodes of node (i, j). Consider again the
finite difference equation (10.9):
6

6   6 
K

L

 L

6

K L



6

K L




Red points depend only on the black points and black points depend only on the red points.
Thus we can carry out one half-sweep updating the red points and then another half-sweep
K L

196

Introduction to Numerical Methods in Chemical Engineering

updating the black points with the new red values. Thus, the RedBlack GaussSeidel method
is the one in which the red nodes are updated using black nodes and then the black nodes are
updated using the updated red nodes. This procedure is repeated till the following convergence
criterion is satisfied: 6KPL  6KPL  F .


EXAMPLE 10.1

Determine the temperature at various nodes shown in Fig. 10.3. The two 6 6

 . The boundary conditions
dimensional heat transfer is given by the equation
Z  [ 
are shown in Fig. 10.3. The size of the slab is 2 m 2 m and Dx = Dy = 0.5 m. Use the Gauss
Seidel method.
400C

T1,3

T3,3

T1,2

T2,2

T3,2

T1,1

20C

T2,3

T2,1

T3,1

20C

20C
Fig. 10.3

Example 10.1

Solution Since all the nodes are interior nodes, therefore the discretized equation at node (i, j)
is given by
6   6   6   6 
6

Thus
K

L

 L

K L

K L

K L

P
6

P
6 
P
6
P
6 
P
6 

P
P
  6  6  

P
6


P
 6  

P
 6


P
P
6   6    


P
6

P
 6

P
 6  


P
6 

P
 6 

P
P
 6  6

Two-Dimensional Steady and Transient Heat Conduction

P
6 

197

P
P
P
6  6   6  

P
6 
P
6 
P
6 



P
 6 

P
6 




P
 6  


P
 6 

P
 6 

P
 6  


P
 6   


Note that the coefficient of the term on the left hand side is the highest among all the other
coefficients in the linear algebraic equation. That is why convergence is obtained when the
GaussSeidel method is used for solving the above set of linear algebraic equations. To start
the iteration, some initial values of all the nine variables are assumed and thereafter their latest
values are used to update the solution. The iterations are performed till there is no change in
P 
P
the value of temperature 6K L  6K L  F . Program 10.1 for the solution of the above problem
is given in the Appendix. The converged solution is
T1,1 = 47.14
T1,2 = 91.25
T1,3 = 182.86

T2,1 = 57.32
T2,2 = 115.00
T2,3 = 220.18

T3,1 = 47.14
T3,2 = 91.25
T3,3 = 182.86

EXAMPLE 10.2 Consider the following body in which the inner face is at 200C and the
outer face is at 100C. The body is very long so that heat transfer takes place in two
dimensions only. The thermal conductivity of the body is 1.21 W/m-K. The dimensions of the

m.
body are shown in Fig. 10.4. Take 'Z '[

3m

1m

3m

1m

200C

2
5

Fig. 10.4

Example 10.2.

100C

198

Introduction to Numerical Methods in Chemical Engineering

Using the GaussSeidel method, solve for the temperatures at nodes 1 to 5.

Solution

Since there is no source term, we get

6P 

6P  


6P 

6P   6P  



6P 

6P   6P  



6P 

6P   6P  



6P   

On modifying the Program 10.1, the following solution is obtained: T1 = 145.83C,
T2 = 141.67C, T3 = 120.83C, T4 = 141.67C, T5 = 145.83C.
6P 

EXAMPLE 10.3

Determine the temperature at various nodes shown in Fig. 10.5. The heat
 6

6

 . The boundary conditions are shown in

Z  [ 
the figure. The size of the slab is 2 m 2 m and Dx = Dy = 0.5 m. Use the RedBlack Gauss
Seidel method.

transfer is given by the equation

400C

R4

R5

B2

R3

B3

R1

20C

B4

B1

R2

Fig. 10.5

20C

20C
Example 10.3.

Solution Before starting the iterations the following initial values of temperatures at the
black nodes are assumed: B1 = 55, B2 = 90, B3 = 90, B4 = 220C. Now we compute values
at the red nodes using the assumed values at the black nodes.
4

      





q%

Two-Dimensional Steady and Transient Heat Conduction

4
4

4

199

       
q%


       
q%



      





q%

       

q%


Now let us update the black node values using the updated values at the red nodes.
4

      

q%

      
$
q%

      
$
q%

      
$
q%

Updating the red nodes using the updated black node values, we get: R1 = 46.80, R2 = 46.80,
R3 = 114.375, R4 = 182.578, R5 = 182.578C. Updating the black nodes using updated red
node values, we get: B1 = 56.994, B2 = 90.938, B3 = 90.938, B4 = 219.88C. Note that even
after two iterations the temperatures are close to the converged values obtained using the
GaussSeidel method in Example 10.1. The iterations are performed till there is no change in
the value of temperature, 6KPL  6KPL  F .


$

 6 6
EXAMPLE 10.4 Discretize the equation

Z  [ 
boundary as shown in Fig. 10.6.

 at node (i, j) of a convection

T h
dq1

i 1, j

i, j + 1

dq4

dq2

i, j

dq3
Dx
2

Convection
boundary
i, j 1

Dx
Fig. 10.6

Dy

Convection boundary condition.

200

Introduction to Numerical Methods in Chemical Engineering

Solution The given differential equation is at steady state and therefore in the control volume
around node (i, j), the summation of S entering the control volume from all the four sides is
FS
6
FS
6
 M#
 M#
zero. From the left and right sides,
, and from top and bottom,
.
[
FV
Z
FV
To determine the area for heat transfer into the control volume, the depth is taken to be unity.
The various energy inputs into the control volume around node (i, j) are
'Z 6


6

FS
FV

M

FS
FV

6
 M '[

FS
FV

M

FS
FV

J '[ 6  6 

K L

K L

'[
6

K L



 L

'Z

'Z 6


K L

6

K L



'[
K L

Thus, from the energy balance at node i, j  , we get

FS FS FS FS




FV
FV
FV
FV

Thus
M

'Z 6

K L

6

K L



'[

6
 M '[

K L

6
K

 L

'Z

'Z 6
M

K L

6

K L



'[

J '[  6

K L

 6f 

where T is the free stream temperature of the surrounding fluid and h is the convective heat
transfer coefficient between the convection boundary surface and fluid.
If Dx = Dy, the equation becomes
M
6  6    M 6  6    M 6  6    J 'Z 6  6f 


Collecting the terms of Ti,j on one side and the rest of the terms on the other side, we get
K L

K L

K L

6

 L

K L

6     6 
K

K L



K L

 6

K L



K L

  $K6f

$K  

K L

where the Biot number is given by

J 'Z
M
An equation of this type is applicable for each node along the convection boundary surface.
$K

Two-Dimensional Steady and Transient Heat Conduction

EXAMPLE 10.5

 6

Discretize the equation

Z 

6

201

 at node (i, j) of an exterior corner

[ 

with convection boundary condition as shown in Fig. 10.7.

T h
i 1, j

i, j
Dy

Dx
2

i 1, j 1

T h

i, j 1

Dx
Fig. 10.7

Solution

Exterior corner with convection boundary condition.

From the energy balance at node (i, j), we get

M

'[ 6

K L

6
K

'Z

 L

'Z 6
M

K L

6

K L



'[

'Z
6


K L

 6f   J

'[
6


K L

 6f 

where T is the free stream temperature of the surrounding fluid and h is the convective heat
transfer coefficient between the convection boundary surface and the fluid. If Dx = Dy, the
equation becomes


M
6


K L

6
K

 L

M
   6

K L

6

K L



J 'Z  6

K L

 6f 

Collecting the terms of Ti, j on one side and the rest of the terms on the other side, we get

6

 6   6 

K L

K L



  $K6f

$K  

 6  6

 at node (i, j) of an interior corner
Z  [ 
with the convection boundary condition as shown in Fig. 10.8.
EXAMPLE 10.6

Discretize the equation

202

Introduction to Numerical Methods in Chemical Engineering

i, j + 1

i 1, j
i, j

i + 1, j
Dy

Dx
2

T h

i, j 1

Dx
Fig. 10.8

Solution
M

Interior corner with convection boundary condition.

From the energy balance at node (i, j), we get

'[ 6

K L

6
K

 L

'Z

6
 M 'Z

K L

6

K L



'[

6
 M '[

K L

6
K

 L

'Z

'Z 6
M

K L

6

K L



'[

'Z
6  6f   J '[ 6  6f 


where T is the free stream temperature of the surrounding fluid and h is the convective heat
transfer coefficient between the convection boundary surface and the fluid. Taking Dx = Dy and
dividing by k, we get

K L


6


K L

K L

 6 
K


   6 

6

K L

K L

  6



K L

6

K L



 6   6 
K L

 $K  6   6f 
K L

Collecting the terms of Ti, j on one side and the rest of the terms on the other side, we get

K L



6
K

 L

   6 

K L

EXAMPLE 10.7

Discretize the equation

boundary as shown in Fig. 10.9.

 L

6

K L



  $K6f

$K  
6
Z

6
[ 

 at node (i, j) of an insulation

Two-Dimensional Steady and Transient Heat Conduction

203

i, j + 1

i 1, j

Dy

i, j

Insulation
boundary
Dx
2
Dx
Fig. 10.9

Insulation boundary condition.

Solution The given differential equation is at steady state and therefore in the control volume
around node (i, j) the summation of S entering the control volume from all the three sides is
zero. There is no heat flux across the insulation boundary. From the energy balance at node
(i, j), we get
M

'Z 6


K L

6

K L

6   6 
'Z 6   6 
 M '[
M 
'Z
'[



'[

K L

K L

K L



If Dx = Dy, the equation becomes


6


K L

6

K L



  6

K L

 6  
K


6  6


K L

K L



Collecting the terms of Ti, j on one side and the rest of the terms on the other side, we get
6

6   6
K

L

K L



6

K L




Note that the insulation boundary equation is obtained by setting h = 0 in the equation for
convection boundary.
K L

EXAMPLE 10.8

Determine the temperature at various nodes shown in Fig. 10.10. The

steady heat transfer is given by the equation

 6
Z 

6
[ 

 . The left face is maintained at

204

Introduction to Numerical Methods in Chemical Engineering

100oC and the top face at 500C, while the other two faces are exposed to an environment at
100oC. The convective heat transfer coefficient between the right and bottom walls to the
surrounding fluid is 10 W/m2-K. The block is 1 m 1 m. Use the GaussSeidel method.
500C

T1,3

T2,3

T3,3

h = 10 W/m2-K

T1,2

T2,2

T3,2

T = 100C

T1,1

T2,1

100C

T3,1
2

T = 100C
Fig. 10.10

h = 10 W/m -K
Example 10.8.


m.

At the interior nodes the discretized equation is

Solution

'Z

'[

6   6 

L

 L

6

K L



6

K L




At nodes T1,1, T2,1, T3,2, and T3,3 the convection boundary condition exists, and at node T3,1 the
exterior corner convection boundary condition exists. These convection boundary conditions
have been described in previous examples. Thus the following nodal equations are obtained:

6P     6 P 

6 P



P 
P
P
6  6    6
P
6 

P 
P
  6    6
P
6


P
P
P
6   6  6 
P

6



P
P
P
P
6   6  6   6
P
6 

P 
P
P
  6  6  6
P
6 

K L







Two-Dimensional Steady and Transient Heat Conduction

P
P
 6  6  

P
6















P
P
P
6    6   6 

P
6 






P
P
6    6    

P
6 

205



Note that the coefficient of the term on the left hand side is the highest among all the other
coefficients in the linear algebraic equation and that is why convergence is obtained when the
GaussSeidel method is used. To start the iteration, some initial values of all the nine variables
are assumed and thereafter their latest values are used to update the solution. The iterations are
performed till there is no change in the value of the temperature at the given node, that is,


6KPL  6KPL  F . Program 10.1 can be modified for the solution of this problem. The converged

solution is (all T in C)

T1,1 = 157.68
T1,2 = 192.34
T1,3 = 280.65
EXAMPLE 10.9

T2,1 = 184.51
T2,2 = 231.03
T2,3 = 330.25

T3,1 = 175.32
T3,2 = 217.01
T3,3 = 309.32

For the L-shaped body shown in Fig. 10.11, determine the temperatures at
6

 6

 . The left surface

Z  [ 
is insulated and the bottom surface is at a uniform temperature of 90C. The entire top surface
is subjected to convection to ambient air at 25C. The heat transfer coefficient between the top
surface and the ambient air is 75 W/m2-K. The right surface is subjected to uniform heat flux
of 4500 W/m2. Dx = Dy = 1 cm. The thermal conductivity of the body, k = 15 W/m-K.

nodes 1 to 9. Steady heat conduction takes place in the body,

Insulated

h = 75 W/m2-K
T = 25C
7
8

Dy = 1 cm
9
Heat flux
4500 W/m2

Surface at 90C
Fig. 10.11

Dx = 1 cm
Example 10.9.

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Introduction to Numerical Methods in Chemical Engineering

Solution

Equation for node 1:

M

'Z 6  6

 '[

'[ 6  6
M
 'Z

'Z
6  6f 


M  6  6   M  6  6  J'Z  6  6f 
6  6  6  6 

J 'Z
6  6f 
M

J 'Z  
 .
M

Thus the equation for node 1 becomes

where

6  6  6    6f  

The coefficient of T1 is the highest; therefore

6

6  6  


Equation for node 2:

M

6  6
'[ 6  6
'[ 6  6
'Z  M  'Z  M 'Z '[




6  6   6  6   6  6 





Equation for node 3:

'[ 6  6
'Z 6  6
'Z  M  '[


6  6 6  6



6
Equation for node 4:
M

J 'Z
6f  6 
M

  6  6   6  

6

M

J 'Z  6  6f 

'Z
'[
6  6f   J 6  6f 



J 'Z
6f  6 
M

  6  6   


'Z 6  6
'Z 6  
6  6

M

 M '[

 '[
 '[
'Z
6  6 6  

 6  6



6

6  6  


Two-Dimensional Steady and Transient Heat Conduction

Equation for node 5:

6  6
 M '[ 
'Z

Equation for node 6:

M

6  6
6  6

6  6
 M '[ 'Z  M 'Z '[  M 'Z '[ 

6  6  6  
6


6  6
'Z 6  6
'[ 6  6
6  6

 M '[
 M 'Z '[  M  'Z
 '[
'Z

'Z
'[
6  6f   J 6  6f 



6  6
6  6
 6  6  6  6  



J 'Z
6f  6 
M

6      6  6   

6



Equation for node 7:

6  
'[ 6  6
'[ 6  6
'Z  M  'Z  M 'Z '[


M



6  6   6  6   6   



6

J 'Z
6f  6 
M

  6  6     


Equation for node 8:

M

6  
'[ 6  6
'[ 6  6
'Z  M  'Z  M 'Z '[




6  6   6  6   6   



6

J 'Z  6  6f 

J 'Z
6f  6 
M

  6  6     


Equation for node 9:

M

J 'Z  6  6f 

'[ 6  6
'Z 6  
'[
'Z  M  '[   




 '[
6  6   6    


 

6

6  


'Z
6  6f 


J 'Z
6f  6 
M

207

208

Introduction to Numerical Methods in Chemical Engineering

Program 10.1 can be modified for the solution of this problem. The converged solution is:
T1 = 83.19, T2 = 82.86, T3 = 81.49, T4 = 86.43, T5 = 86.27, T6 = 85.78, T7 = 86.72, T8 = 87.26,
and T9 = 88.54C.

10.5 ADI Method for Steady Heat Conduction

The Alternating Direction Implicit (ADI) method can also be applied for the solution of the
two-dimensional steady heat conduction equation (10.1)
 6
Z 

6

[ 

Using the central difference scheme, we get

6   6
K

L

6

K L

'Z

 L

K L



 6

K L

'[

6

K L



[see Eq. (10.8)]

This equation can be split into the following two half-steps:


6K 
L
P

P

 6 

K L

'Z





 6K 
L
P

6 P   6 P  6 P 





'[

K L

K L

K L

(10.12)



P 
P
P
  6   6 

6 


(10.13)



'[
'Z

The first half-step is executed on all the nodes. This is followed by computation of the second
half- step on all the nodes (see Fig. 10.12). The ADI method is also called the line-by-line

6KPL


 6KPL
 

j+1
j

Sweep direction

(a) First half-step of iteration

Fig. 10.12

K L

Sweep direction

6KPL
 

i
i+1
(b) Second half-step of iteration

First half-step and second half-step in ADI iteration.

Two-Dimensional Steady and Transient Heat Conduction

209

TDMA, as in each line of nodes taken a tridiagonal set of linear algebraic equations is formed.
TDMA can be used to solve them, and thus the values of nodes along a line are updated.
Initially, Eq. (10.12) is considered for the first half of iteration, in which the sweep direction
is along the x-axis and each line of nodes along the x-axis is updated. Then Eq. (10.13) is
considered for the second half of iteration, in which the sweep direction is along the y-axis and
each line of nodes along the y-axis is updated. The iterations are performed till convergence
in temperature is achieved, 6KPL  6KPL  F . ADI is a line-by-line method, whereas Gauss

Seidel is a pointwise method.
EXAMPLE 10.10

Determine the temperature at various nodes shown in Fig. 10.13. The heat
 6 6
transfer is given by the equation

 . The boundary conditions are shown in
Z  [ 
Fig. 10.13. The size of the slab is 2 m 2 m and Dx = Dy = 0.5 m. Use the ADI method.
400C
T2,4

T1,4

T3,4

T1,3

T0,1

T3,3

T2,2

T3,2

T1,1

20C T0,2

T2,3

T1,2

T0,3

T2,1

T3,1

T4,3

T4,2

20C

T4,1

T1,0

T2,0
T3,0
20C
Fig. 10.13 Example 10.10.

Solution The first half iteration is performed (scanning various i nodes for given j) using the
discretized equation
P

P

P

6   6   6 
K

'Z

K L




6 P   6 P   6 P
K L

K L

'[

K L

Since Dx = Dy, the discretized equation becomes

P

P

P

6   6   6 
K

K L




 6 P   6 P 
K L

K L

At node 1,1
P

P

P

6   6   6




P
P
 6  6

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Introduction to Numerical Methods in Chemical Engineering

Let us assume the following initial temperatures: T1,2 = 90, T2,2 = 110, T3,2 = 90. Since T0,1
is always at 20C, the above equation becomes
P

At node 2,1

6




P

P

P
P
 6   6  6

 6 
P

P

6   6
P

6




P

 6




P

 6







P

     

 

P
P
 6  6

 6 

P
P
 6  6

   

 

At node 3,1
P

P

P

P
P
 6  6

6   6   6 

P

6




P

 6




P

 6




P
P
 6  6

Since T4,1 is always at 20C, the above equation becomes

P

P

P

P
P
 6   6  6

6   6 

     

 

The following tridiagonal set of linear algebraic equations is obtained for various i nodes at
j=1
P 
  6

P 
 
 6 


  6 P  

 

P

The solution by TDMA is 6




P

= 46.43, 6









P

= 55.71, 6




= 46.43C.

Now let us write the equations for various i nodes at j = 2.

At node 1,2
P

P

P

6   6   6 

P
P
 6  6

Let us assume the following initial temperatures: T1,3 = 180, T2,3 = 220, T3,3 = 180.
Since T0,2 is always at 20C, the above equation becomes
P

P

P

P
P
 6   6  6

6   6 

     

 

At node 2,2
P

6
P

P




P

 6

P

6   6   6 




P

 6




P
P
 6  6

P
P
 6  6

   

 

Two-Dimensional Steady and Transient Heat Conduction

211

At node 3,2


P

P

P

P
P
 6  6

6   6   6 



P

P

6   6 

P

P
P
 6   6  6

Since T4,2 is always at 20oC, the above equation becomes

P

P

P

P
P
 6   6  6

6   6 

     

 

The following tridiagonal set of linear algebraic equations is obtained for various i nodes at
j = 2:

P 
  6 

P 
 
 6  



  6 P   



P

P

P

The solution by TDMA is: 6  = 90.10, 6  = 113.98, 6  = 90.10C.
Now let us write the equations for various i nodes at j = 3.
At node 1,3
P

P

P

P
P
 6  6

6   6   6 

Since T0,3 is always at 20C, the above equation becomes

P

6




P

 6




P




P
P
 6  6  6

     

 

At node 2,3



P

6
P

P

P

 6

P

6   6   6 







P

 6

P
P
 6  6

P
P
 6  6

   

 

At node 3,3
P

P

P

P
P
 6  6

6   6   6 

P




P

6  6




P




P
P
 6  6  6

Since T4,3 is always at 20C, the above equation becomes

P

P

6   6 

P

P
P
 6   6  6

     

 

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Introduction to Numerical Methods in Chemical Engineering

The following tridiagonal set of linear algebraic equations is obtained for various i nodes at
j = 3:

P 
  6 

P 
 
 6  



  6 P   



P

P

P

The solution by TDMA is: 6  = 182.46, 6  = 219.72, 6  = 182.46C.
The second half iteration (scanning various j nodes for given i) is performed using the
discretized equation
P

P

P

6   6   6 
K

'Z

K L




6 P   6 P   6 P 


K L

K L

K L

'[

Since Dx = Dy, the discretized equation becomes

P

P

6 P   6 P   6 P 
 
 


 6   6 

P
P
P
6  6  6

 6   6 

K L

At node 1,1

P
6

K L

K L

P
 6

P

P
 6

P

 6




P

P

 6




Since T1,0 is always at 20C, the above equation becomes

P
P
6  6

P

P

At node 1,2
P
P
P
6  6  6
P
P
P
6  6  6

At node 1,3

P
 6  6   6 

     
P

 6   6 

   

P
P
P
6   6  6

P

 

P

 
P

 6   6 

Since T1,4 is always at 400C, the above equation becomes

P
P
6  6

     

 

The following tridiagonal set of linear algebraic equations is obtained for various j nodes at
i = 1:
P 
  6 

P
 
 6 

P

  6 

Two-Dimensional Steady and Transient Heat Conduction

213

P
P
P
The solution by TDMA is: 6 = 46.63, 6  = 90.81, 6 = 182.63C.

At node 2,1
P

P
P
P
6   6   6 

P
6 

P
 6 

P

 6   6
P

P
 6 

 6







P

 6




Since T2,0 is always at 20C, the above equation becomes

P
P
6   6 

P

P

P
 6   6   6




     

 

At node 2,2
P

P
P
P
6   6   6 
P
P
P
6   6   6 

P

 6   6 

   

 

At node 2,3
P

P
P
P
6   6   6 

P

 6   6 

Since T2,4 is always at 400C, the above equation becomes

P
P
6   6 

     

 

The following tridiagonal set of linear algebraic equations is obtained for various j nodes at
i = 2:
P 
  6

P 
 
 6


  6 

P






P
P
P
The solution by TDMA is: 6  = 56.87, 6  = 114.41, 6  = 219.88C.

At node 3,1
P
6 

P
 6 

P

P
6 

 6




P

P
P
6   6 

P

 6




P

P
 6   6   6 

Since T3,0 is always at 20C, the above equation becomes

P
P
6   6 

P

P

P
 6   6   6 

     

At node 3,2
P
P
P
6   6   6 
P
P
P
6   6   6 

P

P

 6   6 

   

 

 

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Introduction to Numerical Methods in Chemical Engineering

At node 3,3
P
P
P
6   6   6 

P

P

 6   6 

Since T3,4 is always at 400C, the above equation becomes

P
P
6   6 

     

 

The following tridiagonal set of linear algebraic equations is obtained for various j nodes at
i = 3:
P 
  6 

P
 
 6  

P

  6  

P
P
P
The solution by TDMA is: 6  = 46.97, 6  = 91.03, 6  = 182.73C.

Program 10.2 for the solution of the above problem is given in the Appendix. After 25
iterations when convergence is obtained, the results from the computer program are: T1,1 = 47.14,
T1,2 = 91.25, T1,3 = 182.86, T2,1 = 57.32, T2,2 = 115.00, T2,3 =220.16, T3,1 = 47.14,
T3,2 = 91.25, T3,3 = 182.86C.
Similar results are obtained in Example 10.1 in which the problem was solved using the
GaussSeidel method.

10.6

ADI Method for Transient Heat Conduction

The ADI method can be extended for the solution of two-dimensional transient heat
conduction. The explicit schemes are stable only with some constraints on Dx and Dt, whereas
implicit schemes are not associated with these constraints. Therefore the ADI method, which
is an implicit method shall be used. Transient heat conduction in two-dimensional space is
given by [see Eq. (9.26)]
6

6
V

Z 

6

[ 

Taking the first half-step in time, we get

P

6

K L




 6 P

'V  

K L



P 
P
P
P
P
P
6   6   6   6    6    6 

B
'Z 
'[ 

Letting D = Dx = Dy and /

B'V
'

, we get

K L

K L

K L

K L

(10.14)

Two-Dimensional Steady and Transient Heat Conduction

P

6K L




 6KPL


Multiplying both sides by





P
P
/ P 
6K  L  6K L  6K L   6KPL   6KPL   6KPL





 6K 
L

K L


6K 
L

P

P

P
P
 P

6     6    6 

/
K

(10.15)


, we get
/

 P 
P
6   6 
/

K L

215

K L

P




 6 P   6 P   6 P


(10.16)

6 P   6 P   6 P  
/

(10.17)

 6 

K L

K L

K L

K L

K L

K L

K L

Now let us carry out the second half of the iteration

6KPL






P 

P
P
  6   6 
6 P   6 P   6 P 
6 

 



B

'Z 
'[

(10.18)







P
P
P
/ P 
6K L   6KPL  6KPL  6K   6K   6K L 

 
L
L

(10.19)

P

 6

K L

'V  

P

6KPL  6K L

Multiplying both sides by

K L

K L

K L

K L


, we get
/


P
 P 
6K  L  6K L 

P

6 P     6 P   6 P 
 

 

/
K L

P

P

6KPL  6KPL  6KPL  6K L  6K L  6K  L


 


K L

K L

P

P

P

6   6   6 
K

K L







(10.20)

/  

(10.21)

ADI is an implicit method and is therefore unconditionally stable; moreover, because it is a

line-by-line method, TDMA can be used to update the temperature for nodes in a line. Initially
Eq. (10.17) is considered for the first half of the iteration. In this equation, Tn is the
P

temperature at time t and 6  are the updated temperatures computed in this first half of
iteration. Sweeping of each line along the x-axis is carried out from bottom to top. Then
P

Eq. (10.21) is considered for the second half of the iteration. In this equation, 6  are known
and 6 P  are computed. The sweeping of each line along the y-axis is carried out from left to
right and the temperature profile at time t + Dt is computed. This temperature profile at t + Dt
can be used to obtain the temperature profile at t + 2Dt by again carrying out the
first half and the second half of the iteration. Thus marching in time is carried out for this
parabolic PDE.

216

Introduction to Numerical Methods in Chemical Engineering

EXAMPLE 10.11 A slab of size 2 m 2 m is initially at 0C, and at t = 0 all the four sides
of the slab are made at 400oC. Take D = Dx = Dy = 0.1 m and a = 1 m2/s. Determine the
temperature of the slab at various nodes at t = 0.5 s. Take Dt = 0.05 s and for computing
consider the upper quadrant of the slab.
Solution The upper quadrant of the slab is shown in Fig. 10.14. The size of the quadrant is
1 m 1 m and 10 parts along an axis are made; therefore D = Dx = Dy = 0.1 m. Let us take

't

0.05 s; therefore /

B'V



'



 . Thus  

 and

400C

(1,11)

6
Z


/



/

  .

(11,11)

400C

(1,1)

(11,1)
6

[
Upper quadrant of slab in Example 10.11.

Fig. 10.14

First half of iteration

Equations for node (1,1) to node (10,1)

P

At node (1,1), using Eq. (10.17) and from symmetry 6 

P

6




P

P




P

P

 6   6 

P

P

6   6   6 

P
6 , we get

P
P
6  6

P
At node (3,1), using Eq. (10.17) and from symmetry 6
P

P
P
6  6

 6 

P
At node (2,1), using Eq. (10.17) and from symmetry 6

6

P

P
6  and 6

P
6 , we get

P
P
6  6

P
6 , we get

Two-Dimensional Steady and Transient Heat Conduction

P
At node (10,1), using Eq. (10.17) and from symmetry 6
P

6






6
P

P
6

P
 6

217

P
6 , we get

 6
P

In the above equation on the right hand side, T11,1 = 400. The above set of 10 equations
constitute a tridiagonal matrix and can be solved using TDMA.
Equations for node (1,2) to node (10,2)
P

At node (1,2), using Eq. (10.17) and from symmetry 6

P

P




P




6 , we get

P
P
P
6  6  6

6   6 

At node (2,2), using Eq. (10.17), we get

P

6




P




P

 6  6




P
P
P
6  6  6

At node (3,2), using Eq. (10.17), we get

P

P

P

6   6   6 

P
P
P
6  6  6

At node (10,2), using Eq. (10.17), we get

P




6 



6
P

P
6

P
 6

P
 6


 6
P

In the above equation on the right hand side, T11,2 = 400. The above set of 10 equations
constitute a tridiagonal matrix and can be solved using TDMA.
Equations for node (1,10) to node (10,10)

P

At node (1,10), using Eq. (10.17), and from symmetry 6


6
P


6
P

P

6 , we get

P
P
P
6  6  6

At node (2,10), using Eq. (10.17), we get

P

P

P

6  6  6

P
P
P
6  6  6

At node (3,10), using Eq. (10.17), we get


6
P


6
P


 6
P

P
P
P
6  6  6

At node (10,10) using Eq. (10.17) we get

P

P


6  6

P

P
P
P

6  6  6  6

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Introduction to Numerical Methods in Chemical Engineering

In the above set of equations on the right hand side, Ti,11 = 400 and T11,10 = 400. The above
set of 10 equations constitute a tri-diagonal matrix and can be solved using TDMA.
Second half of iteration
Equations for node (1,1) to node (1,10)
P

P

At node (1,1), using Eq. (10.21) and from symmetries 6 

P

P
P
6  6 

P

6   6

P
At node (1,2), using Eq. (10.21) and from symmetry 6
P
6

P
6

P

P
 6

P
6

P




P

P




P

6  6




P
6 , we get

P
At node (1,10), using Eq. (10.21) and from symmetry 6

P
P
6   6

P
6 , we get




6  6

P
 6 

P
and 6

P
6 , we get

P
At node (1,3), using Eq. (10.21) and from symmetry 6

P
6

6




P




P
6 , we get

P
6  6  6

In the above equation on the right hand side, T1,11 = 400. The above set of 10 equations
constitute a tridiagonal matrix and can be solved using TDMA.
Equations for node (2,1) to node (2,10)
P

At node (2,1), using Eq. (10.21) and from symmetry 6 

P
6 

P
6 

P

6




P

 6




P

6  , we get
P

 6




At node (2,2), using Eq. (10.21), we get

P
P
P
6   6   6 

P

P

P

6   6   6 

At node (2,3), using Eq. (10.21), we get

P
6 

P
6 

P
 6 

P

6




P

 6




P

 6




At node (2,10), using Eq. (10.21), we get

P
P 
6   6

P

P

P

P 
6  6  6  6

Two-Dimensional Steady and Transient Heat Conduction

219

In the above equation on the right hand side, T2,11 = 400. The above set of 10 equations
constitute a tridiagonal matrix and can be solved using TDMA.
Equations for node (10,1) to node (10,10)


6

At node (2,1), using Eq. (10.21) and from symmetry

P
P 
6  6

P


6

P

P

P

P

, we get

6  6   6

At node (2,2), using Eq. (10.21), we get

P
6

P 
6

P 
 6


6
P

P

 6





 6
P

At node (2,3), using Eq. (10.21), we get

P 
P 
P 
6  6  6

P

P

P

6  6   6

At node (2,10), using Eq. (10.21), we get

P 
6



6
P

P 
6


 6
P



 6
P

P 
 6

In the above set of equations on the right hand side, T11,i = 400 and T10,11 = 400. The above
set of 10 equations constitute a tridiagonal matrix and can be solved using TDMA. Note that
for both the first-half and second-half iterations the tridiagonal matrix that is formed has the
following coefficients:
C

C

C

C

C

D

D

D

D

D

C
D

C
D

C
D

C
D



D



E   E E E E E E E E  
Program 10.3 for the solution of the above problem is given in the Appendix. The temperatures
(in C) at t = 0.5 s are presented in Table 10.2.
Table 10.2
T1,1 = 329.77
T1,2 = 329.83
T1,3 = 330.02
T1,4 = 330.42
T1,5 = 331.19
T1,6 = 332.64
T1,7 = 335.34
T1,8 = 340.39
T1,9 = 349.80
T1,10 = 367.33

T2,1 = 331.09
T2,2 = 331.70
T2,3 = 333.54
T2,4 = 336.68
T2,5 = 341.22
T2,6 = 347.31
T2,7 = 355.10
T2,8 = 364.85
T2,9 = 376.94
T2,10 = 389.30

Temperatures in Example 10.11

T3,1 = 334.21
T3,2 = 334.86
T3,3 = 336.81
T3,4 = 340.10
T3,5 = 344.80
T3,6 = 350.96
T3,7 = 358.61
T3,8 = 367.76
T3,9 = 378.59
T3,10 = 388.85

T4.1 = 339.01
T4,2 = 339.65
T4,3 = 341.58
T4,4 = 344.82
T4,5 = 349.39
T4,6 = 355.29
T4,7 = 362.43
T4,8 = 370.77
T4,9 = 380.49
T4,10 = 389.60

T5,1 = 345.20
T5,2 = 345.80
T5,3 = 347.61
T5,4 = 350.64
T5,5 = 354.86
T5,6 = 360.25
T5,7 = 366.68
T5,8 = 374.10
T5,9 = 382.71
T5,10 = 390.70

220

Introduction to Numerical Methods in Chemical Engineering

T6,1 = 352.52
T6,2 = 353.06
T6,3 = 354.67
T6,4 = 357.35
T6,5 = 361.08
T6,6 = 365.79
T6,7 = 371.37
T6,8 = 377.76
T6,9 = 385.18
T6,10 = 391.98

T7,1 = 360.60
T7,2 = 361.06
T7,3 = 362.42
T7,4 = 364.68
T7,5 = 367.81
T7,6 = 371.75
T7,7 = 376.38
T7,8 = 381.65
T7,9 = 387.81
T7,10 = 393.37

T8,1 = 369.54
T8,2 = 369.90
T8,3 = 370.96
T8,4 = 372.73
T8,5 = 375.16
T8,6 = 378.22
T8,7 = 381.80
T8,8 = 385.87
T8,9 = 390.63
T8,10 = 394.88

T9,1 = 381.09
T9,2 = 381.31
T9,3 = 381.98
T9,4 = 383.07
T9,5 = 384.59
T9,6 = 386.49
T9,7 = 388.71
T9,8 = 391.25
T9,9 = 394.16
T9,10 = 396.86

T10,1 = 388.03
T10,2 = 388.17
T10,3 = 388.60
T10,4 = 389.30
T10,5 = 390.27
T10,6 = 391.47
T10,7 = 392.88
T10,8 = 394.47
T10,9 = 396.38
T10,10 = 397.96

Exercises
10.1 Using the Gauss-Seidel method, determine the temperatures at positions 1, 2, 3 and
4 shown in Fig. 10.15.
700C
4
100C

400C

500C
Fig. 10.15

Exercise 10.1.

(Ans: T1 = 487.5, T2 = 437.5, T3 = 362.5, T4 = 412.5C)

10.2 Using the Gauss-Seidel method, determine the temperature of the heated plate
shown in Fig. 10.16. The dimension of the plate is 40 cm 40 cm and is made of
aluminium. The thermal conductivity of aluminium is 0.5 W/m-K.
100C
T1,3

75C

T2,3

T2,3

T1,2

T2,2

T3,2

T1,1

T2,1

T3,1

0C
Fig. 10.16

Exercise 10.2.

50C

Two-Dimensional Steady and Transient Heat Conduction

221

(Ans: T1,1 = 42.86, T1,2 = 63.17, T1,3 = 78.57, T2,1 = 33.26, T2,2 = 56.25,
T2,3 = 76.12, T3,1 = 33.93, T3,2 = 52.46, T3,3 = 69.64C)
10.3 Using the Gauss-Seidel method, determine the steady state temperatures for nodes
1 to 6 shown in Fig. 10.17. The thermal conductivity of the body is 1.5 W/m-K.
Dx = Dy = 25 cm.
2

1
3

50C

h = 12 W/m2-K, T = 15C

Fig. 10.17

50C

50C
Exercise 10.3.

(Ans: T1 = 27.6, T2 = 27.6, T3 = 41.6, T4 = 41.6, T5 = 47.2, T6 = 47.2C)

10.4 Calculate the steady state temperatures for nodes 1 to 16 shown in Fig. 10.18. Take
Dx = Dy = 20 cm and k = 2.3 W/m-K.
1

h = 23 W/m2-K, T = 25C
2
3
4

10

11

12

13

Insulation

14

15

16

100C

100C
Fig. 10.18

Exercise 10.4.

(Ans: T1 = 35.28, T2 = 35.89, T3 = 38.49, T4 = 48.36, T5 = 55.24, T6 = 56.66, T7 =

61.84, T8 = 74.20, T9 = 72.37, T10 = 73.67, T11 = 78.01, T12 = 86.58,
T13 = 86.91, T14 = 87.63, T15 = 89.94, T16 = 94.13oC)
10.5 A slab of size 2 m 2 m shown in Fig. 10.19 is initially at 0C. At t = 0 s, all the
four sides of the slab are made at 600C. Take Dx = Dy = 0.1 m. Take
a = 1 m2/s. Determine the temperature of the slab at various nodes at t = 0.25 s.
Take Dt = 0.05 s, and for computing, consider the upper quadrant of the slab as
shown in Fig. 10.19.

222

Introduction to Numerical Methods in Chemical Engineering

600C

(1,11)

6
Z

(11,11)

600C

(1,1)

6

[
Fig. 10.19 Exercise 10.5.

(11,1)

(Ans: Program 10.3 can be modified and the temperatures (in C) at t = 0.25 s are
presented in Table 10.3.
Table 10.3

Temperatures in Exercise 10.5

T1,1 = 290.10
T1,2 = 290.34
T1,3 = 291.18
T1,4 = 292.95
T1,5 = 296.35
T1,6 = 302.74
T1,7 = 314.69
T1,8 = 336.96
T1,9 = 378.48
T1,10 = 455.84

T2,1 = 294.61
T2,2 = 297.26
T2,3 = 305.32
T2,4 = 319.18
T2,5 = 339.47
T2,6 = 366.94
T2,7 = 401.84
T2,8 = 443.29
T2,9 = 491.07
T2,10 = 563.32

T3,1 = 308.63
T3,2 = 311.43
T3,3 = 319.95
T3,4 = 334.48
T3,5 = 355.48
T3,6 = 383.30
T3,7 = 417.53
T3,8 = 456.10
T3,9 = 497.67
T3,10 = 562.67

T4.1 = 329.39
T4.2 = 332.19
T4.3 = 340.64
T4.4 = 354.95
T4.5 = 375.40
T4.6 = 402.10
T4.7 = 434.20
T4.8 = 469.16
T4.9 = 505.61
T4.10 = 566.37

T5,1 = 356.77
T5,2 = 359.39
T5,3 = 367.31
T5,4 = 380.66
T5,5 = 399.59
T5,6 = 424.03
T5,7 = 452.99
T5,8 = 483.88
T5,9 = 515.51
T5,10 = 571.09

T6,1 = 390.11
T6,2 = 392.45
T6,3 = 399.47
T6,4 = 411.25
T6,5 = 427.88
T6,6 = 449.20
T6,7 = 474.24
T6,8 = 500.60
T6,9 = 527.28
T6,10 = 576.02

T7,1 = 427.17
T7,2 = 429.12
T7,3 = 435.00
T7,4 = 444.85
T7,5 = 458.70
T7,6 = 476.39
T7,7 = 497.03
T7,8 = 518.57
T7,9 = 540.20
T7,10 = 580.89

T8,1 = 462.90
T8,2 = 464.48
T8,3 = 469.20
T8,4 = 477.09
T8,5 = 488.17
T8,6 = 502.28
T8,7 = 518.67
T8,8 = 535.63
T8,9 = 552.54
T8,10 = 585.36

T9,1 = 496.07
T9,2 = 497.27
T9,3 = 500.88
T9,4 = 506.92
T9,5 = 515.38
T9,6 = 526.13
T9,7 = 538.58
T9,8 = 551.33
T9,9 = 563.91
T9,10 = 589.41

T10,1 = 576.63
T10,2 = 576.89
T10,3 = 577.69
T10,4 = 579.01
T10,5 = 580.87
T10,6 = 583.23
T10,7 = 586.01
T10,8 = 589.01
T10,9 = 592.14
T10,10 = 596.94

Two-Dimensional Steady and Transient Heat Conduction

223

10.6 Solve Exercise 10.5 to determine the temperature profile at 0.5 s.

(Ans: Program 10.3 can be modified and the temperatures (in C) at t = 0.5 s are
presented in Table 10.4.
Table 10.4

Temperatures in Exercise 10.6

T1,1 = 494.66
T1,2 = 494.74
T1,3 = 495.03
T1,4 = 495.63
T1,5 = 496.78
T1,6 = 498.96
T1,7 = 503.02
T1,8 = 510.59
T1,9 = 524.71
T1,10 = 551.00

T2,1 = 496.64
T2,2 = 497.55
T2,3 = 500.31
T2,4 = 505.01
T2,5 = 511.83
T2,6 = 520.96
T2,7 = 532.65
T2,8 = 547.27
T2,9 = 565.42
T2,10 = 583.95

T3,1 = 501.32
T3,2 = 502.29
T3,3 = 505.21
T3,4 = 510.15
T3,5 = 517.20
T3,6 = 526.45
T3,7 = 537.91
T3,8 = 551.64
T3,9 = 567.89
T3,10 = 583.27

T4,1 = 508.51
T4,2 = 509.48
T4,3 = 512.37
T4,4 = 517.23
T4,5 = 524.09
T4,6 = 532.93
T4,7 = 543.65
T4,8 = 556.16
T4,9 = 570.73
T4,10 = 584.40

T5,1 = 517.80
T5,2 = 518.71
T5,3 = 521.42
T5,4 = 525.95
T5,5 = 532.29
T5,6 = 540.37
T5,7 = 550.03
T5,8 = 561.14
T5,9 = 574.06
T5,10 = 586.05

T6,1 = 528.78
T6,2 = 529.59
T6,3 = 532.01
T6,4 = 536.03
T6,5 = 541.62
T6,6 = 548.69
T6,7 = 557.06
T6,8 = 566.64
T6,9 = 577.77
T6,10 = 587.97

T7,1 = 540.91
T7,2 = 541.59
T7,3 = 543.63
T7,4 = 547.02
T7,5 = 551.72
T7,6 = 557.62
T7,7 = 564.57
T7,8 = 572.48
T7,9 = 581.71
T7,10 = 590.05

T8,1 = 554.31
T8,2 = 554.84
T8,3 = 556.44
T8,4 = 559.09
T8,5 = 562.75
T8,6 = 567.33
T8,7 = 572.70
T8,8 = 578.81
T8,9 = 585.94
T8,10 = 592.32

T9,1 = 571.64
T9,2 = 571.97
T9,3 = 572.97
T9,4 = 574.61
T9,5 = 576.89
T9,6 = 579.73
T9,7 = 583.08
T9,8 = 586.87
T9,9 = 591.24
T9,10 = 595.29

T10,1 = 582.04
T10,2 = 582.26
T10,3 = 582.90
T10,4 = 583.95
T10,5 = 585.40
T10,6 = 587.21
T10,7 = 589.32
T10,8 = 591.71
T10,9 = 594.56
T10,10 = 596.94

Appendix

Programs in C++
Program

Title

1.1
1.2

Program for the solution of tridiagonal equations

Program for the solution of linear algebraic equations by the Gauss Elimination
method
Program for the solution of linear algebraic equations by the GaussSeidel method
Program to solve for pressure drop in a pipe (nonlaminar case)
Program to solve for minimum fluidization velocity
Program to solve for terminal velocity
Program for the solution of two simultaneous nonlinear equations
Program to calculate the molar volume in the liquid and vapour phases at the given
temperature and pressure
Program to calculate the bubble point temperature and the dew point temperature
of a mixture of given composition, assuming Raoults law to be true
Program to calculate the compositions of the vapour and liquid phases at the given
temperature and pressure under flash conditions, assuming Raoults law to be true
Program to calculate the bubble point pressure, bubble point temperature, dew
point pressure and dew point temperature of a mixture of given composition,
assuming the modified Raoults law to be true
Program to calculate the compositions of the vapour and liquid phases at the given
temperature and pressure under flash conditions, assuming the modified Raoults
law to be true
Program to calculate the vapour pressure at the given temperature using the Peng
Robinson equation of state by comparing the fugacities of the liquid and vapour
phases
Program to calculate the bubble point pressure using the gammaphi approach
Program to calculate the bubble point pressure using the PengRobinson equation
of state
Program for the solution of two simultaneous chemical reactions in chemical
equilibrium
Program to calculate the adiabatic flame temperature (AFT) for a fuel
Program to solve an ordinary differential equation by the RungeKutta method
Program to determine the velocity of a particle in a pneumatic conveyor

1.3
2.1
2.2
2.3
2.4
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
4.1
4.2

225

226
4.3
4.4
4.5
4.6
4.7
7.1
7.2
8.1
8.2
9.1
9.2
10.1
10.2
10.3

Appendix:

Programs in C++

Program to solve two simultaneous ordinary differential equations by the Runge

Kutta method
Program to solve three simultaneous ordinary differential equations by the Runge
Kutta method
Program to solve three simultaneous ordinary differential equations for the reaction
A B C by the RungeKutta fourth order method
Program to solve four simultaneous ordinary differential equations for the reactions
A + B C and B + C D by the RungeKutta method
Program to solve ordinary differential equations in a non-isothermal tubular reactor
by the RungeKutta method
Program to calculate the concentration profile in a tubular reactor with axial
dispersion (second order reaction)
Program to calculate the concentration profile in a tubular reactor with axial
dispersion in which two parallel reactions take place
Program to calculate the concentration profile along the radius for reaction
diffusion in a spherical catalyst pellet (second order isothermal reaction)
Program to calculate the concentration profile along the radius for reactiondiffusion in a spherical catalyst pellet (non-isothermal, beta = 1)
Program to calculate the temperature profile in a rectangular slab during transient
heat conduction
Program to calculate the concentration profile in a sphere during transient diffusion
of drug from spherical pellet
Program to calculate the temperature profile in a two-dimensional body during
steady heat conduction using the Gauss-Seidel method
Program to calculate the temperature profile in a two-dimensional body during
steady heat conduction using the ADI method
Program to calculate the temperature profile in a two-dimensional body during
transient heat conduction using the ADI method
PROGRAM 1.1

//PROGRAM 1.1
//program for the solution of tridiagonal equations
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int i,j,n,i1,n1,k;
float a[21],b[21],c[21],d[21],x[21],beta[21],gamma[21];
//a is subdiagonal, b is diagonal and c is superdiagonal
for(i=2;i<=7;++i)
{

Appendix: Programs in C++

a[i]=1.0;
}
for(i=1;i<=7;++i)
{
b[i]=-2.0;
}
for(i=1;i<=6;++i)
{
c[i]=1.0;
}
d[1]=-240.0;
for(i=2;i<=6;++i)
{
d[i]=-40.0;
}
d[7]=-60.0;
i=1;
n=7;
beta[i]=b[i];
gamma[i]=d[i]/beta[i];
i1=i+1;
for(j=i1;j<=n;++j)
{
beta[j]=b[j]-a[j]*c[j-1]/beta[j-1];
gamma[j]=(d[j]-a[j]*gamma[j-1])/beta[j];
}
x[n]=gamma[n];
n1=n-i;
for(k=1;k<=n1;++k)
{
j=n-k;
x[j]=gamma[j]-c[j]*x[j+1]/beta[j];
}
cout<<\t\t\t THE SOLUTION BY TDMA<<endl;
for(i=1;i<=7;++i)
{
cout<<x[i]<<endl;
}
getch();
}

PROGRAM 1.2

//PROGRAM 1.2
//program for the solution of linear algebraic equations
//by the Gauss Elimination method
#include<iostream.h>

227

228

Appendix:

Programs in C++

#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int n,m,l,i,j,k,jj,kp1,nn,ip1;
float a[10][11],x[10],sum,big,ab,quot,t;
n=4;
cout<<n<<endl;
m=n+1;
l=n-1;
cout<<Input the elements of A rowwise and elements of B<<endl;
for(i=1;i<=n;i++)
{
for(j=1;j<=m;j++)
{
cin>>a[i][j];
}
}
for(i=1;i<=n;i++)
{
for(j=1;j<=m;j++)
{
cout<<a[i][j]<<endl;
}
}
for(k=1;k<=l;k++)
{
big=fabs(a[k][k]);
jj=k;
kp1=k+1;
for(i=kp1;i<=n;i++)
{
ab=fabs(a[i][k]);
if((big-ab)<0.0)
{
big=ab;
jj=i;
}
}
if((jj-k)>0)
{
for(j=k;j<=m;j++)
{
t=a[jj][j];
a[jj][j]=a[k][j];

Appendix: Programs in C++

a[k][j]=t;
}
}
for(i=kp1;i<=n;i++)
{
quot=a[i][k]/a[k][k];
for(j=kp1;j<=m;j++)
{
a[i][j]=a[i][j]-quot*a[k][j];
}
}
for(i=kp1;i<=n;i++)
{
a[i][k]=0.0;
}
}
x[n]=a[n][m]/a[n][n];
for(nn=1;nn<=l;nn++)
{
sum=0.0;
i=n-nn;
ip1=i+1;
for(j=ip1;j<=n;j++)
{
sum=sum+a[i][j]*x[j];
}
x[i]=(a[i][m]-sum)/a[i][i];
}
for(i=1;i<=n;i++)
{cout<<x[i]<<endl;}
getch();
}

PROGRAM 1.3
//PROGRAM 1.3
//program for the solution of linear algebraic equations
//by the Gauss-Seidel method
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float x1old,x2old,x3old,x1new,x2new,x3new;
x1new=2.0;

229

230

Appendix:

Programs in C++

x2new=3.0;
x3new=4.0;
do
{
x1old=x1new;
x2old=x2new;
x3old=x3new;
x1new=(44.0-x2old-2*x3old)/10.0;
x2new=(51.0-2*x1new-x3old)/10.0;
x3new=(61.0-x1new-2*x2new)/10.0;
}while(fabs(x1new-x1old)>1e-6&&fabs(x2new-x2old)>1e-6&&fabs(x3newx3old)>1e-6);
cout<<x1new<< <<x2new<< <<x3new<<endl;
getch();
}

PROGRAM 2.1
//PROGRAM 2.1
//program to solve for pressure drop in a pipe (nonlaminar case)
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float fricf,epsilon,d,mu,rho,v,fricfnew,f,fdash,Re,deltap,length,a1,a2,a3;
int n;
d=0.004,v=50.0,rho=1.23,mu=1.79e-5,epsilon=0.0015e-3,length=1.0;
cout<<\t\t\t OUTPUT<<endl;
cout<<\nEnter the initial value of fricfact;
cin>>fricf;
a1=epsilon/d;
Re=rho*v*d/mu;
a2=2.51/Re;
n=0;
fricfnew=0.01;
do
{
fricf=fricfnew;
f=(1.0/sqrt(fricf))+2.0*log10((a1/3.7)+(a2/sqrt(fricf)));
a3=-0.5*pow(fricf,-1.5);
fdash=a3+2.0*a2*a3/((a1/3.7)+(a2/sqrt(fricf)));
fricfnew=fricf-f/fdash;
n=n+1;

Appendix: Programs in C++

231

}while(fabs(fricfnew-fricf)>1e-6);
deltap=fricfnew*length*v*v*rho/(2.0*d);
cout<<\t Friction factor is <<fricfnew<<endl;
cout<<Pressure drop is <<deltap<<endl;
cout<<Number of iterations performed <<n<<endl;
getch();
}

PROGRAM 2.2
//PROGRAM 2.2
//program to solve for minimum fluidization velocity
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float epsilon,mu,vmf,phis,dp,rhop,rhog,a1,a2,a3,v,vnew,f,fdash;
const g=9.81;
int n;
dp=0.00012, phis=0.88, rhog=2.374, rhop=1000.0, mu=1.845e-5,
epsilon=0.42;
cout<<\t\t\t OUTPUT<<endl;
cout<<\nEnter the initial value of vmf in m/s ;
cin>>vmf;
a1=1.75*rhog*(1.0-epsilon)/(phis*dp*pow(epsilon,3.0));
a2=150.0*mu*(1.0-epsilon)*(1.0-epsilon)/(phis*phis*dp*dp*pow(epsilon,3));
a3=(1.0-epsilon)*(rhop-rhog)*g;
n=0;
vnew=0.01;
do
{
v=vnew;
f=a1*v*v+a2*v-a3;
fdash=2.0*a1*v+a2;
vnew=v-f/fdash;
n=n+1;
}while(fabs(vnew-v)>1e-6);
cout<<\t Velocity at minimum fluidization is <<vnew<< m/s <<endl;
cout<<Number of iterations performed were <<n<<endl;
getch();
}

232

Appendix:

Programs in C++

PROGRAM 2.3
//PROGRAM 2.3
//program to solve for terminal velocity
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float vt,vtnew,rhop,rhog,dp,cd,rep,mu,a1;
float g=9.81;
int n;
rhog=1.18,rhop=900.0,dp=0.002,mu=1.85e-5;
cout<<\nEnter the value of initial value of terminal velocity in m/
s ;
cin>>vtnew;
do
{
vt=vtnew;
rep=rhog*vt*dp/mu;
cd=24.0*(1.0+0.15*pow(rep,0.687))/rep;
a1=4.0*(rhop-rhog)*g*dp/(3.0*cd*rhog);
vtnew=sqrt(a1);
n=n+1;
}while(fabs(vtnew-vt)>1e-6);
cout<<\t Value of terminal velocity is <<vtnew<<endl;
cout<<number of iterations performed is <<n<<endl;
getch();
}

PROGRAM 2.4
//PROGRAM 2.4
//program for the solution of two simultaneous nonlinear equations
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float x1,x2,x1new,x2new,f1,f2,df1dx1,df1dx2,df2dx1,df2dx2;
float d,deltax1,deltax2;
int n;
x1new=0.1;

Appendix: Programs in C++

233

x2new=0.5;
n=0;
do
{
x1=x1new;
x2=x2new;
f1=pow(2.71828,x1)+x1*x2-1.0;
f2=sin(x1*x2)+x1+x2-1.0;
df1dx1=pow(2.71828,x1)+x2;
df1dx2=x1;
df2dx1=x2*cos(x1*x2)+1.0;
df2dx2=x1*cos(x1*x2)+1.0;
d=df1dx1*df2dx2-df1dx2*df2dx1;
deltax1=(f2*df1dx2-f1*df2dx2)/d;
deltax2=(f1*df2dx1-f2*df1dx1)/d;
x1new=x1+deltax1;
x2new=x2+deltax2;
n=n+1;
}while(fabs(x1new-x1)>1e-6&&fabs(x2new-x2)>1e-6);
cout<<The number of iterations performed is <<n<<endl;
cout<<x1new<< <<x2new<<endl;
getch();
}

PROGRAM 3.1

//PROGRAM 3.1
//program to calculate the molar volume in the liquid and vapour phases at the
//given temperature and pressure
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float w,s,t,tc,k,a,b,r=8.314,lpha,sol[2],vold,vnew,B,tr,b0,b1;
float p,pc,f,f1;
cout<<Enter the value of temperature in deg K and pressure in Pa;
cin>>t>>p;
cout<<Enter the value of critical temperature in deg K and critical
pressure in Pa;
cin>>tc>>pc;
cout<<Enter the value of acentric factor;
cin>>w;
//
//VIRIAL GAS EQUATION OF STATE Z(T,P)
//

234

Appendix:

Programs in C++

tr=t/tc;
b0=.083-0.422*pow(tr,-1.6);
b1=.139-0.172*pow(tr,-4.2);
B=(b0+w*b1)*r*tc/pc;
vnew=r*t/p+B;
cout<<Volume of vapour by virial eos Z(T,P) <<vnew<<m3/mol<<endl;
//
//VIRIAL GAS EQUATION OF STATE Z(T,V)
//
vnew=r*t/p;
do
{
vold=vnew;
f=p*vold/(r*t)-1-B/vold;
f1=p/(r*t)+B/(vold*vold);
vnew=vold-f/f1;
}
while(fabs(vnew-vold)>1e-6);
cout<<Volume of vapour by virial eos Z(T,V) <<vnew<<m3/mol<<endl;
//
//PENGROBINSON CUBIC EQUATION OF STATE
//
int i=0;
k=.37464+1.54226*w-.26992*w*w;
s=1+k*(1-pow(t/tc,.5));
lpha=pow(s,2);
a=.45724*r*r*tc*tc*lpha/pc;
b=.07780*r*tc/pc;
vnew=b;
for(i=0;i<=1;++i)
{
do
{
vold=vnew;
f=pow(vold,3)*p+vold*vold*(p*b-r*t)-vold*(3*p*b*b+2*b*r*t-a);
f=f+(p*b*b*b+b*b*r*t-a*b);
f1=pow(vold,2)*3*p+vold*2*(b*p-t*r)+(a-3*b*b*p-2*r*t*b);
vnew=vold-f/f1;
}
while(fabs(vnew-vold)>1e-6);
sol[i]=vnew;
vnew=r*t/p;
}
cout<<Volume of saturated liquid by Peng-Robinson <<sol[0]<<m3/
mol<<endl<<

Appendix: Programs in C++

235

Volume of saturated vapour by Peng-Robinson <<sol[1]<<m3/mol\n;

//
//REDLICHKWONG CUBIC EQUATION OF STATE
//
i=0;
a=.42748*r*r*pow(tc,2.5)/pc;
b=.08664*r*tc/pc;
vnew=b;
for(i=0;i<=1;++i)
{
do
{
vold=vnew;
f=pow(vold,3)*p-r*t*vold*vold-vold*(p*b*b+b*r*t-a/sqrt(t))-a*b/
sqrt(t);
f1=pow(vold,2)*3*p-vold*2*r*t-(p*b*b+b*r*t-a/sqrt(t));
vnew=vold-f/f1;
}
while(fabs(vnew-vold)>1e-6);
sol[i]=vnew;
vnew=r*t/p;
}
cout<<Volume of saturated liquid by RedlichKwong <<sol[0]<<m3/
mol<<endl<<
Volume of saturated vapour by RedlichKwong <<sol[1]<<m3/mol\n;
//
//VAN DER WAALS CUBIC EQUATION OF STATE
//
i=0;
a=27*r*r*tc*tc/(64*pc);
b=r*tc/(8*pc);
vnew=b;
for(i=0;i<=1;++i)
{
do
{
vold=vnew;
f=pow(vold,3)*p-vold*vold*(p*b+r*t)+a*vold-a*b;
f1=pow(vold,2)*3*p-vold*2*(b*p+t*r)+a;
vnew=vold-f/f1;
}
while(fabs(vnew-vold)>1e-6);
sol[i]=vnew;
vnew=r*t/p;
}

236

Appendix:

Programs in C++

cout<<Volume of saturated liquid by van der Waals <<sol[0]<<m3/

mol<<endl<<
Volume of saturated vapour by van der Waals <<sol[1]<<m3/mol\n;
getch();
}

PROGRAM 3.2
//PROGRAM 3.2
//program to calculate the BPT and DPT
//of a mixture of given composition, assuming Raoults law to be true
//BPT is calculated by taking the given composition to be in liquid phase
//DPT is calculated by taking the given composition to be in vapour phase
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float p,p1sat,p2sat,p1satn,t1sat,t2sat;
float told,tnew,x1,x2,y1,y2,z1,a1,b1,c1,a2,b2,c2;
float f,f1;
cout<<\nEnter the mole fraction of component 1;
cin>>z1;
cout<<\nEnter the pressure in kPa;
cin>>p;
// the Antoine constants are for acetone (1) and water (2). For use of
// these constants temperature is in deg C and pressure in kPa.
a1=14.39155;
b1=2795.317;
c1=230.002;
a2=16.26205;
b2=3799.887;
c2=226.346;
//CALCULATION OF BUBBLE POINT TEMPERATURE
x1=z1;
x2=1-z1;
t1sat=b1/(a1-log(p))-c1;
t2sat=b2/(a2-log(p))-c2;
tnew=x1*t1sat+x2*t2sat;
do
{
told=tnew;
p1sat=exp(a1-b1/(told+c1));

Appendix: Programs in C++

237

p2sat=exp(a2-b2/(told+c2));
f=p-x1*p1sat-x2*p2sat;
f1=-x1*p1sat*b1/((told+c1)*(told+c1))-x2*p2sat*b2/
((told+c2)*(told+c2));
tnew=told-f/f1;
}while(fabs(tnew-told)>1e-6);
cout<<\nThe bubble point temperature is:<<tnew;
//CALCULATION OF DEW POINT TEMPERATURE
y1=z1;
y2=1-z1;
t1sat=b1/(a1-log(p))-c1;
t2sat=b2/(a2-log(p))-c2;
tnew=y1*t1sat+y2*t2sat;
do
{
told=tnew;
p1sat=exp(a1-b1/(told+c1));
p2sat=exp(a2-b2/(told+c2));
f=(1/p)-(y1/p1sat)-(y2/p2sat);
f1=(y1*b1/((told+c1)*(told+c1)))/(p1sat)+(y2*b2/
((told+c2)*(told+c2)))/(p2sat);
tnew=told-f/f1;
}while(fabs(tnew-told)>1e-6);
cout<<\nThe dew point temperature is <<tnew;
getch();
}

PROGRAM 3.3
//PROGRAM 3.3
//program to calculate the compositions of the vapour and liquid phases
//at the given
//temperature and pressure under flash conditions, assuming Raoults law
//to be true
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int i;
float psat[4],k[4],z[4],x[4],y[4],dpp,bpp,V,p,Vo,f,f1;
// dpp is the dew point pressure, bpp is bubble point pressure and
// V is the number of moles in the vapour phase.
psat[1]=195.75,psat[2]=97.84,psat[3]=50.32;

238

Appendix:

Programs in C++

cout<<Enter the composition of acetone (1), acetonitrile (2),

nitromethane (3);
cin>>z[1]>>z[2]>>z[3];
bpp=z[1]*psat[1]+z[2]*psat[2]+z[3]*psat[3];
dpp=1/(z[1]/psat[1]+z[2]/psat[2]+z[3]/psat[3]);
cout<<Bubble point pressure of the mixture is <<bpp<< kPa<<endl;
cout<<Dew point pressure of the mixture is <<dpp<< kPa<<endl;
cout<<\nEnter the pressure in kPa in between DPP and BPP \n;
cin>>p;
for(i=1;i<4;i++)
{
k[i]=psat[i]/p;
}
cout<<\n Enter an assumed value for the vapour fraction V;
cin>>V;
f = f1 = 0.0;
do
{
Vo=V;
for(i=1;i<4;i++)
{
f=f+z[i]*(k[i]-1)/(1-Vo+Vo*k[i]);
f1=f1-z[i]*(k[i]-1)*(k[i]-1)/pow((1-Vo+Vo*k[i]),2);
}
V=Vo-f/f1;
}
while(fabs(V-Vo)>1e-6);
for(i=1;i<4;i++)
{
x[i]=z[i]/(1-V+V*k[i]);
y[i]=x[i]*k[i];
}
cout<<Mole fraction of acetone in the liquid phase is <<x[1]<<endl;
cout<<Mole fraction of acetone in the vapour phase is <<y[1]<<endl;
cout<<Mole fraction of acetonitrile in the liquid phase is <<x[2]<<endl;
cout<<Mole fraction of acetonitrile in the vapour phase is <<y[2]<<endl;
cout<<Mole fraction of nitromethane in liquid phase is <<x[3]<<endl;
cout<<Mole fraction of nitromethane in vapour phase is <<y[3]<<endl;
cout<<Number of moles in vapour phase is <<V<<endl;
cout<<x[1]+x[2]+x[3]=<<x[1]+x[2]+x[3]<<endl;
cout<<y[1]+y[2]+y[3]=<<y[1]+y[2]+y[3]<<endl;
getch();
}

Appendix: Programs in C++

239

PROGRAM 3.4
//PROGRAM 3.4
//program to calculate the bubble point pressure, bubble point temperature,
//dew point pressure and dew point temperature, assuming the modified
//Raoults law to be true
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float p,t,a1,b1,c1,a2,b2,c2,p1sat,p2sat,r=8.314,pold,pnew,g11,g22,t1sat,t2sat;
float tnew,told,x1,x2,y1,y2,h12,h21,g1,g2,m,a12=437.98*4.186,a21=1238*4.186;
float V1=76.92,V2=18.07;
a1=16.678;
b1=3640.2;
c1=219.61;
a2=16.2887;
b2=3816.44;
c2=227.02;
//the component 1 is acetone and 2 is water. The pressure in Antoine equation
//is in kPa and temperature in deg C. a12 and a21 are in cal/mol.
//
//CALCULATION OF BPP (temperature and liquid phase composition are given)
cout<<Calculation of BPP<<endl;
cout<<Enter the value of temperature in deg C and mole fraction x1;
cin>>t>>x1;
x2=1-x1;
p1sat=exp(a1-b1/(c1+t));
p2sat=exp(a2-b2/(c2+t));
h12=V2*exp(-a12/(r*(t+273.15)))/V1;
h21=V1*exp(-a21/(r*(t+273.15)))/V2;
m=h12/(x1+x2*h12)-h21/(x2+x1*h21);
g1=exp(-log(x1+x2*h12)+x2*m);
g2=exp(-log(x2+x1*h21)-x1*m);
p=x1*g1*p1sat+x2*g2*p2sat;
cout<<BPP=<<p<<kPa\n;
//
//CALCULATION OF BPT (pressure and liquid phase composition are given)
cout<<Calculation of BPT<<endl;
cout<<Enter the value of pressure in kPa and x1\n;
cin>>p>>x1;
x2=1-x1;
t1sat=b1/(a1-log(p))-c1;
t2sat=b2/(a2-log(p))-c2;

240

Appendix:

Programs in C++

tnew=x1*t1sat+x2*t2sat;
do
{
told=tnew;
p1sat=exp(a1-b1/(c1+told));
p2sat=exp(a2-b2/(c2+told));
h12=V2*exp(-a12/(r*(told+273.15)))/V1;
h21=V1*exp(-a21/(r*(told+273.15)))/V2;
m=h12/(x1+x2*h12)-h21/(x2+x1*h21);
g1=exp(-log(x1+x2*h12)+x2*m);
g2=exp(-log(x2+x1*h21)-x1*m);
p1sat=p/(g1*x1+g2*x2*(p2sat/p1sat));
tnew=b1/(a1-log(p1sat))-c1;
}
while(fabs(tnew-told)>.0001);
cout<<BPT=<<tnew<<deg C\n;
//
//CALCULATION OF DPP (temperature and vapour phase composition are given)
cout<<Calculation of DPP<<endl;
cout<<Enter the temperature in deg C and y1\n;
cin>>t>>y1;
y2=1-y1;
p1sat=exp(a1-b1/(c1+t));
p2sat=exp(a2-b2/(c2+t));
g1=g2=1;
g11=g22=1;
pnew=1/(y1/(g1*p1sat)+y2/(g2*p2sat));
do
{
pold=pnew;
do
{
g1=g11;
g2=g22;
x1=y1*pold/(g1*p1sat);
x2=y2*pold/(g2*p2sat);
x1=x1/(x1+x2);
x2=1-x1;
h12=V2*exp(-a12/(r*(t+273.15)))/V1;
h21=V1*exp(-a21/(r*(t+273.15)))/V2;
m=h12/(x1+x2*h12)-h21/(x2+x1*h21);
g11=exp(-log(x1+x2*h12)+x2*m);
g22=exp(-log(x2+x1*h21)-x1*m);
}
while((fabs(g11-g1)>.001)&&(fabs(g22-g2)>.001));
pnew=1/(y1/(g1*p1sat)+y2/(g2*p2sat));
}

Appendix: Programs in C++

241

while(fabs(pnew-pold)>.0001);
cout<<DPP=<<pnew<<kPa\n;
//
//CALCULATION OF DPT (pressure and vapour phase composition are given)
cout<<Calculation of DPT<<endl;
cout<<Enter the pressure in kPa and y1\n;
cin>>p>>y1;
y2=1-y1;
t1sat=b1/(a1-log(p))-c1;
t2sat=b2/(a2-log(p))-c2;
tnew=y1*t1sat+y2*t2sat;
g11=g22=1;
do
{
told=tnew;
p1sat=exp(a1-b1/(c1+told));
p2sat=exp(a2-b2/(c2+told));
do
{
g1=g11;
g2=g22;
x1=y1*p/(g1*p1sat);
x2=y2*p/(g2*p2sat);
x1=x1/(x1+x2);
x2=1-x1;
h12=V2*exp(-a12/(r*(told+273.15)))/V1;
h21=V1*exp(-a21/(r*(told+273.15)))/V2;
m=h12/(x1+x2*h12)-h21/(x2+x1*h21);
g11=exp(-log(x1+x2*h12)+x2*m);
g22=exp(-log(x2+x1*h21)-x1*m);
}
while((fabs(g11-g1)>.0001)&&(fabs(g22-g2)>.0001));
p1sat=p*(y1/g1+y2*p1sat/(g2*p2sat));
tnew=b1/(a1-log(p1sat))-c1;
}
while(fabs(tnew-told)>.0001);
cout<<DPT=<<tnew<<deg C\n;
getch();
}

PROGRAM 3.5
//PROGRAM 3.5
//program to calculate the compositions of the liquid and vapour phases under
//flash conditions, assuming the modified Raoults law to be true
#include<iostream.h>

242

Appendix:

Programs in C++

#include<conio.h>
#include<math.h>
void main()
{
clrscr();
// the component 1 is acetone and 2 is water. The pressure in Antoine equation
// is in kPa and temperature in deg C. a12 and a21 are in cal/mol.
float t,p,z1,z2,a12=292.66,a21=1445.26,V1=74.05,V2=18.07,h12,h21;
float r=1.987,m,g1,g2,g1n,g2n,gb1,gb2,gd1,gd2;
float p1sat,p2sat,k1,k2,V,Vnew,bpp,dpp,pnew,pold;
float A1,A2,B1,B2,C1,C2;
float x1,x2,y1,y2,f,f1;
cout<<Enter the temperature in deg C;
cin>>t;
cout<<Enter the overall composition of species 1;
cin>>z1;
z2=1-z1;
//Listing the values of the Antoine parameters
A1=14.39155;
A2=16.26205;
B1=2795.817;
B2=3799.887;
C1=230.002;
C2=226.346;
//Calculation of BPP
x1=z1;
x2=z2;
p1sat=exp(A1-(B1/(t+C1)));
p2sat=exp(A2-(B2/(t+C2)));
h12=V2*exp(-a12/(r*(t+273.15)))/V1;
h21=V1*exp(-a21/(r*(t+273.15)))/V2;
m=(h12/(x1+x2*h12))-(h21/(x2+x1*h21));
g1=exp(-log(x1+x2*h12)+x2*m);
g2=exp(-log(x2+x1*h21)-x1*m);
p=x1*g1*p1sat+x2*g2*p2sat;
cout<<BPP=<<p<<kPa\n;
bpp=p;
gb1=g1;
gb2=g2;
//Calculation of DPP
y1=z1;
y2=z2;
p1sat=exp(A1-(B1/(t+C1)));
p2sat=exp(A2-(B2/(t+C2)));
g1=g2=1;
pnew=1/(y1/(g1*p1sat)+y2/(g2*p2sat));

Appendix: Programs in C++

g1n=g1;g2n=g2;
do
{
pold=pnew;
do
{
g1=g1n;
g2=g2n;
x1=y1*pold/(g1*p1sat);
x2=y2*pold/(g2*p2sat);
x1=x1/(x1+x2);
x2=1-x1;
h12=V2*exp(-a12/(r*(t+273.15)))/V1;
h21=V1*exp(-a21/(r*(t+273.15)))/V2;
m=(h12/(x1+x2*h12))-(h21/(x2+x1*h21));
g1n=exp(-log(x1+x2*h12)+x2*m);
g2n=exp(-log(x2+x1*h21)-x1*m);
}
while(fabs(g1n-g1)>.0001&&fabs(g2n-g2)>.0001);
pnew=1/(y1/(g1n*p1sat)+y2/(g2n*p2sat));
}
while(fabs(pnew-pold)>.0001);
cout<<DPP=<<pnew<<\n;
dpp=pnew;
gd1=g1n;
gd2=g2n;
cout<<Enter a pressure between <<dpp<< and <<bpp<<\n;
cin>>p;
V=(bpp-p)/(bpp-dpp);
g1=((p-dpp)*(gb1-gd1))/(bpp-dpp)+gd1;
g2=((p-dpp)*(gb2-gd2))/(bpp-dpp)+gd2;
//Calculation of distribution coefficients
do
{
g1n=g1;
g2n=g2;
k1=g1n*p1sat/p;
k2=g2n*p2sat/p;
do
{
V=Vnew;
y1=(k1*z1)/(1-V+V*k1);
y2=(k2*z2)/(1-V+V*k2);
x1=y1/k1;
x2=y2/k2;
f=y1-x1+y2-x2;

243

244

Appendix:

Programs in C++

f1=-(z1*(k1-1)*(k1-1)/((1-V+V*k1)*(1-V+V*k1))+
z2*(k2-1)*(k2-1)/((1-V+V*k2)*(1-V+V*k2)));
Vnew=V-f/f1;
}
while(fabs(Vnew-V)>.00001);
h12=V2*exp(-a12/(r*(t+273.15)))/V1;
h21=V1*exp(-a21/(r*(t+273.15)))/V2;
m=(h12/(x1+x2*h12))-(h21/(x2+x1*h21));
g1=exp(-log(x1+x2*h12)+x2*m);
g2=exp(-log(x2+x1*h21)-x1*m);
}
while(fabs(g1-g1n)>.0001&&fabs(g2-g2n)>.0001);
cout<<The number of moles in vapour phase is<<Vnew<<\n;
cout<<x1+x2=<<(x1+x2)<<\n;
cout<<y1+y2=<<(y1+y2)<<\n;
cout<<x1=<<x1<<\n;
cout<<y1=<<y1<<\n;
getch();
}

PROGRAM 3.6
//PROGRAM 3.6
//program to calculate the vapour pressure at the given
//temperature using the PengRobinson eos by comparing the fugacities of the
//liquid and vapour phases
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float w,s,t,tc,k,a,b,r=8.314,lpha,vold,vnew;
float vliq,vvap,zliq,zvap,c,d,fl,fv,pnew,p,pc,f,f1;
cout<<Enter the temperature in deg K and assumed pressure in Pa;
cin>>t>>pnew;
cout<<Enter the value of the critical temperature in deg K and the
critical pressure in Pa;
cin>>tc>>pc;
cout<<Enter the value of the acentric factor;
cin>>w;
k=.37464+1.54226*w-.26992*w*w;
s=1+k*(1-pow(t/tc,.5));
lpha=pow(s,2);
a=.45724*r*r*tc*tc*lpha/pc;
b=.07780*r*tc/pc;

Appendix: Programs in C++

245

do
{
p=pnew;
vnew=b;
do
{
vold=vnew;
f=pow(vold,3.0)*p+vold*vold*(p*b-r*t)-vold*(3.0*p*b*b+2.0*b*r*t-a);
f=f+(p*b*b*b+b*b*r*t-a*b);
f1=pow(vold,2.0)*3.0*p+vold*2.0*(b*p-t*r)+(a-3.0*b*b*p-2.0*r*t*b);
vnew=vold-f/f1;
}
while(fabs(vnew-vold)>1e-6);
vliq=vnew;
zliq=p*vliq/(r*t);
c=(a/(2.0*sqrt(2.0)*b*r*t))*(log((zliq+(1.0+sqrt(2.0))*b*p/(r*t))/
(zliq+(1.0-sqrt(2.0))*b*p/(r*t))));
fl=p*exp(zliq-1-log(zliq-p*b/(r*t))-c);
vnew=r*t/p;
do
{
vold=vnew;
f=pow(vold,3.0)*p+vold*vold*(p*b-r*t)-vold*(3.0*p*b*b+2.0*b*r*t-a);
f=f+(p*b*b*b+b*b*r*t-a*b);
f1=pow(vold,2.0)*3.0*p+vold*2.0*(b*p-t*r)+(a-3.0*b*b*p-2.0*r*t*b);
vnew=vold-f/f1;
}
while(fabs(vnew-vold)>1e-6);
vvap=vnew;
zvap=p*vvap/(r*t);
d=(a/(2.0*sqrt(2.0)*b*r*t))*(log((zvap+(1.0+sqrt(2.0))*b*p/(r*t))/
(zvap+(1.0-sqrt(2.0))*b*p/(r*t))));
fv=p*exp(zvap-1.0-log(zvap-b)-d);
pnew=p*fl/fv;
}
while(fabs(pnew-p)>1e-6);
cout<<The saturated vapour pressure at <<t<< deg K is <<pnew<<
Pa<<endl;
getch();
}

PROGRAM 3.7
//PROGRAM 3.7
//program to calculate the bubble point pressure using the gammaphi approach
#include<iostream.h>

246

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Programs in C++

#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float p,t,p1sat,p2sat,r=8.314,pnew,vc1,vc2,x1,x2,y1,y2,h12,h21,b11;
float b22,b12,vc12,pc1,pc2,pc12,w1,w2,w12,tc1,tc2,tc12,zc1,zc2,zc12;
float fc1,fc2,snew=0.0,g1,g2,f1,f2,b0,b1,tr1,tr2,tr12,k1,k2,sold,v1;
float v2,a12,a21,z,d12,A1,A2,B1,B2,C1,C2;
// read the values of tc1,tc2,pc1,pc2,w1,w2,zc1,zc2
// the data given are for the methanol (1) - water (2) system
// A1, B1, C1, A2, B2, C2 denote the Antoine constants in this program
a12=107.38*4.186;a21=469.55*4.186;
tc1=512.6;tc2=647.1;pc1=80.97*pow(10,5);pc2=220.55*pow(10,5);
w1=0.564;w2=0.345;zc1=0.224;zc2=0.229;v1=40.73*pow(10,-6);
v2=18.07*pow(10,-6);
//feed the temperature in degree C
t=100.0;x1=0.958;x2=1-x1;
A1=16.5938;
A2=16.2620;
B1=3644.3;
B2=3799.89;
C1=239.76;
C2=226.35;
p1sat=exp(A1-B1/(C1+t));
p2sat=exp(A2-B2/(C2+t));
p1sat=p1sat*1000; // converting kPa to Pa
p2sat=p2sat*1000;
t=t+273.15;
h12=(v2/v1)*exp(-a12/(r*t));
h21=(v1/v2)*exp(-a21/(r*t));
z=h12/(x1+x2*h12)-h21/(x2+x1*h21);
g1=exp(-log(x1+x2*h12)+x2*z);
g2=exp(-log(x2+x1*h21)-x1*z);
tr1=t/tc1;
b0=.083-0.422*pow(tr1,-1.6);
b1=.139-0.172*pow(tr1,-4.2);
b11=(r*tc1/pc1)*(b0+w1*b1);
tr2=t/tc2;
b0=.083-0.422*pow(tr2,-1.6);
b1=.139-0.172*pow(tr2,-4.2);
b22=(r*tc2/pc2)*(b0+w2*b1);
w12=(w1+w2)*0.5;
tc12=pow((tc1*tc2),0.5);
zc12=(zc1+zc2)*0.5;
vc1=zc1*r*tc1/pc1;vc2=zc2*r*tc2/pc2;

Appendix: Programs in C++

247

vc12=pow((pow(vc1,0.333333)+pow(vc2,0.33333))*0.5,3);
pc12=zc12*r*tc12/vc12;
tr12=t/tc12;
b0=.083-0.422*pow(tr12,-1.6);
b1=.139-0.172*pow(tr12,-4.2);
b12=(r*tc12/pc12)*(b0+w12*b1);
d12=2*b12-b11-b22;
p=x1*g1*p1sat+x2*g2*p2sat;
y1=x1*g1*p1sat/p;y2=x2*g2*p2sat/p;
pnew = p;
do
{
p=pnew;
f1=p1sat*(exp(b11*p1sat/(r*t)))*(exp((v1*(p-p1sat)/(r*t))));
f2=p2sat*(exp(b22*p2sat/(r*t)))*(exp((v2*(p-p2sat)/(r*t))));
do
{
sold=snew;
fc1=exp((p/(r*t))*(b11+y2*y2*d12));
fc2=exp((p/(r*t))*(b22+y1*y1*d12));
k1=g1*f1/(fc1*p);
k2=g2*f2/(fc2*p);
snew=x1*k1+x2*k2;
y1=x1*k1/snew;
y2=x2*k2/snew;
}
while(fabs(snew-sold)>1e-6);
pnew=(x1*g1*f1/fc1)+(x2*g2*f2/fc2);
y1=x1*g1*f1/(fc1*pnew);y2=x2*g2*f2/(fc2*pnew);
}
while(fabs(pnew-p)>1e-6);
cout<<fc1=<<fc1<<endl<<fc2=<<fc2<<endl;
cout<<g1=<<g1<<endl<<g2=<<g2<<endl;
cout<<k1=<<k1<<endl<<k2=<<k2<<endl;
cout<<p=<<p<<endl<<y1=<<y1<<endl;
getch();
}

PROGRAM 3.8
//PROGRAM 3.8
//program to calculate the bubble point pressure using the PengRobinson eos
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{

248

Appendix:

Programs in C++

float t,x1,x2,y1,y2,tc1,tc2,v,vnew,pnew,p,zliq,zvap,avap,bvap;
float fc1l,fc2l,fc1v,fc2v,y1n,y2n;
float k1,k2,w1,w2,f,f1,lpha1,lpha2,r,snew,sold,pc1,pc2;
float aliq,bliq,b1,b2,a11,a22,a12,m1,m2;
clrscr();
//the data are for the CO2 (1) n-pentane (2) system
t=377.65;x1=0.5;
cout<<The value of x1=<<x1<<endl;
cout<<Enter an assumed value of y1 greater than x1 \n;
cin>>y1;
tc1=304.2;tc2=469.7;pc1=73.83e5;pc2=33.70e5;w1=0.224;w2=0.252;
r=8.314;x2=1-x1;y2=1-y1;
k1=0.37464+1.54226*w1-0.26992*w1*w1;
k2=0.37464+1.54226*w2-0.26992*w2*w2;
m1=1+k1*(1-pow(t/tc1,0.5));
m2=1+k2*(1-pow(t/tc2,0.5));
lpha1=m1*m1;
lpha2=m2*m2;
a11=0.455724*r*r*tc1*tc1*lpha1/pc1;
a22=0.455724*r*r*tc2*tc2*lpha2/pc2;
a12=(pow(a11*a22,0.5));
b1=0.07780*r*tc1/pc1;
b2=0.07780*r*tc2/pc2;
aliq=(x1*x1*a11+x2*x2*a22+2*x1*x2*a12);
bliq=x1*b1+x2*b2;
pnew=50e5; // assumed value for pressure in Pa
snew=0.0;
do
{
p=pnew;
vnew=bliq;
do
{
v=vnew;
f=pow(v,3)*p+v*v*(p*bliq-r*t)-v*(3*p*bliq*bliq+2*bliq*r*t-aliq);
f=f+(p*bliq*bliq*bliq+bliq*bliq*r*t-aliq*bliq);
f1=pow(v,2)*3*p+v*2*(bliq*p-r*t)+(aliq-3*bliq*bliq*p-2*r*t*bliq);
vnew=v-(f/f1);
}
while(fabs(vnew-v)>1e-6);
zliq=p*vnew/(r*t);
fc1l=exp((b1/bliq)*(zliq-1)-log(zliq-bliq*p/(r*t))-(aliq/
(2*sqrt(2)*r*t*bliq))*
((2*(x1*a11+x2*a12)/aliq)-(b1/bliq))*log((zliq+(2.414*bliq*p/
(r*t)))/(zliq(.414*bliq*p/(r*t)))));

Appendix: Programs in C++

249

fc2l=exp((b2/bliq)*(zliq-1)-log(zliq-bliq*p/(r*t))-(aliq/
(2*sqrt(2)*r*t*bliq))*
((2*(x1*a12+x2*a22)/aliq)-(b2/bliq))*log((zliq+(2.414*bliq*p/
(r*t)))/(zliq(.414*bliq*p/(r*t)))));
do
{
sold=snew;
avap=(y1*y1*a11+y2*y2*a22+2*y1*y2*a12);
bvap=y1*b1+y2*b2;
vnew=r*t/p;
do
{
v=vnew;
f=pow(v,3)*p+v*v*(p*bvap-r*t)-v*(3*p*bvap*bvap+2*bvap*r*t-avap);
f=f+(p*bvap*bvap*bvap+bvap*bvap*r*t-avap*bvap);
f1=pow(v,2)*3*p+v*2*(bvap*p-r*t)+(avap-3*bvap*bvap*p-2*r*t*bvap);
vnew=v-(f/f1);
}
while(fabs(vnew-v)>1e-6);
zvap=p*vnew/(r*t);
fc1v=exp((b1/bvap)*(zvap-1)-log(zvap-bvap*p/(r*t))-(avap/
(2*sqrt(2)*r*t*bvap))*
((2*(y1*a11+y2*a12)/avap)-(b1/bvap))*log((zvap+(2.414*bvap*p/
(r*t)))/(zvap(.414*bvap*p/(r*t)))));
fc2v=exp((b2/bvap)*(zvap-1)-log(zvap-bvap*p/(r*t))-(avap/
(2*sqrt(2)*r*t*bvap))*
((2*(y1*a12+y2*a22)/avap)-(b2/bvap))*log((zvap+(2.414*bvap*p/
(r*t)))/(zvap(.414*bvap*p/(r*t)))));
k1=fc1l/fc1v;k2=fc2l/fc2v;cout<<k1=<<k1<<endl<<k2=<<k2<<endl;
snew=k1*x1+k2*x2;
y1=k1*x1/snew;
y2=k2*x2/snew;
}
while(fabs(snew-sold)>1e-6);
pnew=p*snew;
}
while(fabs(pnew-p)>1e-6);
cout<<k1=<<k1<<endl<<k2=<<k2<<endl<<bpp=<<pnew<<endl<<y1=<<y1<<endl;
getch();
}

250

Appendix:

Programs in C++

PROGRAM 3.9
//PROGRAM 3.9
//program for the solution of two simultaneous chemical reactions
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float x1,x2,x1new,x2new,f1,f2,df1dx1,df1dx2,df2dx1,df2dx2;
float d1,d2,d3,d4,d5,d6,d7,d8,d9,d10,d11,d,deltax1,deltax2;
int n;
x1new=0.9;
x2new=0.5;
n=0;
do
{
x1=x1new;
x2=x2new;
d1=(x1-x2)*pow((3*x1+x2),3);
d2=(1-x1)*(5-x1-x2)*pow((6+2*x1),2);
f1=(d1/d2)-0.575;
f2=(x2*(3*x1+x2)/((x1-x2)*(5-x1-x2)))-2.21;
d3=pow((3*x1+x2),2)*(12.0*x1-8.0*x2)/((1-x1)*(5-x1 x2)
*(6+2*x1)*(6+2*x1));
d4=pow((3*x1+x2),3)*(x1-x2)*(8*x1*x1+6*x1*x2-24*x1+2*x2-16);
d5=pow((1-x1),2)*pow((5-x1-x2),2)*pow((6+2*x1),3);
df1dx1=d3-(d4/d5);
d6=3*(x1-x2)*(3*x1+x2)*(3*x1+x2)-pow((3*x1+x2),3);
d7=(1-x1)*(5-x1-x2)*(6+2*x1)*(6+2*x1);
d8=((x1-x2)*(pow((3*x1+x2),3)))/((1-x1)*(5-x1-x2)*(5-x1-x2)
*(6+2*x1)*(6+2*x1));
df1dx2=(d6/d7)+d8;
d9=(x1-x2)*(x1-x2)*(5-x1-x2)*(5-x1-x2);
df2dx1=3*x2/((x1-x2)*(5-x1-x2))-(x2*(3*x1+x2)*(5-2*x1))/d9;
d10=(3*x1+2*x2)/((x1-x2)*(5-x1-x2));
d11=x2*(3*x1+x2)*(2*x2-5)/((pow((x1-x2),2))*pow((5-x1-x2),2));
df2dx2=d10-d11;
d=df1dx1*df2dx2-df1dx2*df2dx1;
deltax1=(f2*df1dx2-f1*df2dx2)/d;
deltax2=(f1*df2dx1-f2*df1dx1)/d;
x1new=x1+deltax1;
x2new=x2+deltax2;
n=n+1;

Appendix: Programs in C++

251

}while(fabs(x1new-x1)>1e-6&&fabs(x2new-x2)>1e-6);
cout<<The number of iterations performed is <<n<<endl;
cout<<x1new<< <<x2new<<endl;
getch();
}

PROGRAM 3.10
//PROGRAM 3.10
//program to calculate the adiabatic flame temperature (AFT) for a fuel
//case of complete conversion
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float sa,sb,sc,sd,da,db,dc,dd,t,tnew,t0=298.15,t1,n1,n2,n3,n4,f,f1,h0;
float u1=1,u2=3.5,u3=2,u4=3;
// n1, n2, n3, n4 are the number of moles entering of species
// 1, 2, 3, 4 respectively and u1, u2, u3, and u4 are their stoichiometric
// coefficients. The data is given for the reaction
// C2H6 + 3.5O2 = 2CO2 + 3H2O
// C2H6 is 1, O2 is 2, CO2 is 3 and H2O is 4
float a1=1.648,a2=6.085,a3=5.316,a4=7.700;
float b1=4.124e-2,b2=.3631e-2,b3=1.4285e-2,b4=.04594e-2;
float c1=-1.530e-5,c2=-.1709e-5,c3=-.8362e-5,c4=.2521e-5;
float d1=1.740e-9,d2=.3133e-9,d3=1.784e-9,d4=-.8587e-9;
cout<<Enter the value of n1,n2,n3,n4\n;
cin>>n1>>n2>>n3>>n4;
cout<<\nEnter the inlet temperature in deg C;
cin>>t1;
t1=t1+273.15;
sa=n1*a1+n2*a2+n3*a3+n4*a4;
sb=n1*b1+n2*b2+n3*b3+n4*b4;
sc=n1*c1+n2*c2+n3*c3+n4*c4;
sd=n1*d1+n2*d2+n3*d3+n4*d4;
da=u4*a4+u3*a3-u2*a2-u1*a1;
db=u4*b4+u3*b3-u2*b2-u1*b1;
dc=u4*c4+u3*c3-u2*c2-u1*c1;
dd=u4*d4+u3*d3-u2*d2-u1*d1;
h0=(u4*(-57.7979)+u3*(-94.052)-u2*0-u1*(-20.236))*1000;
tnew=1000;
//for various old values of tnew the final answer is the same
do
{

252

Appendix:

Programs in C++

t=tnew;
f=sa*(t-t1)+(sb/2)*(t*t-t1*t1)+(sc/3)*(t*t*t-t1*t1*t1)+(sd/4)
*(t*t*t*t-t1*t1*t1*t1);
f=f+h0+da*(t-t0)+(db/2)*(t*t-t0*t0)+(dc/3)*(t*t*t-t0*t0*t0)+(dd/4)
*(t*t*t*t-t0*t0*t0*t0);
f1=sa+sb*t+sc*t*t+sd*t*t*t+da+db*t+dc*t*t+dd*t*t*t;
tnew=t-f/f1;
}while(fabs((tnew-t)/tnew)>1e-6);
cout<<AFT=<<tnew;
getch();
}

PROGRAM 4.1
//PROGRAM 4.1
//program to solve an ordinary differential equation by the RungeKutta method
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float h,x0,xf,y,k1,k2,k3,k4;
int n;
x0=0.00000,y=2.00000;
float func(float,float);
cout<<\t\t\t OUTPUT<<endl;
cout<<\nEnter the value of x at which y is required: ;
cin>>xf;
cout<<\tEnter the value of step length (h): ;
cin>>h;
n=(xf-x0)/h;
for(int i=0;i<=n-1;i++)
{
k1=h*func(x0,y);
k2=h*func(x0+0.5*h,y+0.5*k1);
k3=h*func(x0+0.5*h,y+0.5*k2);
k4=h*func(x0+h,y+k3);
y=y+((k1+2.0*k2+2.0*k3+k4)/6.0);
x0=x0+h;
}
cout<<\t Value found by Runge-Kutta method at given x: <<y;
cout<<endl;
getch();
}
float func(float x, float y)
{

Appendix: Programs in C++

253

float f=-y/(1.0+x);
return(f);
}

PROGRAM 4.2
//PROGRAM 4.2
//program to determine the velocity of a particle in a pneumatic conveyor
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float h,z0,z,zf,y0,y,vp,k1,k2,k3,k4;
int n;
z0=0.00000,y0=0.00000;
float func(float,float);
cout<<\t\t\t OUTPUT<<endl;
cout<<\nEnter the value of z in m at which vp is required: ;
cin>>zf;
cout<<\tEnter the value of step length (h): ;
cin>>h;
n=(zf-z0)/h;
for(int i=0;i<=n-1;i++)
{
k1=h*func(z0,y0);
k2=h*func(z0+0.5*h,y0+0.5*k1);
k3=h*func(z0+0.5*h,y0+0.5*k2);
k4=h*func(z0+h,y0+k3);
y=y0+((k1+2.0*k2+2.0*k3+k4)/6.0);
z0=z0+h;
y0=y;
vp=sqrt(y);
cout<<\t Value found at z = <<z0<< = <<vp<<endl;
}
cout<<\t Value found by Runge-Kutta method at given z: <<vp;
cout<<endl;
getch();
}
float func(float a, float b)
{
float rep=19.648*(12.0-sqrt(b));
float cd=24.0*(1.0+0.15*pow(rep,0.687))/rep;
float f=6.55*cd*(12.0-sqrt(b))*(12.0-sqrt(b))-19.594;
return(f);
}

254

Appendix:

Programs in C++

PROGRAM 4.3
//PROGRAM 4.3
//program to solve two simultaneous ordinary differential equations
//by Runge-Kutta method
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float h,x0,xf,y,z,k1,k2,k3,k4,l1,l2,l3,l4;
int n;
x0=0.00000,y=2.00000,z=1.00000;
float func1(float,float,float);
float func2(float,float,float);
cout<<\t\t\t OUTPUT<<endl;
cout<<\nEnter the value of x at which y and z are required: ;
cin>>xf;
cout<<\tEnter the value of step length (h): ;
cin>>h;
n=(xf-x0)/h;
for(int i=0;i<=n-1;i++)
{
k1=h*func1(x0,y,z);
l1=h*func2(x0,y,z);
k2=h*func1(x0+0.5*h,y+0.5*k1,z+0.5*l1);
l2=h*func2(x0+0.5*h,y+0.5*k1,z+0.5*l1);
k3=h*func1(x0+0.5*h,y+0.5*k2,z+0.5*l2);
l3=h*func2(x0+0.5*h,y+0.5*k2,z+0.5*l2);
k4=h*func1(x0+h,y+k3,z+l3);
l4=h*func2(x0+h,y+k3,z+l3);
y=y+((k1+2.0*k2+2.0*k3+k4)/6.0);
z=z+((l1+2.0*l2+2.0*l3+l4)/6.0);
x0=x0+h;
}
cout<<\t Value at given x: <<y<< <<z;
cout<<endl;
getch();
}
float func1(float x, float y, float z)
{
float f=z;
return(f);
}
float func2(float x, float y, float z)
{

Appendix: Programs in C++

255

float f=-y;
return(f);
}

PROGRAM 4.4
//PROGRAM 4.4
//program to solve three simultaneous ordinary differential equations
//by the Runge-Kutta method
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
double h,t0,tf,temp1,temp2,temp3,k1,k2,k3,k4;
double l1,l2,l3,l4,m1,m2,m3,m4;
long n;
t0=0.00000,temp1=20.00000,temp2=20.00000,temp3=20.00000;
double func1(double,double,double,double);
double func2(double,double,double,double);
double func3(double,double,double,double);
cout<<\t\t\t OUTPUT<<endl;
cout<<\nEnter the value of t in sec at which temperatures are required: ;
cin>>tf;
cout<<\tEnter the value of the step length (h): ;
cin>>h;
n=(tf-t0)/h;
cout<<The number n is = <<n<<endl;
for(long i=0;i<=n-1;i++)
{
k1=h*func1(t0,temp1,temp2,temp3);
l1=h*func2(t0,temp1,temp2,temp3);
m1=h*func3(t0,temp1,temp2,temp3);
k2=h*func1(t0+0.5*h,temp1+0.5*k1,temp2+0.5*l1,temp3+0.5*m1);
l2=h*func2(t0+0.5*h,temp1+0.5*k1,temp2+0.5*l1,temp3+0.5*m1);
m2=h*func3(t0+0.5*h,temp1+0.5*k1,temp2+0.5*l1,temp3+0.5*m1);
k3=h*func1(t0+0.5*h,temp1+0.5*k2,temp2+0.5*l2,temp3+0.5*m2);
l3=h*func2(t0+0.5*h,temp1+0.5*k2,temp2+0.5*l2,temp3+0.5*m2);
m3=h*func3(t0+0.5*h,temp1+0.5*k2,temp2+0.5*l2,temp3+0.5*m2);
k4=h*func1(t0+h,temp1+k3,temp2+l3,temp3+m3);
l4=h*func2(t0+h,temp1+k3,temp2+l3,temp3+m3);
m4=h*func3(t0+h,temp1+k3,temp2+l3,temp3+m3);
temp1=temp1+((k1+2.0*k2+2.0*k3+k4)/6.0);
temp2=temp2+((l1+2.0*l2+2.0*l3+l4)/6.0);
temp3=temp3+((m1+2.0*m2+2.0*m3+m4)/6.0);

256

Appendix:

Programs in C++

t0=t0+h;
}
cout<<\t Value at given t: <<temp1<< <<temp2<< <<temp3;
cout<<endl;
getch();
}
double func1(double t, double temp1, double temp2, double temp3)
{
double f=0.065-0.0021*temp1;
return(f);
}
double func2(double t, double temp1, double temp2, double temp3)
{
double f=0.002*temp1-0.0021*temp2+0.025;
return(f);
}
double func3(double t, double temp1, double temp2, double temp3)
{
double f=0.002*temp2-0.0021*temp3+0.025;
return(f);
}

PROGRAM 4.5
//PROGRAM 4.5
//program to solve three simultaneous ordinary differential equations
//for the reaction a -> b -> c by the Runge-Kutta fourth order method
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float h,t0,tf,a,b,c,k1,k2,k3,k4;
float l1,l2,l3,l4,m1,m2,m3,m4;
int n;
t0=0.00000,a=1.00000,b=0.00000,c=0.00000;
float func1(float,float,float,float);
float func2(float,float,float,float);
float func3(float,float,float,float);
cout<<\t\t\t OUTPUT<<endl;
cout<<\nEnter the value of t in sec at which concentrations are required: ;
cin>>tf;
cout<<\tEnter the value of step length (h): ;
cin>>h;
n=(tf-t0)/h;

Appendix: Programs in C++

257

cout<<The number n is <<n<<endl;

for(int i=0;i<=n-1;i++)
{
k1=h*func1(t0,a,b,c);
l1=h*func2(t0,a,b,c);
m1=h*func3(t0,a,b,c);
k2=h*func1(t0+0.5*h,a+0.5*k1,b+0.5*l1,c+0.5*m1);
l2=h*func2(t0+0.5*h,a+0.5*k1,b+0.5*l1,c+0.5*m1);
m2=h*func3(t0+0.5*h,a+0.5*k1,b+0.5*l1,c+0.5*m1);
k3=h*func1(t0+0.5*h,a+0.5*k2,b+0.5*l2,c+0.5*m2);
l3=h*func2(t0+0.5*h,a+0.5*k2,b+0.5*l2,c+0.5*m2);
m3=h*func3(t0+0.5*h,a+0.5*k2,b+0.5*l2,c+0.5*m2);
k4=h*func1(t0+h,a+k3,b+l3,c+m3);
l4=h*func2(t0+h,a+k3,b+l3,c+m3);
m4=h*func3(t0+h,a+k3,b+l3,c+m3);
a=a+((k1+2.0*k2+2.0*k3+k4)/6.0);
b=b+((l1+2.0*l2+2.0*l3+l4)/6.0);
c=c+((m1+2.0*m2+2.0*m3+m4)/6.0);
t0=t0+h;
}
cout<<\t Value at given t: <<a<< <<b<< <<c<<endl;
getch();
}
float func1(float t, float a, float b, float c)
{
float f=-a;
return(f);
}
float func2(float t, float a, float b, float c)
{
float f=a-b;
return(f);
}
float func3(float t, float a, float b, float c)
{
float f=b;
return(f);
}

PROGRAM 4.6
//PROGRAM 4.6
//program to solve four simultaneous ordinary differential equations
//for the reactions a + b -> c and b + c -> d by the Runge-Kutta method
#include<iostream.h>
#include<conio.h>

258

Appendix:

Programs in C++

#include<math.h>
void main()
{
clrscr();
double h,t0,tf,a,b,c,d,k1,k2,k3,k4;
double l1,l2,l3,l4,m1,m2,m3,m4,n1,n2,n3,n4;
long n;
t0=0.00000,a=1.00000,b=1.00000,c=0.00000,d=0.00000;
double func1(double,double,double,double,double);
double func2(double,double,double,double,double);
double func3(double,double,double,double,double);
double func4(double,double,double,double,double);
cout<<\t\t\t OUTPUT<<endl;
cout<<\nEnter the value of t in sec at which concentrations are required: ;
cin>>tf;
cout<<\tEnter the value of step length (h): ;
cin>>h;
n=(tf-t0)/h;
cout<<The number n is = <<n<<endl;
for(long i=0;i<=n-1;i++)
{
k1=h*func1(t0,a,b,c,d);
l1=h*func2(t0,a,b,c,d);
m1=h*func3(t0,a,b,c,d);
n1=h*func4(t0,a,b,c,d);
k2=h*func1(t0+0.5*h,a+0.5*k1,b+0.5*l1,c+0.5*m1,d+0.5*n1);
l2=h*func2(t0+0.5*h,a+0.5*k1,b+0.5*l1,c+0.5*m1,d+0.5*n1);
m2=h*func3(t0+0.5*h,a+0.5*k1,b+0.5*l1,c+0.5*m1,d+0.5*n1);
n2=h*func4(t0+0.5*h,a+0.5*k1,b+0.5*l1,c+0.5*m1,d+0.5*n1);
k3=h*func1(t0+0.5*h,a+0.5*k2,b+0.5*l2,c+0.5*m2,d+0.5*n2);
l3=h*func2(t0+0.5*h,a+0.5*k2,b+0.5*l2,c+0.5*m2,d+0.5*n2);
m3=h*func3(t0+0.5*h,a+0.5*k2,b+0.5*l2,c+0.5*m2,d+0.5*n2);
n3=h*func4(t0+0.5*h,a+0.5*k2,b+0.5*l2,c+0.5*m2,d+0.5*n2);
k4=h*func1(t0+h,a+k3,b+l3,c+m3,d+n3);
l4=h*func2(t0+h,a+k3,b+l3,c+m3,d+n3);
m4=h*func3(t0+h,a+k3,b+l3,c+m3,d+n3);
n4=h*func4(t0+h,a+k3,b+l3,c+m3,d+n3);
a=a+((k1+2.0*k2+2.0*k3+k4)/6.0);
b=b+((l1+2.0*l2+2.0*l3+l4)/6.0);
c=c+((m1+2.0*m2+2.0*m3+m4)/6.0);
d=d+((n1+2.0*n2+2.0*n3+n4)/6.0);
t0=t0+h;
}
cout<<\t Value at given t: <<a<< <<b<< <<c<< <<d<<endl;
getch();
}

Appendix: Programs in C++

double func1(double
{
double f=-a*b;
return(f);
}
double func2(double
{
double f=-a*b-b*c;
return(f);
}
double func3(double
{
double f=a*b-b*c;
return(f);
}
double func4(double
{
double f=b*c;
return(f);

259

t, double a, double b, double c, double d)

t, double a, double b, double c, double d)

t, double a, double b, double c, double d)

t, double a, double b, double c, double d)

PROGRAM 4.7
//PROGRAM 4.7
//program to solve ordinary differential equations in a non-isothermal
//tubular reactor by the Runge-Kutta method
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float h,z0,zf,x,t,k1,k2,k3,k4,l1,l2,l3,l4;
int n;
z0=0.00000,x=0.00000,t=294.15;
float func1(float,float,float);
float func2(float,float,float);
cout<<\t\t\t OUTPUT<<endl;
cout<<\nEnter the value of z in m at which x and t are required: ;
cin>>zf;
cout<<\tEnter the value of step length (h): ;
cin>>h;
n=(zf-z0)/h;
for(int i=0;i<=n-1;i++)

260

Appendix:

Programs in C++

k1=h*func1(z0,x,t);
l1=h*func2(z0,x,t);
k2=h*func1(z0+0.5*h,x+0.5*k1,t+0.5*l1);
l2=h*func2(z0+0.5*h,x+0.5*k1,t+0.5*l1);
k3=h*func1(z0+0.5*h,x+0.5*k2,t+0.5*l2);
l3=h*func2(z0+0.5*h,x+0.5*k2,t+0.5*l2);
k4=h*func1(z0+h,x+k3,t+l3);
l4=h*func2(z0+h,x+k3,t+l3);
x=x+((k1+2.0*k2+2.0*k3+k4)/6.0);
t=t+((l1+2.0*l2+2.0*l3+l4)/6.0);
z0=z0+h;
}
cout<<\t Value at given z: <<x<< <<t<<endl;
cout<<endl;
getch();
}
float func1(float z, float x, float t)
{
float f=0.0527*(1-x)*exp(33.68*(1-388.71/t));
return(f);
}
float func2(float z, float x, float t)
{
float f=7.665*(388.71-t)-29554.1*0.0527*(1-x)*exp(33.68*(1-388.71/t));
return(f);
}

PROGRAM 7.1
//PROGRAM 7.1
//program to calculate the concentration profile in a
//tubular reactor with axial dispersion (second order reaction)
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int i,j,n,i1,n1,k,iter;
float a[101],b[101],c[101],d[101],x[101],x1[101],beta[101],gamma[101];
for(i=2;i<=20;++i)
{a[i]=2.0004;
}
a[21]=2.0008;
c[1]=2.0008;
for(i=2;i<=20;++i)

Appendix: Programs in C++

{c[i]=0.0004;
}
d[1]=-20004.0;
for(i=2;i<=21;++i)
{d[i]=0.0;
}
for(i=1;i<=21;++i)
{x[i]=0.0;
}
iter=0;
do
{
iter=iter+1;
for(i=1;i<=21;++i)
{x1[i]=x[i];}
b[1]=-20005.9992-x1[1];
for(i=2;i<=21;++i)
{b[i]=-2.0008-x1[i];
}
i=1;
n=21;
beta[i]=b[i];
gamma[i]=d[i]/beta[i];
i1=i+1;
for(j=i1;j<=n;++j)
{
beta[j]=b[j]-a[j]*c[j-1]/beta[j-1];
gamma[j]=(d[j]-a[j]*gamma[j-1])/beta[j];
}
x[n]=gamma[n];
n1=n-i;
for(k=1;k<=n1;++k)
{
j=n-k;
x[j]=gamma[j]-c[j]*x[j+1]/beta[j];
}
}while(fabs(x[12]-x1[12])>1e-6&&fabs(x[18]-x1[18])>1e-6);
cout<<\t\t\t THE SOLUTION BY TDMA<<endl;
for(i=1;i<=21;++i)
{
cout<<x[<<i<<] = <<x[i]<<endl;
}
cout<<Number of iterations is <<iter;
getch();
}

261

262

Appendix:

Programs in C++

PROGRAM 7.2
//PROGRAM 7.2
//program to calculate the concentration profile in a tubular reactor
//with axial dispersion in which two parallel reactions take place
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int n,m,l,i,j,k,jj,kp1,nn,ip1;
float a[90][91],x[90],x1[90],sum,big,ab,quot,t;
n=84;
cout<<n<<endl;
m=n+1;
l=n-1;
for(i=1;i<=n;i++)
{
for(j=1;j<=m;j++)
{
a[i][j]=0.0;
}
}
for(i=1;i<=84;i++)
{x[i]=0.01;}
do
{
for(i=1;i<=84;i++)
{x1[i]=x[i];}
a[1][1]=-20005.9992-x1[2];
a[1][5]=2.0008;
a[2][2]=-20005.9992-x1[1]-x1[3];
a[2][6]=2.0008;
a[3][3]=-20005.9992-x1[2];
a[3][7]=2.0008;
a[4][4]=-20005.9992;
a[4][8]=2.0008;
a[5][1]=2.0004;
a[5][5]=-2.0008-x1[6];
a[5][9]=0.0004;
a[6][2]=2.0004;
a[6][6]=-2.0008-x1[5]-x1[7];
a[6][10]=0.0004;
a[7][3]=2.0004;
a[7][7]=-2.0008-x1[6];

Appendix: Programs in C++

a[7][11]=0.0004;
a[8][4]=2.0004;
a[8][8]=-2.0008;
a[8][12]=0.0004;
a[9][5]=2.0004;
a[9][9]=-2.0008-x1[10];
a[9][13]=0.0004;
a[10][6]=2.0004;
a[10][10]=-2.0008-x1[9]-x1[11];
a[10][14]=0.0004;
a[11][7]=2.0004;
a[11][11]=-2.0008-x1[10];
a[11][15]=0.0004;
a[12][8]=2.0004;
a[12][12]=-2.0008;
a[12][16]=0.0004;
a[13][9]=2.0004;
a[13][13]=-2.0008-x1[14];
a[13][17]=0.0004;
a[14][10]=2.0004;
a[14][14]=-2.0008-x1[13]-x1[15];
a[14][18]=0.0004;
a[15][11]=2.0004;
a[15][15]=-2.0008-x1[14];
a[15][19]=0.0004;
a[16][12]=2.0004;
a[16][16]=-2.0008;
a[16][20]=0.0004;
a[17][13]=2.0004;
a[17][17]=-2.0008-x1[18];
a[17][21]=0.0004;
a[18][14]=2.0004;
a[18][18]=-2.0008-x1[17]-x1[19];
a[18][22]=0.0004;
a[19][15]=2.0004;
a[19][19]=-2.0008-x1[18];
a[19][23]=0.0004;
a[20][16]=2.0004;
a[20][20]=-2.0008;
a[20][24]=0.0004;
a[21][17]=2.0004;
a[21][21]=-2.0008-x1[22];
a[21][25]=0.0004;
a[22][18]=2.0004;
a[22][22]=-2.0008-x1[21]-x1[23];
a[22][26]=0.0004;

263

264

Appendix:

Programs in C++

a[23][19]=2.0004;
a[23][23]=-2.0008-x1[22];
a[23][27]=0.0004;
a[24][20]=2.0004;
a[24][24]=-2.0008;
a[24][28]=0.0004;
a[25][21]=2.0004;
a[25][25]=-2.0008-x1[26];
a[25][29]=0.0004;
a[26][22]=2.0004;
a[26][26]=-2.0008-x1[25]-x1[27];
a[26][30]=0.0004;
a[27][23]=2.0004;
a[27][27]=-2.0008-x1[26];
a[27][31]=0.0004;
a[28][24]=2.0004;
a[28][28]=-2.0008;
a[28][32]=0.0004;
a[29][25]=2.0004;
a[29][29]=-2.0008-x1[30];
a[29][33]=0.0004;
a[30][26]=2.0004;
a[30][30]=-2.0008-x1[29]-x1[31];
a[30][34]=0.0004;
a[31][27]=2.0004;
a[31][31]=-2.0008-x1[30];
a[31][35]=0.0004;
a[32][28]=2.0004;
a[32][32]=-2.0008;
a[32][36]=0.0004;
a[33][29]=2.0004;
a[33][33]=-2.0008-x1[34];
a[33][37]=0.0004;
a[34][30]=2.0004;
a[34][34]=-2.0008-x1[33]-x1[35];
a[34][38]=0.0004;
a[35][31]=2.0004;
a[35][35]=-2.0008-x1[34];
a[35][39]=0.0004;
a[36][32]=2.0004;
a[36][36]=-2.0008;
a[36][40]=0.0004;
a[37][33]=2.0004;
a[37][37]=-2.0008-x1[38];
a[37][41]=0.0004;
a[38][34]=2.0004;

Appendix: Programs in C++

a[38][38]=-2.0008-x1[37]-x1[39];
a[38][42]=0.0004;
a[39][35]=2.0004;
a[39][39]=-2.0008-x1[38];
a[39][43]=0.0004;
a[40][36]=2.0004;
a[40][40]=-2.0008;
a[40][44]=0.0004;
a[41][37]=2.0004;
a[41][41]=-2.0008-x1[42];
a[41][45]=0.0004;
a[42][38]=2.0004;
a[42][42]=-2.0008-x1[41]-x1[43];
a[42][46]=0.0004;
a[43][39]=2.0004;
a[43][43]=-2.0008-x1[42];
a[43][47]=0.0004;
a[44][40]=2.0004;
a[44][44]=-2.0008;
a[44][48]=0.0004;
a[45][41]=2.0004;
a[45][45]=-2.0008-x1[46];
a[45][49]=0.0004;
a[46][42]=2.0004;
a[46][46]=-2.0008-x1[45]-x1[47];
a[46][50]=0.0004;
a[47][43]=2.0004;
a[47][47]=-2.0008-x1[46];
a[47][51]=0.0004;
a[48][44]=2.0004;
a[48][48]=-2.0008;
a[48][52]=0.0004;
a[49][45]=2.0004;
a[49][49]=-2.0008-x1[50];
a[49][53]=0.0004;
a[50][46]=2.0004;
a[50][50]=-2.0008-x1[49]-x1[51];
a[50][54]=0.0004;
a[51][47]=2.0004;
a[51][51]=-2.0008-x1[50];
a[51][55]=0.0004;
a[52][48]=2.0004;
a[52][52]=-2.0008;
a[52][56]=0.0004;
a[53][49]=2.0004;
a[53][53]=-2.0008-x1[54];

265

266

Appendix:

Programs in C++

a[53][57]=0.0004;
a[54][50]=2.0004;
a[54][54]=-2.0008-x1[53]-x1[55];
a[54][58]=0.0004;
a[55][51]=2.0004;
a[55][55]=-2.0008-x1[54];
a[55][59]=0.0004;
a[56][52]=2.0004;
a[56][56]=-2.0008;
a[56][60]=0.0004;
a[57][53]=2.0004;
a[57][57]=-2.0008-x1[58];
a[57][61]=0.0004;
a[58][54]=2.0004;
a[58][58]=-2.0008-x1[57]-x1[59];
a[58][62]=0.0004;
a[59][55]=2.0004;
a[59][59]=-2.0008-x1[58];
a[59][63]=0.0004;
a[60][56]=2.0004;
a[60][60]=-2.0008;
a[60][64]=0.0004;
a[61][57]=2.0004;
a[61][61]=-2.0008-x1[62];
a[61][65]=0.0004;
a[62][58]=2.0004;
a[62][62]=-2.0008-x1[61]-x1[63];
a[62][66]=0.0004;
a[63][59]=2.0004;
a[63][63]=-2.0008-x1[62];
a[63][67]=0.0004;
a[64][60]=2.0004;
a[64][64]=-2.0008;
a[64][68]=0.0004;
a[65][61]=2.0004;
a[65][65]=-2.0008-x1[66];
a[65][69]=0.0004;
a[66][62]=2.0004;
a[66][66]=-2.0008-x1[65]-x1[67];
a[66][70]=0.0004;
a[67][63]=2.0004;
a[67][67]=-2.0008-x1[66];
a[67][71]=0.0004;
a[68][64]=2.0004;
a[68][68]=-2.0008;
a[68][72]=0.0004;

Appendix: Programs in C++

a[69][65]=2.0004;
a[69][69]=-2.0008-x1[70];
a[69][73]=0.0004;
a[70][66]=2.0004;
a[70][70]=-2.0008-x1[69]-x1[71];
a[70][74]=0.0004;
a[71][67]=2.0004;
a[71][71]=-2.0008-x1[70];
a[71][75]=0.0004;
a[72][68]=2.0004;
a[72][72]=-2.0008;
a[72][76]=0.0004;
a[73][69]=2.0004;
a[73][73]=-2.0008-x1[74];
a[73][77]=0.0004;
a[74][70]=2.0004;
a[74][74]=-2.0008-x1[73]-x1[75];
a[74][78]=0.0004;
a[75][71]=2.0004;
a[75][75]=-2.0008-x1[74];
a[75][79]=0.0004;
a[76][72]=2.0004;
a[76][76]=-2.0008;
a[76][80]=0.0004;
a[77][73]=2.0004;
a[77][77]=-2.0008-x1[78];
a[77][81]=0.0004;
a[78][74]=2.0004;
a[78][78]=-2.0008-x1[77]-x1[79];
a[78][82]=0.0004;
a[79][75]=2.0004;
a[79][79]=-2.0008-x1[78];
a[79][83]=0.0004;
a[80][76]=2.0004;
a[80][80]=-2.0008;
a[80][84]=0.0004;
a[81][77]=2.0008;
a[81][81]=-2.0008-x1[82];
a[82][78]=2.0008;
a[82][82]=-2.0008-x1[81]-x1[83];
a[83][79]=2.0008;
a[83][83]=-2.0008-x1[82];
a[84][80]=2.0008;
a[84][84]=-2.0008;
a[1][85]=-20004.0;
a[2][85]=-20004.0;

267

268

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Programs in C++

a[3][85]=-x1[1]*x1[2];
a[4][85]=-x1[2]*x1[3];
a[5][85]=0.0;
a[6][85]=0.0;
a[7][85]=-x1[5]*x1[6];
a[8][85]=-x1[6]*x1[7];
a[9][85]=0.0;
a[10][85]=0.0;
a[11][85]=-x1[9]*x1[10];
a[12][85]=-x1[10]*x1[11];
a[13][85]=0.0;
a[14][85]=0.0;
a[15][85]=-x1[13]*x1[14];
a[16][85]=-x1[14]*x1[15];
a[17][85]=0.0;
a[18][85]=0.0;
a[19][85]=-x1[17]*x1[18];
a[20][85]=-x1[18]*x1[19];
a[21][85]=0.0;
a[22][85]=0.0;
a[23][85]=-x1[21]*x1[22];
a[24][85]=-x1[22]*x1[23];
a[25][85]=0.0;
a[26][85]=0.0;
a[27][85]=-x1[25]*x1[26];
a[28][85]=-x1[26]*x1[27];
a[29][85]=0.0;
a[30][85]=0.0;
a[31][85]=-x1[29]*x1[30];
a[32][85]=-x1[30]*x1[31];
a[33][85]=0.0;
a[34][85]=0.0;
a[35][85]=-x1[33]*x1[34];
a[36][85]=-x1[34]*x1[35];
a[37][85]=0.0;
a[38][85]=0.0;
a[39][85]=-x1[37]*x1[38];
a[40][85]=-x1[38]*x1[39];
a[41][85]=0.0;
a[42][85]=0.0;
a[43][85]=-x1[41]*x1[42];
a[44][85]=-x1[42]*x1[43];
a[45][85]=0.0;
a[46][85]=0.0;
a[47][85]=-x1[45]*x1[46];
a[48][85]=-x1[46]*x1[47];

Appendix: Programs in C++

a[49][85]=0.0;
a[50][85]=0.0;
a[51][85]=-x1[49]*x1[50];
a[52][85]=-x1[50]*x1[51];
a[53][85]=0.0;
a[54][85]=0.0;
a[55][85]=-x1[53]*x1[54];
a[56][85]=-x1[54]*x1[55];
a[57][85]=0.0;
a[58][85]=0.0;
a[59][85]=-x1[57]*x1[58];
a[60][85]=-x1[58]*x1[59];
a[61][85]=0.0;
a[62][85]=0.0;
a[63][85]=-x1[61]*x1[62];
a[64][85]=-x1[62]*x1[63];
a[65][85]=0.0;
a[66][85]=0.0;
a[67][85]=-x1[65]*x1[66];
a[68][85]=-x1[66]*x1[67];
a[69][85]=0.0;
a[70][85]=0.0;
a[71][85]=-x1[69]*x1[70];
a[72][85]=-x1[70]*x1[71];
a[73][85]=0.0;
a[74][85]=0.0;
a[75][85]=-x1[73]*x1[74];
a[76][85]=-x1[74]*x1[75];
a[77][85]=0.0;
a[78][85]=0.0;
a[79][85]=-x1[77]*x1[78];
a[80][85]=-x1[78]*x1[79];
a[81][85]=0.0;
a[82][85]=0.0;
a[83][85]=-x1[81]*x1[82];
a[84][85]=-x1[82]*x1[83];
for(k=1;k<=l;k++)
{
big=fabs(a[k][k]);
jj=k;
kp1=k+1;
for(i=kp1;i<=n;i++)
{
ab=fabs(a[i][k]);
if((big-ab)<0.0)
{

269

270

Appendix:

Programs in C++

big=ab;
jj=i;
}
}
if((jj-k)>0)
{
for(j=k;j<=m;j++)
{
t=a[jj][j];
a[jj][j]=a[k][j];
a[k][j]=t;
}
}
for(i=kp1;i<=n;i++)
{
quot=a[i][k]/a[k][k];
for(j=kp1;j<=m;j++)
{
a[i][j]=a[i][j]-quot*a[k][j];
}
}
for(i=kp1;i<=n;i++)
{
a[i][k]=0.0;
}
}
x[n]=a[n][m]/a[n][n];
for(nn=1;nn<=l;nn++)
{
sum=0.0;
i=n-nn;
ip1=i+1;
for(j=ip1;j<=n;j++)
{
sum=sum+a[i][j]*x[j];
}
x[i]=(a[i][m]-sum)/a[i][i];
}
}while(fabs(x[21]-x1[21])>1e-6&&fabs(x[84]-x1[84])>1e-6);
for(i=1;i<=n;i++)
{cout<<x[i]<<endl;}
getch();
}

Appendix: Programs in C++

271

PROGRAM 8.1
//PROGRAM 8.1
//program to calculate the concentration profile along the radius for
//reaction-diffusion in a spherical catalyst pellet (second order
//isothermal reaction)
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int i,j,n,i1,n1,k,iter;
float a[105],b[105],x1[105],c[105],d[105],x[105],beta[105],gamma[105];
for(i=1;i<=100;++i)
{x[i]=0.0;
}
//loop starts from here
iter=0;
do
{
iter=iter+1;
for(i=1;i<=100;++i)
{x1[i]=x[i];
}
for(i=2;i<=100;++i)
{a[i]=1.0-(1.0/(i-1.0));
}
b[1]=-6.0-0.01*x1[1];
for(i=2;i<=100;++i)
{b[i]=-2.0-0.01*x1[i];
}
c[1]=6.0;
for(i=2;i<=99;++i)
{c[i]=1.0+(1.0/(i-1.0));;
}
for(i=1;i<=99;++i)
{d[i]=0.0;
}
d[100]=-100.0/99.0;
i=1;
n=100;
beta[i]=b[i];
gamma[i]=d[i]/beta[i];
i1=i+1;
for(j=i1;j<=n;++j)
{

272

Appendix:

Programs in C++

beta[j]=b[j]-a[j]*c[j-1]/beta[j-1];
gamma[j]=(d[j]-a[j]*gamma[j-1])/beta[j];
}
x[n]=gamma[n];
n1=n-i;
for(k=1;k<=n1;++k)
{
j=n-k;
x[j]=gamma[j]-c[j]*x[j+1]/beta[j];
}
}while(fabs(x[1]-x1[1])>1e-6&&fabs(x[100]-x1[100])>1e-6);
cout<<\t\t\t THE SOLUTION BY TDMA<<endl;
for(i=1;i<=100;++i)
{
cout<<x[<<i<<] = <<x[i]<<endl;
}
cout<<Number of iterations is <<iter;
getch();
}

PROGRAM 8.2
//PROGRAM 8.2
//program to calculate the concentration profile along the radius for
//reaction-diffusion in a spherical catalyst pellet (non-isothermal, beta=1)
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int i,j,n,i1,n1,k,iter;
float a[105],b[105],x1[105],c[105],d[105],x[105],beta[105],gamma[105];
for(i=1;i<=100;++i)
{x[i]=0.0;
}
iter=0;
//loop starts from here
do
{
iter=iter+1;
for(i=1;i<=100;++i)
{x1[i]=x[i];
}
for(i=2;i<=100;++i)

Appendix: Programs in C++

{a[i]=1.0-(1.0/(i-1.0));
}
b[1]=-6.0-0.01*exp((1.0-x1[1])/(2.0-x1[1]));
for(i=2;i<=100;++i)
{b[i]=-2.0-0.01*exp((1.0-x1[i])/(2.0-x1[i]));
}
c[1]=6.0;
for(i=2;i<=99;++i)
{c[i]=1.0+(1.0/(i-1.0));;
}
for(i=1;i<=99;++i)
{d[i]=0.0;
}
d[100]=-100.0/99.0;
i=1;
n=100;
beta[i]=b[i];
gamma[i]=d[i]/beta[i];
i1=i+1;
for(j=i1;j<=n;++j)
{
beta[j]=b[j]-a[j]*c[j-1]/beta[j-1];
gamma[j]=(d[j]-a[j]*gamma[j-1])/beta[j];
}
x[n]=gamma[n];
n1=n-i;
for(k=1;k<=n1;++k)
{
j=n-k;
x[j]=gamma[j]-c[j]*x[j+1]/beta[j];
}
}while(fabs(x[1]-x1[1])>1e-6&&fabs(x[100]-x1[100])>1e-6);
cout<<\t\t\t THE SOLUTION BY TDMA<<endl;
for(i=1;i<=100;++i)
{
cout<<x[<<i<<] = <<x[i]<<endl;
}
cout<<Number of iterations is <<iter;
getch();
}

PROGRAM 9.1
//PROGRAM 9.1
//program to calculate the temperature profile in a rectangular
//slab during transient heat conduction

273

274

Appendix:

Programs in C++

#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int i,j,n,i1,n1,k;
float a[21],b[21],c[21],d[21],x[21],beta[21],gamma[21];
float x1old,x2old,x3old,x4old,time,timef;
x[1]=20.0;
x[2]=20.0;
x[3]=20.0;
x[4]=20.0;
time=0.0;
timef=3.0;
//a is subdiagonal, b is diagonal and c is superdiagonal
a[2]=1.0;
a[3]=1.0;
a[4]=1.0;
b[1]=-1.5;
b[2]=-3.0;
b[3]=-3.0;
b[4]=-3.0;
c[1]=1.0;
c[2]=1.0;
c[3]=1.0;
for(time=0.1;time<timef;time=time+0.1)
{
x1old=x[1];
x2old=x[2];
x3old=x[3];
x4old=x[4];
d[1]=-0.5*x1old;
d[2]=-x2old;
d[3]=-x3old;
d[4]=-x4old-300.0;
i=1;
n=4;
beta[i]=b[i];
gamma[i]=d[i]/beta[i];
i1=i+1;
for(j=i1;j<=n;++j)
{
beta[j]=b[j]-a[j]*c[j-1]/beta[j-1];
gamma[j]=(d[j]-a[j]*gamma[j-1])/beta[j];
}

Appendix: Programs in C++

275

x[n]=gamma[n];
n1=n-i;
for(k=1;k<=n1;++k)
{
j=n-k;
x[j]=gamma[j]-c[j]*x[j+1]/beta[j];
}
cout<<\t\t\t THE SOLUTION BY TDMA AT TIME = <<time<< seconds<<endl;
cout<<x[1]<< <<x[2]<< <<x[3]<< <<x[4]<<endl;
}
getch();
}

PROGRAM 9.2
//PROGRAM 9.2
//program to calculate the concentration profile in a sphere
//during transient diffusion of drug from spherical pellet
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int i,j,n,i1,n1,k;
float a[21],b[21],c[21],d[21],x[21],beta[21],gamma[21];
float x1old,x2old,x3old,x4old,x5old,x6old,x7old,x8old,x9old,x10old,time,timef;
for(i=1;i<=10;++i)
{
x[i]=68.9;
}
time=0.0;
timef=10800.0;
//a is subdiagonal, b is diagonal and c is superdiagonal
for(i=2;i<=10;++i)
{
a[i]=-(1.0-1.0/(i-1.0));
}
for(i=2;i<=10;++i)
{
b[i]=3544.5;
}
b[1]=591.4;
for(i=2;i<=9;++i)
{

276

Appendix:

Programs in C++

c[i]=-(1.0+1.0/(i-1.0));
}
c[1]=-1.0;
for(time=0.0;time<timef;time=time+1.0)
{
x1old=x[1];
x2old=x[2];
x3old=x[3];
x4old=x[4];
x5old=x[5];
x6old=x[6];
x7old=x[7];
x8old=x[8];
x9old=x[9];
x10old=x[10];
d[1]=x1old*590.4;
d[2]=x2old*3542.5;
d[3]=x3old*3542.5;
d[4]=x4old*3542.5;
d[5]=x5old*3542.5;
d[6]=x6old*3542.5;
d[7]=x7old*3542.5;
d[8]=x8old*3542.5;
d[9]=x9old*3542.5;
d[10]=x10old*3542.5;
i=1;
n=10;
beta[i]=b[i];
gamma[i]=d[i]/beta[i];
i1=i+1;
for(j=i1;j<=n;++j)
{
beta[j]=b[j]-a[j]*c[j-1]/beta[j-1];
gamma[j]=(d[j]-a[j]*gamma[j-1])/beta[j];
}
x[n]=gamma[n];
n1=n-i;
for(k=1;k<=n1;++k)
{
j=n-k;
x[j]=gamma[j]-c[j]*x[j+1]/beta[j];
}
}
cout<<\t\t\t THE SOLUTION BY TDMA AT TIME = <<time<< seconds<<endl;
for(i=1;i<=10;++i)

Appendix: Programs in C++

277

{
cout<<x[i]<<endl;
}
getch();
}

PROGRAM 10.1
//PROGRAM 10.1
//program to calculate the temperature profile in a 2-D body
//during steady heat conduction using the GaussSeidel method
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
float t11old,t12old,t13old,t11new,t12new,t13new;
float t21old,t22old,t23old,t21new,t22new,t23new;
float t31old,t32old,t33old,t31new,t32new,t33new;
t11new=t12new=t13new=101.0;
t21new=t22new=t23new=101.0;
t31new=t32new=t33new=101.0;
do
{
t11old=t11new;
t12old=t12new;
t13old=t13new;
t21old=t21new;
t22old=t22new;
t23old=t23new;
t31old=t31new;
t32old=t32new;
t33old=t33new;
t11new=(t12old+50+0.5*t21old+100.0/3.0)*3/7;
t12new=(t11new+t13old+t22old+100)/4.0;
t13new=(t12new+t23old+600)/4;
t21new=(t22old+0.5*t11new+0.5*t31old+100/3)*3/7;
t22new=(t12new+t32old+t23old+t21new)/4;
t23new=(t13new+t22new+t33old+500)/4;
t31new=(0.5*t21new+0.5*t32old+100/3)*3/4;
t32new=(t22new+0.5*t31new+0.5*t33old+100/3)*3/7;
t33new=(t23new+250+0.5*t32new+100/3)*3/7;
}while(fabs(t11new-t11old)>1e-6&&fabs(t12new-t12old)>1e6&&fabs(t13new-t13old)>1e-6

278

Appendix:

Programs in C++

&&fabs(t21new-t21old)>1e-6&&fabs(t22new-t22old)>1e-6&&fabs(t23newt23old)>1e-6
&&fabs(t31new-t31old)>1e-6&&fabs(t32new-t32old)>1e-6&&fabs(t33newt33old)>1e-6);
cout<<t11new<< <<t12new<< <<t13new<<endl;
cout<<t21new<< <<t22new<< <<t23new<<endl;
cout<<t31new<< <<t32new<< <<t33new<<endl;
getch();
}

PROGRAM 10.2
//PROGRAM 10.2
//program to calculate the temperature profile in a 2D body
//during steady heat conduction using the ADI method
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int i,j,ii,jj,n,nn,nmax,i1,n1,k;
float a[21],b[21],c[21],d[21],x[21],beta[21],gamma[21], t[21][21];
float tstar[21][21];
a[2]=1.0;
a[3]=1.0;
b[1]=-4.0;
b[2]=-4.0;
b[3]=-4.0;
c[1]=1.0;
c[2]=1.0;
cout<<Enter the maximum number of iterations ;
cin>>nmax;
t[0][1]=tstar[0][1]=20.0;
t[0][2]=tstar[0][2]=20.0;
t[0][3]=tstar[0][3]=20.0;
t[1][0]=tstar[1][0]=20.0;
t[2][0]=tstar[2][0]=20.0;
t[3][0]=tstar[3][0]=20.0;
t[4][1]=tstar[4][1]=20.0;
t[4][2]=tstar[4][2]=20.0;
t[4][3]=tstar[4][3]=20.0;
t[1][4]=tstar[1][4]=400.0;
t[2][4]=tstar[2][4]=400.0;
t[3][4]=tstar[3][4]=400.0;

Appendix: Programs in C++

for(i=1;i<=3;i++)
{
for(j=1;j<=3;j++)
{
t[i][j]=20.0;
}
}
for(nn=1;nn<=nmax;nn++)
{
for(jj=1;jj<=3;jj++)
{
d[1]=-t[0][jj]-t[1][jj+1]-tstar[1][jj-1];
d[2]=-t[2][jj+1]-tstar[2][jj-1];
d[3]=-t[4][jj]-t[3][jj+1]-tstar[3][jj-1];
i=1;
n=3;
beta[i]=b[i];
gamma[i]=d[i]/beta[i];
i1=i+1;
for(j=i1;j<=n;++j)
{
beta[j]=b[j]-a[j]*c[j-1]/beta[j-1];
gamma[j]=(d[j]-a[j]*gamma[j-1])/beta[j];
}
x[n]=gamma[n];
n1=n-i;
for(k=1;k<=n1;++k)
{
j=n-k;
x[j]=gamma[j]-c[j]*x[j+1]/beta[j];
}
tstar[1][jj]=x[1];
tstar[2][jj]=x[2];
tstar[3][jj]=x[3];
}
for(ii=1;ii<=3;ii++)
{
d[1]=-t[ii][0]-tstar[ii+1][1]-tstar[ii-1][1];
d[2]=-tstar[ii+1][2]-tstar[ii-1][2];
d[3]=-t[ii][4]-tstar[ii+1][3]-tstar[ii-1][3];
i=1;
n=3;
beta[i]=b[i];
gamma[i]=d[i]/beta[i];
i1=i+1;

279

280

Appendix:

Programs in C++

for(j=i1;j<=n;++j)
{
beta[j]=b[j]-a[j]*c[j-1]/beta[j-1];
gamma[j]=(d[j]-a[j]*gamma[j-1])/beta[j];
}
x[n]=gamma[n];
n1=n-i;
for(k=1;k<=n1;++k)
{
j=n-k;
x[j]=gamma[j]-c[j]*x[j+1]/beta[j];
}
t[ii][1]=x[1];
t[ii][2]=x[2];
t[ii][3]=x[3];
}
}
cout<<\t\t\t THE SOLUTION BY ADI<<endl;
cout<<t[1][1]<< <<t[1][2]<< <<t[1][3]<<endl;
cout<<t[2][1]<< <<t[2][2]<< <<t[2][3]<<endl;
cout<<t[3][1]<< <<t[3][2]<< <<t[3][3]<<endl;
getch();
}

PROGRAM 10.3
//PROGRAM 10.3
//program to calculate the temperature profile in a 2D body
//during transient heat conduction using the ADI method
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
clrscr();
int i,j,ii,jj,n,nn,nmax,i1,n1,k,kk,count;
float a[21],b[21],c[21],d[21],x[21],beta[21],gamma[21],t[21][21];
float tstar[21][21],time,timef;
timef=0.5;
for(k=1;k<=10;k++)
{
a[k]=-1.0;
b[k]=2.4;
c[k]=-1.0;

Appendix: Programs in C++

c[1]=-2.0;
for(k=1;k<=11;k++)
{
t[11][k]=400.0;
tstar[11][k]=400.0;
t[k][11]=400.0;
tstar[k][11]=400.0;
}
for(i=1;i<=10;i++)
{
for(j=1;j<=10;j++)
{
t[i][j]=0.0;
tstar[i][j]=0.0;
}
}
for(time=0.0;time<=timef;time=time+0.05)
{
for(jj=1;jj<=10;jj++)
{
if(jj==1)
{
for(ii=1;ii<=10;ii++)
{
d[ii]=2*t[ii][2]-1.6*t[ii][1];
}
d[10]=d[10]+400.0;
}
else
{
for(ii=1;ii<=10;ii++)
{
d[ii]=t[ii][jj+1]+t[ii][jj-1]-1.6*t[ii][jj];
}
d[10]=d[10]+400.0;
}
i=1;
n=10;
beta[i]=b[i];
gamma[i]=d[i]/beta[i];
i1=i+1;
for(j=i1;j<=n;++j)
{
beta[j]=b[j]-a[j]*c[j-1]/beta[j-1];
gamma[j]=(d[j]-a[j]*gamma[j-1])/beta[j];
}

281

282

Appendix:

Programs in C++

x[n]=gamma[n];
n1=n-i;
for(k=1;k<=n1;++k)
{
j=n-k;
x[j]=gamma[j]-c[j]*x[j+1]/beta[j];
}
for(count=1;count<=10;count=count+1)
{
tstar[count][jj]=x[count];
}
}
for(ii=1;ii<=10;ii++)
{
if(ii==1)
{
for(jj=1;jj<=10;jj++)
{
d[jj]=2*tstar[ii+1][1]-1.6*tstar[ii][1];
}
d[10]=d[10]+400.0;
}
else
{
for(jj=1;jj<=10;jj++)
{
d[jj]=tstar[ii-1][jj]+tstar[ii+1][jj]-1.6*tstar[ii][jj];
}
d[10]=d[10]+400.0;
}
i=1;
n=10;
beta[i]=b[i];
gamma[i]=d[i]/beta[i];
i1=i+1;
for(j=i1;j<=n;++j)
{
beta[j]=b[j]-a[j]*c[j-1]/beta[j-1];
gamma[j]=(d[j]-a[j]*gamma[j-1])/beta[j];
}
x[n]=gamma[n];
n1=n-i;
for(k=1;k<=n1;++k)
{

Appendix: Programs in C++

j=n-k;
x[j]=gamma[j]-c[j]*x[j+1]/beta[j];
}
for(count=1;count<=10;count=count+1)
{
t[ii][count]=x[count];
}
}
}
cout<<\t\t\t THE SOLUTION BY ADI AT TIME = <<time<< s<<endl;
for(i=1;i<=10;i++)
{
for(j=1;j<=10;j++)
{
cout<<t[<<i<<][<<j<<] = <<t[i][j]<<\t;
}
}
getch();
}

283

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New York, 1995.
Beers, K.J., Numerical Methods for Chemical Engineering: Applications in MATLAB,
Cambridge University Press, Cambridge, UK, 2007
Bird, R.B., Stewart, W.E., and Lightfoot, E.N., Transport Phenomena, 2nd ed., John Wiley,
New York, 2002.
Butt, J.B., Reaction Kinetics and Reactor Design, Prentice Hall, Englewood Cliffs,
New Jersey, 1980.
Carnahan, B., Luther, H.A., and Wilkes, J.O., Applied Numerical Methods, John Wiley,
New York, 1969
Cengel, Y.A., Heat Transfer: A Practical Approach, 2nd ed., Tata McGraw-Hill, New Delhi,
2003
Chapra, S.C. and Canale, R.P., Numerical Methods for Engineers, 3rd ed., Tata McGraw-Hill,
New Delhi, 1998.
Chung, T.J., Computational Fluid Dynamics, Cambridge University Press, New York, 2002.
Cooper, A.R. and Jeffreys, G.V., Chemical Kinetics and Reactor Design, Oliver and Boyd,
Edinburgh, 1971
Felder, R.M. and Rousseau, R.W., Elementary Principles of Chemical Processes, John Wiley,
New York, 2000.
Finlayson, B.A., Nonlinear Analysis in Chemical Engineering, McGraw-Hill, New York,
1980.
Finlayson, B.A., Introduction to Chemical Engineering Computing, John Wiley, New York,
2006.
Fogler, H.S., Elements of Chemical Reaction Engineering, 4th ed., Pearson Education/Prentice
Hall, Upper Saddle River, New Jersey, 2006.
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Fox, R.W., and McDonald, A.T., Introduction to Fluid Mechanics, 5th ed., John Wiley,
New York, 2004.
Gear, C.W., Numerical Initial Value Problems in Ordinary Differential Equations, Prentice
Hall, Englewood Cliffs, New Jersey, 1971.
Gupta, S.K., Numerical Methods for Engineers, Wiley Eastern, New Delhi, 1995.
Hill, C.G., Jr., Introduction to Chemical Kinetics and Reactor Design, John Wiley, New York,
1977.
Holland, C.D. and Anthony, R.G., Fundamentals of Chemical Reaction Engineering, Prentice
Hall, Englewood Cliffs, New Jersey, 1979
Holman, J.P., Heat Transfer, 8th ed., McGraw-Hill, New York, 1997.
Jain, M.K., Iyengar, S.R.K., and Jain, R.K., Numerical Methods for Scientific and
Engineering Computation, 5th ed., New Age International, New Delhi, 2007.
Jenson, V.G. and Jeffreys, G.V., Mathematical Methods in Chemical Engineering, 2nd ed.,
Academic Press, New York, 1977.
Kreyszig, E., Advanced Engineering Mathematics, 8th ed., John Wiley, New York, 1999.
Levenspiel, O., Chemical Reaction Engineering, 3rd ed., John Wiley, New York, 2001.
Mickley, H.S., Sherwood, T.K., and Reed, C.E., Applied Mathematics in Chemical
Engineering, 2nd ed., McGraw-Hill, New York, 1957.
Munson, B.R., Young, D.F., and Osiishi, T.H., Fundamentals of Fluid Mechanics, 5th ed.,
John Wiley, New York, 2006.
Press, W.H., Teukolsky, S.A., Vetterling, W.T., and Flannery, B.P., Numerical Recipes: The
Art of Scientific Computing, 3rd ed., Cambridge University Press, Cambridge, UK, 2007.
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Thermodynamics, 6th ed., McGraw-Hill, New York, 2001.
Tannehill, J.C., Anderson, D.A., and Pletcher, R.H., Computational Fluid Mechanics and
Heat Transfer, 2nd ed., Taylor and Francis, Washington, D.C., 1997.
Versteeg, H.K. and Malalasekera, W., An Introduction to Computational Fluid Dynamics
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and Mass Transfer, 4th ed., John Wiley, New York, 2001.

Index
Activity coefficient, 37
Adiabatic flame temperature, 4950
Alternating direction implicit (ADI) method,
208220
for steady heat conduction, 208214
for transient heat conduction, 214220
Antoine equation, 34
Axial dispersion, 119

Backward difference scheme, 86

Batch reactor, 6974
Block tridiagonal matrix, 150
Boundary conditions, 87
Dirichlet, 87
mixed, 87
Neumann, 87
Boundary value problem (BVP), 85
Bubble point temperature, 3334, 38
using modified Raoults law, 38
using Raoults law, 3334

Central difference scheme, 86, 113

Chemical reaction and diffusion
first order reaction, 155158
non-isothermal conditions, 161168
in a pore, 97
second order reaction, 158161
in a spherical catalyst pellet, 155168
Chemical reaction engineering, 6879, 119170
boundary value problems, 119170
initial value problems, 6879
Chemical reaction equilibriumtwo simultaneous reactions, 4748

Classification of partial differential equations,

171
elliptic, 171
hyperbolic, 171
parabolic, 171
Colebrook equation, 20
Comparison of central and upwind difference
schemes, 113114
Control volume, 193
Convectiondiffusion problems, 105
Crank-Nicolson method, 173
Cubic equations of state, 3133
Peng-Robinson, 33
Redlich-Kwong, 32
van der Waals, 31

Danckwerts boundary conditions, 121

Dew point temperature, 3435, 3940
using modified Raoults law, 3940
using Raoults law, 3435
Diffusion, 9799, 105, 155, 186188
of drug from a spherical gel matrix, 186188
Dirichlet boundary condition, 87
Discretization
in one-dimensional space, 86, 172
in two-dimensional space, 192194
of differential equations, 86, 172, 192194
Double pipe heat exchanger, 5556
Drag coefficient, 23, 60

Effective diffusion coefficient, 114

Elliptic partial differential equation, 171

287

288

Index

Ergun equation for packed beds, 21

Explicit method, 172

Fin, 94
Finite difference schemes, 86, 105107, 172173
backward difference, 86
central difference, 86
forward difference, 86
FTCS Crank-Nicolson scheme, 173
FTCS explicit scheme, 172
FTCS implicit scheme, 173
upwind difference, 105107
Flash calculations, 3537, 4042
using modified Raoults law, 4042
using Raoults law, 3537
Forward difference scheme, 86
Forward in time and central in space (FTCS)
difference scheme, 172173
Fourier stability analysis, 174176
Friction factor, 2021

Gamma-phi approach, 4344

Gauss-Seidel method, 10
Gaussian elimination method, 5

Heat conduction, 93, 176, 195, 208, 214

one-dimensional steady, 93
one-dimensional transient, 176
two-dimensional steady, 195, 208
two-dimensional transient, 214

Implicit method, 172

Initial value problems (IVP), 5379
batch reactor, 69
in chemical reaction engineering, 6879
nonisothermal plug flow reactor, 76
plug flow reactor, 74
stirred tank reactor, 69

L Hospitals rule, 182, 187

Line-by-line TDMA (see ADI method)
Linear algebraic equations, 112
Log mean temperature difference, 56

Minimum fluidization velocity, 21

Neumann boundary conditions, 87

Newtons method, 17
Newton-Raphson method (see Newtons method)
Nonlinear algebraic equations, 1729
Numerical diffusion term, 114

One-dimensional
steady heat conduction, 93
transient diffusion in a sphere, 186188
transient heat conduction, 176185
in a cylinder, 181183
in a rectangular slab, 176181
in a sphere, 183185
Optimum step size, 53
Ordinary differential equation, 53, 87, 105, 155
Overall heat transfer coefficient, 56

P-x-y diagram, 4347

using cubic equation of state, 4447
using gamma-phi approach, 4344
Partial differential equation (PDE), 171
parabolic, 176185, 214220
Particle Reynolds number, 24
Peclet number, 108114
local, 109
effective, 114
Plug flow reactor, 74
Pneumatic conveying, 60
Pressure drop in a pipe under nonlaminar
conditions, 20

Raoults law, 3337

Rate constant, 69, 120, 129, 155, 158
first order reaction, 69, 120, 155
second order reaction, 129, 158
Red-black Gauss-Seidel method, 195
Relaxation
parameter, 194
technique, 194195
Gauss-Seidel, 194
overrelaxation, 195
underrelaxation, 195

Index

Reynolds number, 20
Round-off error, 53, 87
Runge-Kutta fourth order method, 54

Stability, 87, 174176

Standard enthalpy change of reaction, 49
Step size, 53
Stirred tank with coil heater, 57
series of, 66
System
of linear algebraic equations, 112
of nonlinear algebraic equations, 25
of ordinary differential equations, 63, 131
boundary value problem, 131
initial value problem, 63

Taylor series expansion, 85

Terminal velocity, 23
Thomas algorithm (see Tridiagonal matrix
algorithm)
Tridiagonal matrix, 1
algorithm (TDMA), 2
diagonal elements, 1
sub-diagonal elements, 1
super-diagonal elements, 1
Tridiagonal set of linear algebraic equations, 1,
94, 96, 99, 110, 111, 124, 126, 128, 130,

289

158, 160, 166, 168, 178, 180, 182, 185,

188, 210214, 217219
Truncation error, 53, 87
Tubular reactor with axial dispersion, 119153
first order reaction, 120128
multiple reactions, 131153
second order reaction, 129131
Two-dimensional
steady heat conduction, 192214
using ADI method, 208
using Gauss-Seidel method, 194
using red-black Gauss-Seidel method, 195
transient heat conduction, 214220
using ADI method, 214220

Upwind difference schemes, 105108

first-order, 105
second-order, 106108

Vapourliquid equilibrium calculations, 3347

using Gamma-Phi approach, 4344
using modified Raoults law, 3742
using Phi-Phi approach, 4447
using Raoults law, 3337
Vapour pressure using cubic equation of state,
4243
Von Neumann stability analysis, 174176

INTRODUCTION TO

NUMERICAL METHODS IN
CHEMICAL ENGINEERING
Pradeep Ahuja

his book is an exhaustive presentation of the numerical methods used in chemical

engineering. Intended primarily as a textbook for BE/BTech students of chemical
engineering, the book will also be useful to research and development/process professionals in the
fields of chemical, biochemical, mechanical and biomedical engineering.
The initial chapters discuss the linear and nonlinear algebraic equations. The ensuing chapters cover
the problems in chemical engineering thermodynamics as well as initial value problems, boundary
value problems and convectiondiffusion problems. Topics related to chemical reaction, dispersion
and diffusion as well as steady and transient heat conduction are treated in the final chapters. The
book covers a large number of numerical methods including tridiagonal matrix algorithm (TDMA)
method, Newtons method, RungeKutta fourth-order method, Upwind Difference Scheme (UDS)
method and Alternating Direction Implicit (ADI) method. Strong emphasis is given on applications
and uses of numerical analysis specifically required at the undergraduate level.
The book contains numerous worked-out examples and chapter-end exercises. The answers to all
chapter-end exercises are provided. The Appendix contains a total of 33 programs in C++ related to
the various numerical methods explained in the book.
THE AUTHOR
PRADEEP AHUJA, Ph.D., is Reader in the Department of Chemical Engineering and Technology,
Institute of Technology, Banaras Hindu University, Varanasi. He has more than a decades experience
in teaching chemical engineering at the BE/BTech level. He has published several research papers in
national and international journals. Dr. Ahuja is a recipient of the AICTE Career Award for Young
Teachers and a life member of the Indian Institute of Chemical Engineers (IIChE).

Our other useful books

Chemical Engineering Thermodynamics, Pradeep Ahuja
Process Control: Concepts, Dynamics and Applications, S.K. Singh
Heat Transfer: Principles and Applications, Binay K. Dutta
Principles of Mass Transfer and Separation Processes, Binay K. Dutta
Colloid and Interface Science, Pallab Ghosh
Process Simulation and Control Using ASPEN , Amiya K. Jana
ISBN:978-81-203-4018-3

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