Modeling and Simulation of Interface Mass Transfor With Chemical Reaction

Addis Ababa University
School of Graduate Studies

Faculty of Technology
Department of Chemical Engineering

Modeling and Simulation of Interface Mass
Transfer with Chemical Reaction

By
Nigus Gabbiye

Advisors
Dr.-Ing Nurelegne Tefera
Dr. D Venkatanarasaiah

A thesis submitted to the Graduate Studies of Addis Ababa University in partial
fulfillment of the Degree of Masters of Science in Chemical Engineering
(Process Engineering)

Addis Ababa
September, 2004

v

Acknowledgement

First of all I would like to thank my God for giving me patience to accomplish my thesis
work successfully. I am most greatful to my advisor Dr.Ing. Nurelegne Tefera for advising
and directing me through out my thesis work. I would like to thank my second advisor Dr.
D .Venkatanarasaiah for his advising and giving comments up on my thesis work.
My thanks are due to my parents and many colleagues for giving me a strong moral and
advice.
Acknowledgment would also be due to the Department of Chemical Engineering and my
colleagues, because after all these years it is from there and them that I got all the
knowledge crucial for this thesis work.

iv

Abstract

Most analytical solutions of interfacial mass transfer is restricted to one
dimensional diffusion equations, while most numerical models make use of the
physically less realistic stagnant film model. The model here has developed
that simulates interface mass transfer with chemical reaction of two
immiscible liquids. It was developed by simultaneously solving the Higbie
Penetration model for the phenomenon of mass transfer accompanying by
chemical reaction. By comparing the model result with other literature results
it was concluded that the model developed for two dimensional diffusion
convection equations simulates the concentration and temperature
distribution satisfactorily.
It has been shown that under some circumstance substantial difference exists
between the literature result and numerical approximation.

vi
Table of contents
Pages
Abstract..iv
Acknowledgement..v
Table of contentsvi
List of figures..viii
List of tables..x
1. Introduction1
2. Literature Review. 4
2.1 Mass transfer concept................................................................................................... 4
2.2 Models for mass transfer at Fluid Fluid interface ..................................................... 5
2.2.1 The Two film theory ............................................................................................. 6
2.2.2 Penetration theory ................................................................................................. 7
2.2.3 Mass transfer Coefficient .................................................................................... 10
2.2.4 Mass transfer with chemical reaction.................................................................. 12
2.3 Numerical Solution Methods ..................................................................................... 14
3. The transport equations in Capillary space...17
3.1 The transport equation in the bulk of the fluid phase................................................. 18
3.1.1 Buoyancy and the Boussinesq Approximation ................................................... 18
3.1.2 Description of the flow in the capillary space..................................................... 21
3.1.3 Vortices transport and poison equation............................................................... 24
3.2 The transport equation at the interface....................................................................... 26
3.2.1 Reyhlogical Properties at the interface ............................................................... 26
3.2.2. The tension equilibrium at the phase interface .................................................. 28
3.2.3 The Vorticity Transport equation at the interface............................................... 30
3.3 Mass and heat transport equation............................................................................... 31
3.3.1 Mass and heat transport equations in capillary space ......................................... 32
3.3.2 Mass and Heat Transport equations at the phase interface. ................................ 35
4. Numerical Approach of the transport equation.39
4.1 The nature of numerical Methods and Discretisation Concept.................................. 39
4.1.1 The nature of Numerical Methods ...................................................................... 39
vii
4.1.2 The discretisation Concept.................................................................................. 39
4.2 Discretisation of Transport equations ........................................................................ 41
4.2.1 Discretisation of temporal changes ..................................................................... 41
4.2.2 The vorticity transport equation in the bulk phase.............................................. 42
4.2.3 The poison equation............................................................................................ 47
4.2.4 The velocity field ................................................................................................ 47
4.2.5 Mass and heat transport equation in the bulk phases .......................................... 48
4.2.6 Mass transfer equation at the interface................................................................ 58
4.2.7 Heat transfer equation at the interface ................................................................ 63
4.2.8 The vorticity equation at the interface ................................................................ 65
4.3 Discretisation of boundary and initial conditions ...................................................... 70
4.3.1 Horizontal boundary............................................................................................ 70
4.3.2 Interface Boundaries ........................................................................................... 71
4.3.3 Vertical boundaries ............................................................................................. 71
4.3.4 Initial conditions ................................................................................................. 73
4.3.5 Algorithm............................................................................................................ 78
4.3.6 Solution of the discretised equation.................................................................... 78
5. Results and discussion..85
5.1 Simulation of Concentration Profile .......................................................................... 87
5.1.1 Mass transfer with out chemical reaction............................................................ 87
5.1.2 Mass transfer with chemical reaction.................................................................. 93
5.2 Simulation of temperature Profile.............................................................................. 96
5.3 Validation of the simulation result100
6. Conclusion and Recommendation..103
6.1 Conclusion ............................................................................................................... 103
6.2 Recommendation.................................................................................................... 104
Symbols..106
Reference110
APPENDICES112
Appendix A: Prediction of physical Properties of substances ....................................... 112
Appendix B: Mathematical manipulation of the Discretisation Equations................... 115
viii

List of figures
Figure 2. 1 Concentration profiles between two phases. ....................................................... 5
Figure 2. 2 Interfacial renewal according to Higbie [5]........................................................ 8
Figure 2. 3 Concentration profile in stagnant fluid element as a function of time ................ 9
Figure 3. 1 Two dimensional representation of the capillary space.17
Figure 3. 2 Velocity profile of laminar flow in capillary tube..22
Figure 3. 3 the force balance in the x - direction at the interface.28
Figure 4. 1Representation of non uniform mesh.................................................................. 41
Figure 4. 2 Space discretization of vorticity transport equation ......................................... 43
Figure 4. 3Control Volumes for calculation of temperature and concentration distributions
...................................................................................................................................... 48
Figure 4. 4 Control volume for mass and heat transport equations at the interface............. 59
Figure 4. 5 w grid points at the interface........................................................................ 66
Figure 4. 6 Algorithms for the simulation of mass and heat transport discretisation
equations using implicit scheme. ................................................................................ 79
Figure 5. 1 One dimensional Concentration profiles during mass transfer at the interface as
function of distance from the interface, in the water phase negative, in the
Cyclohexane phase positive, Analytical Solution........................................................ 88
a function of distance from the interface, in the water phase negative, in the
Cyclohexane phase positive, Numerical solutions....................................................... 89
Figure 5. 3 Two dimensional Concentration profile of the diffusing component................ 91
ix
Figure 5. 4 Concentration profiles during mass transfer at the interface as a function of
distance from the interface, in the water phase negative, in the Cyclohexane phase
positive, average value along the horizontal direction for two dimension................... 92
positive, average value along the horizontal direction for two dimension. ................. 94
Figure 5.6 Concentration profiles during mass transfer at the interface as a function of
positive, average value along the horizontal direction for two dimension................... 95
Figure 5. 7 One dimensional temperatures profile at the interface as function of distance
from the interface, in the water phase negative, in the Cyclohexane phase positive ,for
U
o
= 5 w m
-1
k
-1
............................................................................................................ 97
Figure 5. 8 Two dimensional temperature distribution of the system, for U
o
= 5 w m
-1
k
-1
98
Figure 5. 9 Temperatures profile at the interface as function of distance from the interface,
in the water phase negative, in the Cyclohexane phase positive for k m w U
o
/ 5 = ,
Average value of temperature along the horizontal direction for two dimensions. ..... 99
Figure 5. 10 Concentration profile as a function of distance from the interface, Comparison
of numerical solution with analytical solution........................................................... 101
Figure 5. 11 Temperature distributions as function of distance from the interface,
Comparison of numerical solution with other literature [13]..................................... 102

x

List of tables
Table 3. 1Summary of the transport equations in the capillary flow. .................................. 37

Table 4.1The function ( ) Pe A for different schemes ..... 55
Table 5. 1 Parameter used for the simulation....................................................................... 86

1
1. Introduction
Reaction that occurs at the interface between two immiscible liquids is of intrinsic
fundamental significance in heterogeneous catalysis and separation processes. E.g. in
solvent extraction process, reactive distillation and phase transfer catalysis .This interfacial
Phenomenas are associated with momentum, energy and mass transfer at the phase
interface and they are attributed to local gradients of interfacial tension and called
marangoni effects. Gradients in interfacial tension are caused because of gradients in
reactant and product or surfactant concentration and temperature changes with in the
interface.
A phenomenon of mass transfer with chemical reaction takes place whenever two phases
which are not at chemical equilibrium with one another are brought in to contact [1]. Such
phenomena are made up of a number of elementary steps, which may be summarized as
follows.
i. Diffusion of reactants from the bulk of phases one to interface between the
two phases. Physical equilibrium may be assumed prevail at the interface;
whenever the concentration of the reactant at the interface is finite in one
phase, it is also finite in the other.
ii. Diffusion of reactants from the interface to wards the bulk of phase two.
iii. Chemical reaction with in phase two.
iv. Diffusion of reactants initially present with in phase two, and/or of reaction
products, with in phase two itself, due to concentration gradients which are
set up by the chemical reaction.
2
The two phases involved in chemical reaction may be either both or one fluid or the other
solid. If phase two is fluid the problem to be considered is far more complicated, because
the fluid mechanics of that phase need to be considered. In view of this consideration,
attention will be focused in this work on the case where the fluids are liquids.
Liquid-Liquid systems are hydro-dynamically unstable leading to formation of waves
slugs and pulses, and possibly atomization. In addition the interfacial instability generated
near the gas-liquid or liquid-liquid interface results in the appearance of convective flows
which increase significantly the transfer coefficients
Knowledge about the parameter affecting the hydro-dynamic instability in the fluid-fluid
systems helps us in better design of reactors and separation columns. The parameters
affects the hydro-dynamic instability are density difference and surface tensional changes
due to concentration gradients. Concentration gradient deepens with simultaneous mass
transfer with chemical reaction.
Concentration gradients in the liquid-liquid system can be estimated using the following
experimental techniques namely, potentiometer or amperometric, optical measurements
(Laser induced fluorescence (LIF) etc. These experimental methods are economically
expensive and time consuming to get the concentration gradients at the liquid-liquid
interface. In addition these measurements can be made only in the bulk of the system with a
great care and it is very difficult to measure the interfacial composition. Therefore with the
help of high-speed computers we can adopt numerical simulation method to simulate the
concentration changes at the liquid-liquid interface.
Majority of the recent publications on numerical simulation of multi-phase flow
phenomena are used finite volume method with Euler-Euler or Euler- LaGrange
3
approaches. Numerical difference method gives us pure mathematical solution where as
finite volume method involves the physical significance of the problem.
In this study, both one and two-dimensional computer code for simulation of convection-
diffusion model are described. The code is implemented in mat lab. The partial differential
equation is converted to a system of linear equations with the finite volume method. The
system of equations is solved with an iterative line by line method, Tri-Diagonal matrix
Algorithm.

4
2. Literature Review
2.1 Mass transfer concept

Mass transfer is the net movement of a component in a mixture from one location to
another location where the component exists at different concentration. Often the transfer
component takes place between phases across an interface [2].
Mass transfer occurs by two basic mechanisms:
1. Molecular diffusion: by random and spontaneous microscopic movement individual
molecules in a gas, liquid or solid is transferred as a result of thermal motion.
2. Eddy (turbulent) diffusion by random microscopic fluid motion.
Molecular and / or eddy diffusion frequently involves the movement of different species in
opposite direction. When a net flow occurs in one of these directions, the total rate of mass
transfer of individual species is increased or decreased by this bulk flow or convection
effects, which is a third mechanism of mass transfer. Molecular diffusion is extremely slow,
whereas eddy diffusion, when it occurs is order of magnitude more rapid.
Fig ure3.1 shows typical concentration gradient in the bulk of the two phases.

5

Figure 2. 1 Concentration profiles between two phases.

2.2 Models for mass transfer at Fluid Fluid interface
Of greater interest in separation processes is mass transfer across an interface between a gas
and a liquid or between two liquid phases. Such interface exists in absorption, extraction,
and stripping. Because no materials accumulate at the interface, the rate of transfer on each
sides of the interface must be the same, and therefore the concentration gradient
automatically adjust themselves so that they are proportional to the resistance to transfer in
the particular phase. In addition, if there is no resistance to transfer at the interface, the
concentration on each side will be related to each other by the phase equilibrium
relationship. The following theoretical models have been developed to describe mass
transfer from a fluid to such an interface [2].
6

2.2.1 The Two film theory
Many different theories have been developed to calculate mass transfer coefficient .The
difficulty of the particular model lies in the consideration of the properties of the fluid
phase at the interface which highly influences the mass transfer rate. Simple theoretical
model for turbulent mass transfer to or from a fluid phase boundary was suggested in 1904
by Nernst [2] who postulated that the entire resistance to mass transfer in a given turbulent
phase is in thin, stagnant region of that phase at the interface, called the film. The two film
theory states laminar sub layer at both side of the interface so that mass transfer process can
be described by diffusion. The main transport resistance lies between the two turbulent
mixing bulk phases. I.e. there is no resistance to solute transfer across the interface
separating the phases, Whitman [3]. The equation of the two film theory is given by:-
( ) ( )
int 2 2 int 1 1
. . C n D C n D = (2.1)
This describes the continuity of the diffusive mass transfer of both phases in the normal
direction (n).
By the help of the diffusivity and film thickness over the changes of the concentration
between the bulk phases and the interface one gets the mass transfer coefficients.

( )
( ) b
D
h
a
D
h
D
D
2 . 2
2 . 2
2
2
2
1
1
1
=
=

7
The two film theory, which is easy to understand and apply, is often criticized because it
appears to predict that the rate of mass transfer is directly proportional to the molecular
diffusivity. This dependency is at odd with the experimental data, which indicates
a dependency of
n
D , where n ranges from about 0.5 to 0.75. Especially a strong increase
of mass concentration at the interface can not be explained correctly .However if
AB
D
is
replaced with
D
h , which is then estimated from the Chilton - Colburn analogy [2] one can
obtain
D
h proportional to AB D
3 / 2
, which is in better agreement with experimental data.
Regardless of whether the criticism of the film theory is valid, the theory has seen and
continuous to be widely used in the design of mass transfer equipment.
Next to film theory the other models considers convective transport of near the interface
with the bulk phase as discussed below.
2.2.2 Penetration theory
The first penetration model originates from Higbie [4] where the mass transfer process is
described as follows: the interface is assumed to be covered with small stagnant fluid
elements and mass transfer occurs in to the element. After the contact time with the
interface, the element return to the well mixed bulk of the fluid from which they came,
while new element originating from the bulk take their place at the interface. Coming from
the bulk, all stagnant elements have a uniform initial concentration
K
C . At the interface
mass transfer occurs by molecular diffusion. This diffusion process is essentially transient.
Figure 2:3 is a qualitative sketch of the concentration profile versus the distance from the
interface for several times. The depth of penetration of k in to the element is assumed to be
small with respect to the thickness of the element .
8
Non-stationary diffusion takes place at the phase interface during the residence
time
0 1
t t = [5]. As only the direction perpendicular to the interface is significant, Ficks
second law for non-stationary one-dimensional diffusion applies:

Figure 2. 2 Interfacial renewal according to Higbie [5]

2
2
y
C
D
t
C K
K
K
(2.3)
Subject to the conditions:
Initial conditions:
K K
C C and t = > = , 0 0 (2.4a)
Boundary conditions
( )
( ) c C C y and t
b C C y and t
k K
Ki K
4 . 2 0
4 . 2 , 0 0
= = >
= = >

The last boundary condition can be used because the penetration depth is much smaller than
the thickness of the element. So a semi - infinite medium can be assumed.
9
The solution found for the above equation becomes
t D
y
erf
C C
C C
k k ai
k ki
2
(2.5)
Differentiating the above equation gives the molar flux of component k at the interface:

( )
k ki
k
y
k
k k
C C
t
D
y
C
D J =
=
=

0
(2.6)

t
D
h
k
D
= Mass transfer coefficient.

This shows that the mass transfer rate decreases with increasing time, which is caused by a
decrease of
y
C
k
at the interface. The rate of mass transfer can be lumped in the

parameter , which is called the contact time or the penetration time.
t
c
t
t
t > t > t
y
1
2
3
3 2
1

Figure 2. 3 Concentration profile in stagnant fluid element as a function of time
( = maximum time: contact time in the Higbie penetration model)
10
The modification of the Higbie penetration model has been developed by Danckwerts [4].
Instead a constant contact time , he assumed that the chance of a surface element being
replaced with in a given time is independent of its age. Thus, each element has an equal
chance of being replaced during the next time unit. The fraction of elements that is replaced
per unit time is assumed to be S ( ).
1
s Thus, the following can be derived.

( )
k ki k k
C C S D J =
(2.7)
The penetration model of Danckwerts is known as the surface renewal model. There are
also theories that describes mass transfer models; Film-surface renewal theory Dobbins,
and Surface-stretch theory Lightfoot and his Coworkers [3]. In this study the penetration
model is used. This is because it considers both molecular diffusion and bulk diffusions at
the interface.
The Penetration theory is most useful when mass transfer involves bubbles or droplets, or
flow over random packing [2].
2.2.3 Mass transfer Coefficient
On the bases of the theories discussed above, the rate of mass transfer in the bulk flow is
directly proportional to the deriving force expressed as a molar concentration difference,
and therefore
( )
Ko Ki D K
C C h N = (2.8)
D
h is the mass transfer coefficient. In the two - film theory
D
h is directly proportional to
the diffusivity and inversely proportional to the square root of the film thickness. According
to the penetration theory, it is proportional to the square root of the diffusivity and, when all
surface elements are exposed for equal time, it is inversely proportional to the square root
11
of the time of exposure; when random surface renewal is assumed, it is proportional to the
square root of the rate of renewal.
In the process where mass transfer takes place across a phase boundary, the same
theoretical approach can be applied to each of the phases, though does not follow that the
theory is best applied to both phases. For example, the film model might be to one phase
and the penetration model to the other.
When the film theory is applicable to each phase (the two - film theory), the process is
steady state through out and the interface composition does not then vary with time. For
this case the two film coefficient can be readily be combined. Because material does not
accumulate at the interface, the mass transfer on each side of the phase boundary will be the
same and for two phases it follows that
( ) ( )
2 2 2 1 1 1 Ko Ki D Ki Ko D A
C C h C C h N = = (2.9)
If there is no resistance to transfer at the interface
1 Ki
C and
2 Ki
C will be corresponding
values in the phase equilibrium relationship. Usually the value of the concentration at the
interface is not known and the mass transfer coefficient is considered for the over all
process. Over all transfer coefficients are then defined by:-
( ) ( )
2 2 2 1 1 1 Ko Ke D Ke Ko D K
C C h C C h N = = (2.10)
where
1 Ke
C is the concentration in phase one in equilibrium with
2 Ko
C in phase two, and
2 Ke
C is the concentration in phase two in equilibrium with
1 Ko
C in phase one. If the
equilibrium relation is linear
2
1
2
1
2
1
Ko
Ke
Ke
Ko
Ki
Ki
C
C
C
C
C
C
N = = = (2.11)
Where N is proportional constant (distribution coefficient).
12
The relationship between the various transfers coefficients are obtained as follows.

2 1 1
1 1
D D
h
N
h K
+ = (2.12)
Similarly
2 1 2
1 1 1
D D
h Nh K
+ = (2.13)
And hence
2 1
1
K
N
K
= (2.14)
These relationships between the various coefficients are valid provided that the transfer rate
is linearly related to the deriving force (concentration gradient) and that the equilibrium
relationship is a straight line [6]. They are therefore applicable for the two - film theory,
and for any instant of time for the penetration theory. In general, application to time -
average coefficients obtained from the penetration theory is not permissible because the
condition at the interface will be time - dependent unless all of the resistance lies in one of
the phases.
2.2.4 Mass transfer with chemical reaction
The theoretical under standing of mass transfer at the fluid interface with chemical reaction
is described by Hatta [4]. Hatta theory is based on the film theory model. He assumed that a
fast irreversible chemical reaction at the interface.

C B A
C B A
+
(2.15)
The transfer component A reacts with B in the absorbing phase to produce C at the
interface. The molar concentration of A and B decreases from its original values in the bulk
phase towards the interface. This simple model leads

+ =
, int , B
B
A
A
B
A A D A
C
D
D
C h n
(2.16)
13
Equation (2.16) equals the general equation developed for mass transfer with out reaction
equation (2.1). One gets therefore after dividing equation (2.16) by interface
concentration
int , k
C
, the mass transfer coefficient becomes as follows:-

+ =
,
,
1
A
B
A A
B B
D Dr
C
C
D
D
h h
(2.17a)

+ =
,
,
1
A
B
A A
B B
D
Dr
C
C
D
D
h
h
(2.17b)
This ratio is called the reaction factor. It describes the increase of mass transfer coefficient
if the mass transport is associated with chemical reaction. The reaction factor is dependent
on concentration and has the value of one if there is no chemical reaction. In the absorbing
phase calculation based on the surface renewal theory leads to a similar expression for the
reaction factor.
By performing a reaction through a liquid interface a concentration difference of the
product forms near the interface. It has been shown that in many cases, those gradients lead
to hydrodynamic instabilities, which then breaks non - linearly in to a pattern on sets slow
convection [7].
Although interfacial effects accompanying solute transfer have been subject of several
analyses [8], no generalized model has yet evolved which would enable the effect of
interfacial activities up on transfer rates to be predicted quantitatively. Such analysis are
complicated by superimposed effects such as convective flow induced by density gradients.
Berg and Moring (1969) [8] demonstrated that such gradients might retard or enhance the
convection generated by the marangoni effect. A further complication may rise from the
14
heat of solution accompanying the transfer of solute across an interface, since this can
influence both interfacial tension and any density gradients.
2.3 Numerical Solution Methods
A lot of works have been done for solving convective-diffusion problems for determined
velocity field. However, except in some very special circumstances, it is not possible to
specify the flow field; rather, one must calculate the local velocity component and the
density fields from the appropriate governed equation [9]. The velocity components are
governed by the momentum equations.
There are three distinct streams of numerical solutions techniques: finite difference, finite
element and spectral methods [10].The main difference between the three separate streams
are associated with the way in which the transport variables are approximated and with the
discretisation processes.
Finite difference methods: - Finite difference methods describe the unknowns transport
equation by means of point samples at the node points of a grid of coordinate lines.
Finite element methods: - Finite element methods use simple piecewise functions (e.g.
linear or quadratic) valid on elements to describe the local variations of unknowns transport
variable
.
Spectral methods: - Spectral methods approximate the unknowns by means of truncated
Fourier series or series of Chebyshev polynomials. Unlike the finite difference or finite
element approach the approximations are not local but valid throughout the entire
computational domain
Finite volume methods: - The finite volume method was originally developed as a special
finite difference formulation. It is the most well - established and thoroughly validated
15
general purpose CFD techniques. It is central to four of the five main commercial available
CFD codes: PHOENICS, FLUENT, FLOW3D AND STAR.CD. The numerical algorithm
consists of the following steps.
Formal integration of the governing equations of fluid flow over all the control
volumes of the solution domain.
Discretisation involves the substitution of a variety of finite - difference - type
approximations for the term in the integrated equation representing flow processes
such as convection, diffusion and sources. This converts the integral equation in to a
system of algebraic equations.
Solution of the algebraic equations by an iterative method.
The first step, the control volume integration, distinguishes the finite volume method from
all other CFD techniques. The resulting statements express the (exact) conservation of
relevant transport properties for each finite size cells. This clear relationship between the
numerical algorithm and the underlying physical conservation principles forms one of the
main attractions of the finite volume method and makes its concepts much more simple to
understand by engineers than finite or spectral methods.
The conservation of a general transport variable with in a finite control volume can be
expressed as a balance between the various processes tending to increase or decrease it.
volume
control
the inside
of creation
of rate Net
volume
control the
to in diffusion
to due
of flux Net
volume
control the
to in convection
to due
of flux Net
time to respect
with volume
hecontrl of
change of Rate
int
(2.18)

16
The above sets of equations are complex so an iterative solution approach is required. The
most popular solution procedures are TDMA line - line solver of the algebraic equations
and the SIMPLE algorithm to ensure correct linkage between pressure and velocity [10].
It is aimed in the present study to develop a mathematical model for interface mass transfer
with chemical reaction in liquid-liquid systems, incorporating the changes due to density
and surface tension on the transport coefficients It is also aimed to go for numerical
simulation using finite volume method (FVM) and to develop a general computer code.
One dimensional as well as two-dimensional computer code for solution of convection -
diffusion is described. The code is implemented in mat lab. The partial differential equation
is converted to a system of linear equations with the finite volume method. The system of
equations is solved with an iterative method.

17
3. The transport equations in Capillary space
In developing the mathematical model of the transport equations in the capillary space it
has been considered that the flow is caused by natural convection. Natural convection is
generated mainly due to density variation combined with gravity. Density variation and
buoyancy driven flows can result from solute concentration or temperature changes. The
convective terms of mass and heat transport equations are dependent on the velocity
generated by buoyancy driven flow.

( )
0
,
=
y
t H C

( )
0
, 0
=
y
t C

Figure 3. 4 Two dimensional representation of the capillary space
18

As shown in figure 3.1 two layers of liquids are superimposed one another. The upper layer
is cyclohexane and the bottom layer is water solution. Initially the bottom layer of depth h
contains only water solution containing one molar solution of sodium hydroxide no acetic
acid( ) 0 =
o
C , and the upper layer of depth h H , contains acetic acid( )
o
C C = . Mass
transfer is therefore from the upper phase to the lower phase. Thus the transfer mechanism
has been modeled mathematically using micro balance model.
3.1 The transport equation in the bulk of the fluid phase
As it has been discussed above there are two phases for this particular study. Initially the
two phases are separated by hypothetical stretch (layer). Hence it is possible to treat the two
bulk phases independently by the usual differential equations of mass, heat and momentum
balances. But as time goes the interface of the two phases behaves differently. Hence the
interface of the phases needs a special treatment. All about these are discussed in the
subsequent sections.
3.1.1 Buoyancy and the Boussinesq Approximation
The variation in the fluid density which underlie free convention preclude the use of
Nervier stokes equation [11]. We begin instead with the Cauchy forms of conservation of
momentum, written as
+ + = g
Dt
DV
P (3.1)
With forced convection, it is often desirable to work with dynamic pressure p instead of
the actual pressureP .
g p
o
= P (3.2)
19
o
is the constant density in some arbitrarily chosen reference state.
The pressure and gravitational terms in the momentum equation can be written as
g p g
o o
) ( + = P (3.3)
Using equation (3.3) in equation (3.1) the momentum equation becomes
+ = g p
Dt
DV
o
) ( (3.4)
The term ( )
o
may view as a force per unit volume due to buoyancy. In essence, it is
the force responsible for free convection. If
o
= every where, the pressure and
gravitational terms reduce P , as forced convection. This suggests that we associate the
gradient in dynamic pressure with forced convection.
In free convection problems involving a pure, non isothermal fluid, the unknowns are the
velocity, pressure, temperature and density [11]. The basic equations are continuity,
conservation of momentum, and conservation of energy (all with variable ), together with
an equation of state for the fluid. The equation of state, which is of the form ( ) T p, = ,
makes the fluid dynamic problem dependant on the heat transfer problem, even if all other
fluid properties are constant. For an isothermal mixture in which the density depends on the
local composition, the energy equation is replaced by one or more species composition.
Clearly, the analysis of buoyancy - driven flow may be extremely complicated. The
solution to the general set of equations is so difficult that almost all published works has
employed what is called the Boussinesq Approximation [11]
Generally there are two parts for the Boussinesq Approximation
i. The first is the assumption that varies linearly with temperature and/or
concentration
20
( ) ( )
o i
Cio To
o
Cio To
o
C C
C
T T
T

+ =
, ,

(3.5)
( ) ) ( 1
o i i o
o
C C T T + + =
(3.6)

Cio To o
i
Cio To o
C T
, ,
1
,
1

i
and are the thermal and the solutal expansion coefficient respectively.
ii. The second part of the Boussinesq approximation is the assumption that the variable
density can be replaced every where by the constant value
o
, except in the
term( )g
o
. This is crucial, because it leads to the continuity equation for constant
density fluid and allows the viscous stress to be evaluated as in the Navier stokes equation.
For Liquids the necessary condition is . 1
0
<<
Hence it is possible to use equation (3.1)

provided that the density is constant except in gravitational terms. In this paper the second
approximation of the Boussinesq Approximation is applied due to its simplicity.
Using the Boussinesq Approximation the continuity and momentum equations for pure
Newtonian fluids with constant becomes
0 = V (3.7)
( ) g p V V V
t
V
o o

+ = +
1
2
(3.8)
Actually this approach yields what is still a difficult set of coupled differential equations,
one which is much more amendable to analysis. Especially the second approximation
simplifies the dependency of the momentum equation on temperature.

21
3.1.2 Description of the flow in the capillary space
The flow in the capillary is considered to be two dimensional for this particular model.
Hence the z component of the velocity w is zero due to the geometrical configuration of
the system. It is assumed that the flow is laminar. To proof the above assumption, the
Reynolds number at thermal convection in an infinite length of the capillary tube
( y x, ) and mm Z 1 = is considered. The fluid particle shall have temperature
difference of k T 10 = compare to the surrounding fluid. The volume expansion
coefficient
1 3
10

k
T
(Benzene) the gravitational force
2
10

= ms g , neglect the effect of
the fluid viscosity over the distance of , 1 . 0 m y = the velocity of the fluid particle will be

1 1
14 . 0 10 001 . 0 10 1 . 0 2
2

=
=
ms ms
T g y
T
V
(3.9)
The characteristic length can be determined by the hydraulic diameter
h
d

x
Z
Z
x Z
Zx
U
A
d
h
+
=
+
= =
1
2
2 2
4 4
(3.10)
Where U = perimeter, A Area, x and Z are side of the capillary tube. If x , the
hydraulic diameter will be

= = =
x
m m Z d
h
002 . 0 001 . 0 2 2 lim
(3.11)
The capillary is hydraulic equivalent with a pipe of Z d
h
2 = . The kinetic viscosity of a
fluid is given by (
1 2 7
10 8 . 6

= s m v ). This will give a rough estimate of the Reynolds
number Re
412
10 8 . 6
002 . 0 14 . 0
Re
7

= =
h
d V
(3.12)
22
Since the Reynolds number is less than 2300, the flow considered above in the capillary
space is laminar.

Figure 3. 5 Velocity profile of laminar flow in capillary tube

In the absence of an end effect, the equation of motion for the liquid film in fully developed
laminar flow in the x - direction is given by
p g
z
u
= =

2
2
(3.13)
Usually in fully developed flow, u is independent of the distance x.
Boundary condition
Z and Z z at u
2
1
2
1
, 0 = = (No slip condition at solid surface)
0 , 0 = =
z at
z
u

Integrating equation (3.13) twice with the given boundary conditions

=
2
2
4
1 ) (
Z
z
u z u
(3.14)
23
u is the maximum velocity at 0 = z . The average velocity is obtained by integrating
equation (3.14) in the interval of Z and Z
2
1
2
1

u dz z u
Z
u
Z
Z
3
2
) (
1
2
2
= = (3.15)
The two velocity component therefore

=
2
2
4
1
2
3
) (
Z
z u
z u (3.16a)
and with the same analogy the y - component becomes

=
2
2
4
1
2
3
) (
Z
z V
z V (3.16b)
From equation (3.8) a two dimensional viscous flow problems at constant fluid properties
are generally governed in the Cartesian system by the following three equations.
0 =
y
V
x
u
(3.17a)

x y
u
x
u
y
u
V
x
u
u
t
u
o

1
2
2
2
2
(3.17b)

y
o o
g
x y
V
x
V
y
V
V
x
V
u
t
V
1
2
2
2
2
(3.17c)
The flow is only the function of x, y and t. Substituting equation (3.16) in equation (3.17)
and integrating each term in terms of z in the interval of

2
,
2
Z Z
, the following space
average equations can be obtained.
24

x
u
Z y
u
x
u
y
u
V
x
u
u
t
u
o

1 12
5
6
2 2
2
2
2
(3.18a)
and
y
o o
g
x
V
Z y
V
x
V
y
V
V
x
V
u
t
V
1 12
2 2
2
2
2
(3.18b)
The three unknowns u, v and p often termed as primitive variables. The above system
equations are still very complicated, and an important simplification is obtained by
employing the stream function , defined in the next sub section. In the following section
the average velocities are used and no bar symbol is used u .
3.1.3 Vortices transport and poison equation
The stream function is a mathematical constructs which is extremely useful for solving
incompressible flow problems where only two non vanishing components and two special
components are involved [11]).
For two dimensional flow described by rectangular coordinates, the stream function
( ) y x, is defined by

y
u
=

,
x
V
=

(3.19)
And the vorticity defined by

x
V
y
u
= (3.20)
Where is the vorticity, being only the z component of
z
for the above two dimensional
flow.
The main advantage of these choices is seen by substituting equation (3.19) in a
corresponding continuity equation for incompressible fluid
25
=
y
V
x
u
0 =
x y y x

(3.21)

Thus the stream function is defined in such away that ( ) y x, can be determined for the
given flow, the continuity equation will be satisfied automatically.
Having defined the stream and vorticity functions, it is now possible to solve the transport
equation (3.18). But the pressure term should be eliminated. The pressure term is
eliminated by differentiating each term in equation (3.18a) in terms of y and each term in
equation (3.18b) in terms of x. Then subtracting one from the other, and using the vorticity
(
) from equation (3.20) the final equation becomes

x
g
Z y x y
V
w
y
V
x
u
w
x
u
t
o
y

2 2
2
2
2
12
5
6
(3.22)
The terms ) ( ) (
y
V
and
x
u
can be eliminated using the continuity equation (3.7), and

Equation (3.22) becomes

x
g
Z y x y
V
x
u
t
o
y

2 2
2
2
2
12
5
6
(3.23)
The convective term
y
V and
x
u

in equation (3.23) can be calculated using stream
function (3.19).
2
2
2
2
y x
=

(3.24)

26
3.2 The transport equation at the interface
3.2.1 Reyhlogical Properties at the interface
Components of any solution behave differently at an interface than they do with in the bulk
solution. One example is that their concentration at the interface is different from with in
the bulk phase. This different, called adsorption at the liquid interface manifests itself by a
change in the capillary properties of the interface [12].
The liquid droplet has a tendency to contract as if it is surrounded by a hypothetical
stretched skin. If the drop of liquid is uninfluenced by external forces, such as gravity, it
will adopt a truly spherical shape.
Young first explained surface tension as resulting from the attraction between the
neighboring molecules (Young, 1805) [12]. These forces are isotropic in the interior of the
bulk phase but molecules at the interface are attracted less completely than in the bulk.
Because the free energy of a system tends to a minimum the surface of a pure phase or the
interface between two immiscible liquids will always tend to contract spontaneously.
The interfacial tension is always positive (Landau and Lifshitz, 1958) [12]. If the interfacial
tension, 0 < the interface between two immiscible liquids will tend to increase without
limit, and the phase would mix and cease to exist separately. If 0 > , then the interface
become as small as possible for a given volume of the two phases.
The interfacial tension can be altered by adding a surface active solute. The molecule of a
surfactant tends to concentrate at the interface rather than in the bulk phase and typically
form monomolecular layer.
Gibbs published his classic treaties about adsorption and capillarity in 1875 [12] but his
pioneering was only appreciated year later, and experimental application of the Gibbs
27
equation of adsorption becomes important only in the beginning of this century (Gibbs,
1928). The Gibbs equation is expressed by

dC
d
RT
c
= (3.25)
Where represents the excess number of adsorption particles in a portion of solution
containing a unit area in a comparison with some homogenous solution having exactly the
same volume.
The tension at the interface of between two phases is dynamic in nature. The value of the
tension is dependent on the velocity of deformation of the interface.
The equation of the dynamic surface tension at the interface wants to know the viscosity of
the fluid ( ) and .These interfacial shear viscosity
( )
and interfacial dilatation viscosity
( )
describe the viscous condition of the interface. These viscosities determine the
movement of the molecules between the two phases.
The dynamic surface tension
dyn
depends also on the coordinate system.
For Newtonian fluid and are constant. Therefore for flat interface parallel to the x
and z direction the equation of the dynamic interfacial tension can be formulated as follows

( )

+ + =
z
w
x
u
z
w
x
u
equ dyn

(3.26a)
and in the z direction

( )

+ + =
z
u
x
w
z
w
x
u
equ dyn

(3.26b)
where, u and w are velocity components in x and z direction respectively
28
3.2.2. The tension equilibrium at the phase interface
Along the phase interface if there is concentration and temperature gradient, due to this
there will be also interfacial tension gradient. There exist expansion and contraction of the
interface due to the variation of the interfacial tension at the interface. Normal to the
interface there is a gradient parallel to the velocity component which means at the interface
it generate an impulse. The impulse is transferred to the neighboring liquid phase by the
viscous force .
z x
in
*
z z x
x

+
e
x
Figure 3. 6 The force balance in the x - direction at the interface.

The mathematical description of the interface is discontinuous. At the interface the
density( ) , the viscosity ( ) and the viscous stress ( ) changes suddenly. Therefore the
balance of the force at the interface can be expressed by

0 * =
+ z x
x
z x z x
in in

(3.27)
Multiplying the above equation by the reciprocal of the z x

0 * =
+
x
in in

(3.28)
z x
in

29
For
x
, the x - differentiation of dynamic interfacial tension given in equation (3.26) is

used. If fast diffusing component with low adsorption is assumed, then the interface
viscosities and can be neglected. The interfacial tension is dependent on the local
temperature and concentration. The total differential of the interfacial tension is therefore

x
T
T x
C
C x
equ equ
(3.29)
The terms
T
and
C
euq equ

are measurable at equilibrium in two phase systems.
The viscous stress and * can be expressed in Newtons law of viscosity.

=
x
V
y
u
(3.30a)

*
* *

=
x
V
y
u
(3.30b)
Along a flat locally fixed interface the normal velocity component equals zero ( 0 = V ).
Hence equation (3.30) can be simplified to

int int

=
y
u
(3.31a)

*
int int
* *

=
y
u
(3.31b)
The viscous stress can be also expressed in terms of the Vorticity equation ) 20 . 3 ( and
stream function equation ( ) 19 . 3 as usual. When 0
int
= V the Vorticity equation becomes

int int
y
u
= (3.32a)
30

*
int
int
*
y
u
= (3.32b)
Substituting equation (3.32) in equation (3.31)
int int
=
(3.33a)

*
int
*
int
=
(3.33b)
The force balance becomes
0 * *
int int
=
+
x
(3.34)
In terms of the stream function

0 *
2
2
int
2
2
=
x y y

(3.35)
At the interface there are two unknown parameters * and . To determine these
parameters, the equilibrium tension balance should be satisfied and the Vorticity transport
equation is needed.
3.2.3 The Vorticity Transport equation at the interface
The derivation of the viscous stress at the interface shows that the Vorticity force along the
interface is not generally constant. Therefore the Vorticity equation requires the value of
the two terms ( ) * and and it is also important to consider the sudden change of the
physical properties of the fluid ( ). ,
To formulate those equations at the interface the average of the contribution of both phases
to the impulse balance is required. The momentum equation derived for the bulk phase
using Boussinesq Approximation is not applicable for the interface, because the
31
formulation of the average of the two terms, which is only purely kinematics, violates
conservation equation.
So to get the correct equation we start with the Vorticity equation
x
g
Z y y x y
V
x
u
t
y o

]
]
.
}
\
|
]
]
.
}
\
|
2 2
2
12
5
6
(3.36)
The density and viscosity variation in y - direction is considered normal to the interface.
When the velocity component 0 = V , then 0 =
y
V

, therefore equation (3.36) will be
x
g
Z y y x x
u
t
y o o
2 2
2
12
5
6
(3.37)

t t t
o o o
*
*
2
1
(3.38)

x x x
o o o
*
*
2
1
(3.39)

2
2
2
2
2
2
*
*
2
1
x x x
o o o
(3.40)
( ) * *
2
1
+ = w (3.41)

x x x
*
2
1
(3.42)
Together with the tension equilibrium equation (3.34), we have two equations with two
unknown variables, therefore one can solve simultaneously.
3.3 Mass and heat transport equation
The mass and heat transport equation contains both conductive and convective terms like
momentum transport. The single conductive transport term in multi-component system is
32
independent to each other. Thermal diffusion (mass transport due to temperature gradient),
the heat flow due to concentration gradient, cross diffusion (mass transfer due to
concentration of other components), are neglected in a capillary flow.
In z - direction both temperature and concentration gradient in the capillary are also
neglected

0
z
C
z
T
. The density change in z - direction, which is dependent on
temperature and concentration are also neglected
0
z
. In the convective term, the

velocity is taken to be the average value of the capillary space.
3.3.1 Mass and heat transport equations in capillary space
Problem involving chemical reaction are handled most easily with molar units, so that
k
C
is generally preferred. The molar flux of component k relative to fixed coordinates is
k
N
[11]. Thus, the basic form of the conservation equation for component k is
vk k
k
r N
t
C
+ =
(3.43)
The source term
vk
r
represents net rate of formation or consumption of species k by
chemical reaction per unit volume. Reactions which appear in this manner (i.e., ones which
occur through out the volume of the gas or liquid solution) are called homogeneous. When
there is fluid flow the preferred way to write the total flux is

k k k
J C N + = V
(3.44)
Where, J
k
is the molar flux of k relative to the mass average velocity.
33
Several forms of Ficks law for binary mixtures were presented in Transport analysis by
William M.Deen [11]. For a binary mixture of component k and B at constant density, the
molar flux of k relative to the mass - average velocity is given by
k kB k
C D J = (3.45)
This is an excellent approximation for most liquid solutions, less accurate for gas mixtures
[11]. Although strictly valid only for a binary system, equation (3.45) can be applied also
to certain multi - component mixtures. In multi - component liquid solution or gas mixtures
there are diffusion interactions between each pair of components. However, if all
component but one are present in small amounts, interaction among the minor component
tends to be negligible, and only the binary diffusivity of each minor component k with the
abundant component is important. For this pseudobinary situation at constant density, the
flux equation for each minor component is give by

k k k
C D J = (3.46)
Equation (3.46) is the most frequently used flux equation for liquid solutions, even when
there are more than two components [11].
The differential equation of the mass transport with chemical reaction in a control volume
for component k is described in a conservation form for constant
k
D and as follows.
( ) ( )
V k k k k k
k
r M C D VC
t
C
+ = +
(3.47)
For two dimensional problems and constant diffusion coefficient
k
D equation (3.47) can be
written as follows
V k k
k k
k
k k k
r M
y
C
x
C
D
y
C
V
x
C
u
t
C
+
2
2
2
2
(3.48)
34
v
r is the volume base reaction velocity (production rate per unit volume per unit time).
Through multiplication with the Stoichiometry coefficient
k
and the molar mass
k
M one
can get the source term for mass concentration of component k.
k
is negative for reactants
and positive for products.
The heat transport equation is also described in conservation form as shown below.
( )
( ) ( )
v R P
P
Hr T VT c
t
T c
+ = +
(3.49)
H
R
is the molar reaction enthalpy and dissipation function.
The reaction rate velocity
v
r is dependent on the temperature and concentration of the
system. Both equations (3.48) and (3.49) are interrelating to each other by the reaction rate.
The dissipation function considered is the conversion of kinetic energy in to heat energy
through the friction of the fluid. The estimation of this function shows that the viscous
dissipation due to the given velocity is neglected. The shear force at the surface
= Z z
2
1

had attained its maximum value. Taking the flow velocity of
1
1 . 0

= ms u in the middle of
the capillary, the viscosity of the fluid mPas 1 = , the width of the capillary mm Z 1 = ,
the maximum shear force at the interface will be
Pa Pa u
Z
Z
z
z
u
4 . 0 1 . 0
001 . 0
001 . 0 4 4
2
max
=
= =
=
=

(3.50)
Assume the temperature difference K T 10 = in the capillary for length cm L 1 = , and the
thermal conductivity
1 1
5 . 0

= K wm . The ratio of dissipation energy to heat conduction
becomes
35

6 max
10 6 . 8
01 . 0
10
5 . 0
1 . 0 4 . 0

=
L
T
u
(3.51)
The viscous dissipation energy is
6
10
smaller than the heat flow that is expected; hence it

is possible to neglect it.
In two dimensional Cartesian coordinate with constant and neglected viscous dissipation,
the heat transport equation becomes
( )
( ) ( )
v R
p p
P
Hr
y
T
x
T
y
VT c
x
uT c
t
T c

2
2
2
2
(3.52)
Through both walls of the capillary, there is a heat lost to the surrounding. This can be
described based on the reaction volume of the capillary and width Z by
( ) T T
Z
U
q
s
o
=
2
(3.53)
Where
s
T is surrounding temperature,
o
U is overall heat transfer coefficient given by
io w o
h
s
U
1 1
+ =
(3.54)
For constant specific heat capacity
p
c and density
o
and using Boussinesq approximation
and continuity equation, the heat transport equation becomes
( )
]
]
]

|
|
\
|
T T
Z
U
Hr
c y
T
x
T
a
y
T
V
x
T
u
t
T
s
o
r R
P o
2 1
2
2
2
2
(3.55)
The temperature coefficient (thermal diffusivity) is given by
( )
p o
c
a
=
3.3.2 Mass and Heat Transport equations at the phase interface.
In two film theory (2.2), we only considered the conductive transport of heat and mass. But
now we are considering both types of transport (conductive and convective) of mass and
36
heat. These requires convection - diffusion equation similar to equation (3.48) and (3.55) in
the vicinity of the interface.
The concentration gradient of the transport component at the interface is in general
unsteady. The different in concentration gradient at the interface is the result of different
solubilitys of the transport components between the two liquid phases. The interface
concentrations
int int
* C and C are only in equilibrium if the interface itself does not resist
the mass transport. Based on tow - film theory, Whteman, [3], the relation between the
concentrations can be described by the following equation

int
*
int
C
C
N = (3.56)
The distribution coefficient N is a function of temperature and concentration.
The transport resistance grows for a component that tends to precipitate at the interface.
Therefore the interface becomes broader. At the interface the adsorbed component hinders
the diffusion of a certain component. In this study it is assumed that the two phases are in
equilibrium and the transport resistance at the interface is neglected.
The second equation that is necessary to calculate the unknown interface concentration is
the mass transport equation. Due to the sharp variation of the concentration, the variation of
the diffusion coefficient is taken to be normal to the interface therefore the equation
becomes the arithmetic mean of the two phases.
k k k
k
k
k
k
k k k
r M
y
C
D
y x
C
D
y
C
V
x
C
u
t
C
+
2
2
(3.57)

x
C
x
C
t
C k
k k
*
2
1
(3.58)
37

x
C
u
x
C
u
x
C
u
k
k k
*
2
1
(3.59)

2
* 2
*
2
2
2
2
2
1
x
C
D
x
C
D
x
C
D
k
k
k
k
k
k
(3.60)

( ) v
v v
r r r
*
2
1
+ =
(3.61)
The temperature at the interface is steady, i.e. int
*
int
T T = . With in the fluid phase, there
shall be a constant value of
* * *
, , , ,
o
p
o p
c and c
. Under this condition we built the
differential equation for heat transport equation at the interface as follows
( ) T T
Z
k
r H
y
T
y x
T
y
T
V c
x
T
u
t
T
c
u v R p o p o
+
|
|
\
|
+
]
]
]
2
2
2
(3.62)
Where ( )
p o p o p o
c c c
*
2
1
+ = (3.63)
and
( )
*
2
1
+ = (3.64)
Table 3. 1 Summary of the transport equations in the capillary flow.

Momentum Mass Heat
Bulk Phase
Interface
(3.19), (3.23), (3,24)
(3,19), (3,34), (3,35),(3.37)
(3.48)
(3.56), (5.57)
(3.55)
(3.62)

Generally the following assumption are used in deriving the model equations
Flat interface
Boussinesq Approximation is applied
38
Two dimensional transports with parabolic velocity profile.
Conductive transport are independent to each other
Equilibrium is assumed at the interface.
Viscous dissipation is neglected
The model can be further simplified if only a single component is transported to the
interface. This single component under go chemical reaction immediately it passes the
interface. The second reactant in the second phase should be present in large amount, so
that the concentration does not affect the reaction rate. The reaction release heat in vicinity
of the interface. The reaction considered here is very fast; hence the reaction takes place at
the interface. The component that reaches as reactant to the interface will leave as a
product. Having this simplification we do not have to consider the chemical reaction of the
component so that the reaction term in the mass transport equation (3.57) will be zero. In
the heat transport equation at the interface equation (3.62), the reaction term can be
substituted with the source term. The value of the source term is proportional to the local
mass flux at the interface. Away from the interface the heat source in the transport equation
(3.55) is zero. The model equations are solved using numerical discretisation techniques
discussed in the following chapter.

39

4. Numerical Approach of the transport equation
4.1 The nature of numerical Methods and Discretisation Concept
4.1.1 The nature of Numerical Methods
A numerical solution of a differential equation consists of a set of numbers from which the
distribution of the dependent variable can be constructed. In this sense, a numerical
method is akin (similar) to a laboratory experiment, in which a set of instrumental reading
enables us to establish the distribution of the measured quantities in the domain under
investigation [9]. Most numerical methods employ methods that give a value of at a
finite number of locations called grid points in the calculation domain. The method includes
the tasks of providing a set of algebraic equations for those unknowns and of prescribing an
algorithm for solving the equation.
4.1.2 The discretisation Concept
In focusing attention on the values at the grid points, one can replace the exact solution of
the differential equation with discrete values. One can thus discretise the distribution of ,
and it is appropriate to refer to this class of numerical methods as discretisation methods.
The Algebraic equations involving the unknown values of at chosen grid point, which
we shall now name discretisation equation, are derived from the differential equation
governing .
For a given differential equation, the required discretisation equation can be derived in
many ways. Some of them are Taylor series formulation, Methods of weighted average,
40
Variation formulation and the control volume formulation (Finite volume method). Here
central - difference control volume (Finite volume) method is employed.
The control-volume finite-difference (CVFD) method is widely used in the numerical
simulation of fluid dynamics, heat transfer and combustion. Several commercial CFD
(Computational fluid dynamics) codes are based on this method. Though there is no one
ultimate numerical approximation scheme, the CVFD method has numerous desirable
features. It naturally maintains conservation of species when applied to conservation laws.
It readily handles material discontinuities and conjugate heat transfer problems. It also has
the pedagogical advantage that only simple calculus is required to derive the CVFD
approximation to common conservation equations.
The form of the calculation area is designed based on the given problem. The investigated
capillary is discretised through orthogonal grids. As the mesh size becomes smaller the
solution becomes similar to the exact solution. To optimize saving space and calculation
time the distance of the gridline should be chosen in a way that only those areas where we
expect a great gradient of the transport equation should be finer. For the given problem
therefore the area of the interface requires a finer grid in the vertical direction. The distance
y is calculated recursively and through geometric series.

1 +
=
j
y F y
(4.1)
F is the factor to make the grid finer and it has the value smaller than one. For the
horizontal boundaries the distance reaches its maximum value
max
y
. So in the x - direction
the mesh size is constant X , fig 4.1

41

X
y

Interface

y

z x Figure 4. 1 Representation of non uniform mesh

4.2 Discretisation of Transport equations
4.2.1 Discretisation of temporal changes
The transport equation described the temporary change of the transport values in
differential volume element as a balance of those streams that cross the boundary of the
volume element. For the general function this change is expressed in transit form
t
.
The real temporal development of at the grid point is approximated through the
calculation at the grid time point
m
t . We also have to approximate
t
based on the time

42
discrete value. Often
t
can be discretised using first order back ward differentiation

scheme.

1
1
m m
m
P
m
P m
p
t t t

(4.2)
The linear profile does not necessary display the real profile of the temporal change of the
transport value, especially for periodical changes. A better approximation can be achieved
by using a second order differentiation. For simplicity and to save computer storage first
order backward differentiation is used for this study.
4.2.2 The vorticity transport equation in the bulk phase
The vorticity transport equation is discretised through finite central different method. The
differential quotient at the grid point is approximated through central difference.
The vorticity transport equation as derived in chapter three is given by

x
g
Z y x y
V
x
u
t
o
y

2 2
2
2
2
12
5
6
(4.3)
The time function is discretised at the grid point P. It is discretised using a first order
backward differencing scheme.

t t
m
P
m
P m
P
(4.4)
In equation (4.4) superscript 1 m refers to vorticity at time t t and m refers to vorticity
at timet .
The diffusion term is discretised using central finite difference in x and y direction.
( ) ( )

+
+
]
]
.
}
y
y y
x y x
S S P N P N E P W
2 2
2
2
2
2
(4.5)
43
Where ( )
S N
y y y + =
2
1

For the wall shear term it is discretised at the grid point P.

P P
Z Z

2 2
12 12
(4.6)

Figure 4. 2 Space discretisation of vorticity transport equation

The notation of the grid points are according to the compass notation. The two arrows at the
grid points are representing the two velocity components ( V u & ).
The density term is discretised at the grid point P

x
g
x
g
w e
o
y
P
o
y
(4.7)
The density distribution can be calculated by an appropriate mass law out of temperature
and concentration profiles. Density is calculated at the grid point of temperature and
concentration calculation area.
44
To get a stable and realistic solution the chosen discretisation scheme should have to show
some fundamental properties of real streams. The important ones are:
Conservativeness
Tran sportiveness
Bounded ness
To ensure conservation of for the whole solution domain the flux of leaving a control
volume across a certain face must be equal to the flux of entering the adjacent control
volume through the same face [9]. To achieve this flux through a common face must be
represented in a consistent manner - by one and the same expression in adjacent control
volume.
Diagonal dominance is a desirable feature for satisfying the boundedness criterion .This
states that in the absence of source term, the internal nodal values of the property should
be bounded by its boundary value. Another essential requirement for boundedness is that all
coefficients of the discretised equation should have the same sign (usually all positive) [10].
The transportiveness property states that the transport value is basically transported to the
stream down ward. That means the value at the grid point is determined by the stream up
wards.
In order to satisfy the above properties it is important to select the best formulation to
discretise the give transport equations. Here the upwind differencing scheme is used in the
discretisation of the convective terms of the model equations.
The up - wind scheme in the area of finite difference method approximates the convective
term
x
u
through the stream up ward differentiation. The horizontal second order

approximation of the convective term is given as shown below
45
0 ,
2
4 3
0 ,
2
4 3
<
>
]
]
]
u when
x
u
u when
x
u
x
u
EE E P
P
WW W P
P
P

(4.8)
For the term
y
V
due to non uniform grid lines in the y direction the problem becomes
more complex.
( ) ( )
( )
( ) ( )
( )
0 ,
2
0 ,
2
2 2
2 2
<
+
+ + +
>
+
+ + +
]
]
]
v when
y y y y
y y y y y y
V
v when
y y y y
y y y y y y
V
y
V
NN N NN N
NN
N
N NN N P NN N NN
p
SS S SS S
SS
S
S SS s P SS S SS
p
P

(4.9)
Substituting equation (4.4 to 4.9) in to equation (4.3) and rearranging all the terms, one can
obtain the following equation: Appendix B: 1
b a a a
a a a a a a a
m
P
m m
SS SS
m
NN NN
m
WW WW
m
EE EE
m
S S
m
N N
m
W W
m
E E
m
P P
+ + +
+ + + + + + =
1 1

(4.10)
The discretisation coefficients in the above equation are:
(4.11a)
(4.11b)

(4.11c)
(4.11d)

( )
) 11 . 4 ( ) 0 , max(
5
6
) 11 . 4 ( ) 0 , max(
5
3
) 11 . 4 ( ) 0 , max(
5
3
g V
y y y
y
a
f u
x
a
e u
x
a
P
NN N NN
N
NN
P WW
P EE
+
=
=
=

( )
( )
( )
( )
( )
( )
N S S
P
SS S
SS S
S
N S N
P
NN N
NN N
N
P W
P E
y y y
V
y y
y y
a
y y y
V
y y
y y
a
u
x x
a
u
x x
a

+
+
+
=
+
+
+
=
+ =
+ =
2
0 , max
5
6
2
0 , max
5
6
) 0 , max(
5
12
) 0 , max(
5
12
2
2
46
( )
) 0 , max(
5
6
P
SS S SS
S
SS
V
y y y
y
a

+
= (4.11h)
) 11 . 4 (
) 11 . 4 (
12
) 11 . 4 (
1
2
1
1
k
x
g
b
j
Z
a a a a a a a a a a
i
t
a
w e
o
P
m
SS NN WW EE S N W E P
m
P

=
+ + + + + + + + + =
=

Unsteady state problems can be discretised in many different ways. Some of the well
known schemes are explicit and fully implicit schemes.
The explicit scheme essentially assumes that the old value
1 m
prevails through out the
entire time step except at the time t t + . Explicit scheme is conditionally stable. It has a
great restriction on the time step size. The time step depends on the mesh size ( ) ( )
2
x t
It becomes very expensive to improve spatial accuracy because the maximum possible time
step needs to reduce as the square of x . Consequently this method is not recommended for
general transient problems [10].
The fully implicit scheme assumes that the new value
m
, prevails through out the entire
time step. In fully implicit scheme discretisation both side of the discretisation equation
contain the transport properties (
m
) at the new time step and system of algebraic
equations must be solved at the new time step. The time marching procedure starts with a
give initial distribution of the transport properties (
1 m
). The system of equations
developed is solved after selecting time step t . Next the solution
m
is assigned to
1 m
and the procedure is repeated to progress the solution by a further time step. All the
coefficients of the discretised equations are positive; this makes the implicit scheme
47
unconditionally stable for any time step size. Since the accuracy of the scheme is only first
order in time, small time step are needed to ensure the accuracy of the result. On the ground
of its superior stability the fully implicit scheme is recommended for general purpose CFD
computations [9, 10].
4.2.3 The poison equation
It is used second order central differencing scheme to discretised the Poisson equation. The
discretisation of the Poisson equation (3.20) will result in

( ) ( )
y
y y
x
S P N N P N E P W
p

+

=
2
2
(4.12)

P S S N N W W E E P P
a a a a a + + + = (4.13)
The discretised form of the Poison equation has the following coefficients.

2
1
x
a a
W E
= = (4.14a)

y y
a
N
N

1
= (4.14b)

y y
a
S
S

1
= (4.14c)

S N W E P
a a a a a + + + = (4.14d)
4.2.4 The velocity field
The rule used to calculate the velocity component at the grid point is derived from the
definition of the stream function. The course of the stream function is under gone square
interpolation between the three points
p s n p e w
and , , , , .
48
To calculate the value at the point p for the horizontal velocity component
( )
( )
( )
( )
P N
N S S
N
P N
N S N
S
P
y y y
y
y y y
y
u

+
+
+
(4.15a)
And for the vertical velocity component

x
V
W E
p
(4.15b)
4.2.5 Mass and heat transport equation in the bulk phases
The equation of mass and heat transport equations are discretised with the help of finite
volume method. The line of the grid is divided in to non overlapping rectangular control
volume. In this method the transport equation is integrated over the given control volume.
In the center of the control volume P, the transport value concentration and temperature are
calculated.

Figure 4. 3 Control Volumes for calculation of temperature and concentration distributions
49

To get the discretised equation therefore we need the equations in the form of conservative
equations as shown below.
V k k
k k
k
k k k
r M
y
C
x
C
D
y
C
V
x
C
u
t
C
+
2
2
2
2
(4.16)
The first term of the above equation represents the time change term and is zero for steady
state problems. The finite volume integration of equation (4.16) over a control volume must
be augmented with a further integration over the finite time step t .
Each term in this equation are evaluated and simplified separately. The parts are then
reassembled in to a discrete equation relating at node P to the value at nodes , , W E N
and S .
The temporal mass change in the control volume is approximated with first order
(backward) differencing scheme over the control volume.
y x
t
C C
dxdy
t
C
m
P
m
P
n
s
e
w
m

(4.17)
The convective term in equation (4.16) can be integrated once with out approximation.
( ) ( )
( ) ( )
( ) ( )
s s n n w w e e
s s n n w w e e
n
s
e
w
n
s
e
w
C F C F C F C F
x C v C v y C u C u dxdy
y
VC
dxdy
x
uC
+
+

(4.18)

To evaluate the right hand side of the preceding expression the values of
w e
C C , ,
n
C
s
C and need to be estimated. In the finite volume method, the values are stored only at the
nodes S and N E W P , , , , . The method for determining an interface value (say,
e
C ) from the
50
nodal values (say,
P E
C and C , ) has important consequence for the accuracy of the
numerical model of equation (4.16).
A straight forward method for estimating for the general property
e
in terms of nodal
values
P E
and is linear interpolation (called central differencing scheme). But it has a
disadvantage of not identifying the flow direction [9]. A better estimation is the up-wind
differencing scheme. Because it takes in to account the flow direction when determining the
value at the cell face: the convective value of
e
at a cell face is taken to be equal to the
value at the upstream node. Based on the above explanation the cell face values are given
as shown below.

0
0
< =
> =
e E e
e p e
F if C C
F if C C

The value of
w
C can be define similarly. The conditional statement can be more compactly
written if we define a new operator. We shall define max (a, b) to denote the greater of A
and B, then the up wind differencing scheme implies
( ) ( )
( ) ( )
( ) ( )
( ) ( ) ) 19 . 4 ( 0 , max 0 , max
) 19 . 4 ( , 0 , max 0 , max
19 . 4 ( 0 , max 0 , max
) 19 . 4 ( , 0 , max 0 , max
d F C F C C F
c F C F C C F
b F C F C C F
a F C F C C F
s P s S s s
n N n P n n
w P w W w w
e E e P e e
=
=
=
=

Therefore equation (4.18) becomes
( ) ( )
( ) ( )
( ) ( )
( ) ( )
( ) ( )
) 20 . 4 (
0 , max 0 , max
0 , max 0 , max
0 , max 0 , max
0 , max 0 , max
+

+ + +

= +
s P s S
n N n P
w P w W
e E e P
s s n n w w e e
F C F C
F C F C
F C F C
F C F C
C F C F C F C F

For the reaction term
51

dxdy r M dxdy r M
V k k
n
s
e
w
V k k

(4.21)
The third term in equation (4.18) expresses the balance of transport by diffusion in to a
control volume. The integral can be evaluated exactly with out approximation.
( ) a
x
C C
y D
x
C C
y D
y
x
C
D y
x
C
D dxdy
x
C
D
x
W P P E
w e
n
s
e
w
22 . 4

s
S P
n
P N
s n
n
s
e
w
y
C C
x D
y
C C
x D
x
y
C
D x
y
C
D dydx
y
C
D
y

(4.22b)
Therefore adding equation (4.22a) and (4.22b)
P
s n
S
s
N
n
W E
C
y
x D
y
x D
x
y D
x
y D
C
y
x D
C
y
x D
C
x
y D
C
x
y D
+ + + + + +
(4.22c)
The four diffusive fluxes are replaced by finite difference approximation.
Substituting equation (4.17 to 4.22) in equation (4.16) and rearranging all terms gives as
shown in Appendix B: 2, one can get the following equation.
b C a C a C a C a C a C a
m
P
m m
S S
m
N N
m
W W
m
e e
m
P P
+ + + + =
1 1
(4.23)
Equation (4.23) applies to each internal node in computational nodes.
The coefficients of the discretised equations are given below

( )
( )
( ) ( ) c F
y
x D
a
b F
x
y D
a
a F
x
y D
a
n
N
N
w W
e E
24 . 4 0 , max
) 24 . 4 ( 0 , max
) 24 . 4 ( 0 , max
+ =
+ =
+ =

52
( ) ( )
( )
( ) f b
e
t
y x
a
d F
y
x D
a
m
S
S
S
24 . 4 0
24 . 4
24 . 4 0 , max
1
=
=
+ =

( )
N S E W
m
P N W E P
F F F F a a a a a + + + + =
1
(4.24g)
Where( )
n S e w
F and F F F , , represents the volumetric flow rate through the face of the
control volume. They are calculated using the definition of the stream function.
se ne
ne
se
ne
se
e
dy
y
udy F

= =

(4.25a)

sw nw W
F = (4.25b)

se nw
ne
nw
ne
nw
n
dx
x
Vdx F

= =

(4.25c)

se sw s
F = (4.25d)
Applying the Continuity equation
( ) ( ) ( ) ( ) ( ) 0 + = +
ne nw se sw se ne sw nw N S E W
F F F F (4.26)

1
+ + + + =
m
P S N W E P
a a a a a a (4.27)
The up - wind differencing scheme used to approximate the transport value at the control
volume face over sizes the convective term over the conductive term for small stream
velocities. To improve this several methods have been developed. Some of them are hybrid
differencing, QUICK and Power law scheme [10].
53
The hybrid differencing scheme of Spalding (1972) is based on a combination of central
and upwind differencing schemes [9]. The central differencing scheme which is accurate to
second order, is employed for small peclet number ( ) 2 <
e
P and the upwind scheme, which
is accurate to first order but accounts for transportiveness, is employed for large peclet
numbers
The hybrid differencing scheme uses piecewise formulae based on the local peclet number
to evaluate at the face of the control volume. The scheme is fully conservative and since the
coefficients are all positive it is unconditionally bounded. It satisfies the transportiveness
requirement by using an upwind formulation for large values of peclet number.
A better approximation to the exact solution is given by the power law scheme which is
described in Patankar (1979) [10]. Although some what more complicated than the hybrid
scheme, the Power law expressions are not particularly expensive to compute, and they
provide an extremely good representation of the exponential behavior.
The Quadratic upstream interpolation for convective kinetics (QUICK) scheme of Leonard
(1979) uses a three - point upstream-weighted Quadratic interpolation for cell, face values
[10].
Generally each scheme has its own advantage and disadvantage. The hybrid scheme
produces physically realistic solutions and is highly stable when compared with the higher
order schemes: Hybrid differencing and Power law scheme. Its disadvantage is that the
accuracy in terms of Taylor series truncation error is only first order while third order for
QUICK scheme.
54
Based on the types of the problem one can use one of the scheme mentioned above.
However, for general CFD code hybrid differencing scheme is widely used. Thus, define
the peclet number
D
uL
Pe = , therefore the face values of the peclet becomes
( )
( )
( )
) 28 . 4 (
28 . 4
b 28 .. 4
28 . 4
d
x D
y F
Pe
c
x D
y F
Pe
y D
x F
Pe
a
y D
x F
Pe
s s
s
n n
n
w
w
e
e
=
=
=
=

Pe is the peclet number, the dimensionless parameter that describes the relative strength of
convection to diffusion.
Multiplying the discretisation coefficient by the weighting factor ( ) Pe A

( ) ( ) ( )
( ) ( ) ( ) b o Fw Pe A
x
y D
a
a o Fe Pe A
x
y D
a
w W
e E
29 . 4 , max
29 . 4 , max
+ =
+ =

( ) ( ) ( )
( ) ( ) ( ) d o Fs Pe A
y
x D
a
c o Fn Pe A
y
x D
a
s
S
S
n
N
N
29 . 4 , max
29 . 4 , max
+ =
+ =

The various differencing schemes have different function of ( ) Pe A . The expression ( ) Pe A
for various differencing scheme are summarized in table (4.1) [9].

55
Table 4:1 the function ( ) Pe A for different schemes

Scheme
Formula for ( ) Pe A
Central difference
Pe 5 . 0 1

Up wind 1
Hybrid
( ) ( ) Pe Max 5 . 0 1 , 0

Power law
( ) ( )
5
1 . 0 1 , 0 Pe Max
Exponential (exact)
( )
1 exp
=
Pe
Pe
Pe A

One can get the above equations after solving the convective - conduction equation in the y
direction.
( ) 30 . 4
2
2
dx
C d
D
dx
C
u =

The best formulation is given by the power low method. It can be applied with out
modification for general transport equation in two or three dimensions. The method
switches between the two peclet number ranges 10
e
p and 10 >
e
p . For the power law
the function is given by
( ) ( ) 31 . 4
10
1
1 , 0 max
5
]
]
]
]
\
|
= Pe Pe A
ne

It is more accurate than the upwind and hybrid differencing schemes.
56
The heat transport equation is discretised as shown below with the same analogy as the
mass transport equation
( )
( ) 32 . 4
2 1
2
2
2
2
dxdy
T T
Z
U
Hr
c
y
T
x
T
a
dy dx
y
T
V
x
T
u
t
T
n
s
e
w
s
o
r R
o
n
s
e
w

|
|
|
|
|
\
|
|
|
\
|
=
|
|
\
|

The time function can be discretised
y x
t
T T
dxdy
t
T
m
P
m
P
n
s
e
w
m

(4.33)
The convective term is discretised as follows
( ) ( )
( ) ( )
( ) ( ) ( ) 34 . 4
s s n n w w e e
s s n n w w e e
n
s
e
w
n
s
e
w
T F T F T F T F
x T V T V y T u T u dxdy
y
VT
dxdy
x
uT
+ =
+

Using the up-wind differencing scheme
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( ) d F T F T T F
c F T F T T F
b F T F T T F
a F T F T T F
s P s S s s
n N n P n n
w P w W w w
e E e P e e
35 . 4 0 , max 0 , max
35 . 4 0 , max 0 , max
35 . 4 0 , max 0 , max
35 . 4 0 , max 0 , max
=
=
=
=

( ) ( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( )
( ) 36 . 4
0 , max 0 , max
0 , max 0 , max 0 , max
0 , max 0 , max 0 , max
+
+
+
= +
s P s S
n N n P w P
w W e E e P
s s n n w w e e
F T F T
F T F T F T
F T F T F T
T F T F T F T F

57
Integrating the diffusion term with in the control volume gives as show below
( )
P
S N
S
S
N
N
W E
S
S P
N
P N W P P E
s n
w e
n
s
e
w
n
s
e
w
T
y
x a
y
x a
x
y a
x
y a
T
y
x a
T
y
x a
T
x
y a
T
x
y a
y
T T
x a
y
T T
x a
x
T T
y a
x
T T
y a
x
y
T
a x
y
T
a y
x
T
a y
x
T
a dydx
y
T
a
y
dxdy
x
T
a
x
+ + + + + + =

37 . 4
The discrete contribution of the source term is obtained by assuming that the source term
has a uniform value through out the control volume.
( ) ( ) 38 . 4
2 2
1
2 1
+
= +

P
P o
o
S
P o
o
v H
p o
n
s
e
w
S
P o
o
v H
n
s
e
w p o
T
c
y x U
yT x
c
U
dxdy Hr
c
dxdy T T
c
U
dxdy Hr
c

Substituting equation (4.33 to 4. 38) in equation (4.32) and rearranging all the terms as
shown in appendix B: 3, one can get the following equation
b T a T a T a T a T a T a
m
P
m m
S S
m
N N
m
W W
m
E E
m
P P
+ + + + =
1 1
(4.39)
Where the coefficients of the discretisation equations are
( ) ( ) ( )
( ) ( ) ( ) b F Pe A
x
y a
a
a F Pe A
x
y a
a
w w W
e e E
40 . 4 0 , max
40 . 4 0 , max
+ =
+ =
( ) ( ) ( )
( ) ( ) ( ) d F Pe A
y
x a
a
c F Pe A
y
x a
a
s s
S
S
n n
N
N
40 . 4 0 , max
40 . 4 0 , max
+ =
+ =

58
( )
( )
( ) g T
Z c
y x U
b
f
Z c
y x U
a a a a a a
e
t
y x
a
S
P o
o
P o
o m
S N W E P
m
40 . 4
2
40 . 4
2
40 . 4
2
1
1

=
+ + + + + =
=

The peclet number for the heat transport equation becomes
( )
( )
( ) c
x a
y F
Pe
b
y a
x F
Pe
a
y a
x F
Pe
N n
n
w
w
e
e
41 . 4
41 . 4
41 . 4
=
=
=
( ) d
x a
y F
Pe
S s
s
41 . 4
=
4.2.6 Mass transfer equation at the interface
The control volume is separated in two smallest half at the interface as shown in figure
(4.4). In the upper phase concentration is represented by and C
p
*
the lower phase
p
C . The
concentration in the lower half is determined by the equilibrium relation as follows.

59

Figure 4. 4 Control volume for mass and heat transport equations at the interface

( )
( )
( ) c NC C
b NC C
a C N C
E E
P P
W W
42 . 4
42 . 4
42 . 4
*
*
*
=
=
=

N is the distribution coefficient of the transported component in phase equilibrium. In a
real system N depends on concentration and temperature. Both dependence of distribution
coefficient is neglected here. For initial concentration distribution N is calculated based
specific equilibrium data. And it is kept constant for the rest of the simulation.
It is important to consider the total flux J that is made up of the convection flux ( ) u and
the diffusion flux

, thus,
( )
x
u J
=

(4.43)
60
In this case the control volume is divided in to two parts. The upper part contains the
horizontal flux
* *
e e
J and J , and the lower part contains the horizontal flux of
e w
J and J
S N W W E E totl
J J J J J J J + + + + + =
* *
(4.44)
Using equation (3.48)
( ) 45 . 4 0
0
2
2
2
2
= + +
b J
t
C
rV M
y
C
x
C
D
y
v
C
y
C
V
x
u
C
x
C
u
t
C
total
k
k k
k k
k k
k
k
k k
V k k
k k
k k
k
k
k
total
r M b
y
C
x
C
D
y
v
C
y
C
v
x
u
C
x
C
u J where
=
=
2
2
2
2
:

The temporal mass change is discretised in the same fashion as the bulk phase
( )
t
C N
t
C
t
C
t
C k
k k
+
=
* *
2
1
2
1
(4.46)
y x
t
C C N
dxdy
t
C
m
P
m
P
n
s
e
w
m

1 *
2
1

+

(4.47)
The fluxes at the boundary are given as follows

(4.48a)

With the same analogy as above the other flux can formulated as follows
( )
( ) ( ) 0 , max 0 , max
2
2
2 2
* * *
* *
*
*
* *
*
* *
e E e P
P E e
e
e
e
e e e
e
e
e e e
F C F C
x
C C y D
J
x
C y D
C F J
x
C y D y
C u J
+

61
( ) ( ) ( ) 0 , max 0 , max
2
* * *
* *
e E e P
P E e
e
F C F C N
x
C C
N
y D
J +
(4.48b)
( ) ( ) 0 , max 0 , max
2
* * *
* *
*
w P w W
W P w
w
F C F C
x
C C y D
J +
(4.48c)
( ) ( ) [ ] 0 , max 0 , max
2
* * *
* *
w P w W
W P w
w
F C F C N
x
C C
N
y D
J +
(4.48d)
( ) ( ) [ ] 0 , max 0 , max
*
*
n n n P
n
P n
n n
F C F C
y
C C
x D J +
(4.48e)
( ) ( ) [ ] 0 , max 0 , max
*
*
s P s s
s
s P
s s
F NC F C
y
C NC
x D J +
(4.48f)
Substituting equation (4.47 and 4.48) in equation (4.45) and rearranging all the terms as
shown in appendix B: 4, one can get the following equation
1 * 1 * * *
+ + + + =
m
P
m
S S N N W W E E P P
C a C a C a C a C a C a (4.49)
The coefficients of the discretisation equations are
( ) ( ) ( ) ( ) ( )
( ) ( ) ( ) ( ) ) 50 . 4 ( 0 , max 0 , max
2 2
50 . 4 0 , max 0 , max
2 2
* *
*
* *
*
b F F N Pe A
x
y D
Pe NA
x
y D
a
a F F N Pe A
x
y D
Pe NA
x
y D
a
w w w w w
e e e e E
+ + + =
+ + + =

( ) ( ) ( ) c F Pe NA
y
x D
a
n n
N
N
50 . 4 0 , max
2
*
+ =

( ) ( )
( )
( )
( ) f kC b
e
t
y x N
a
d F Pe A
y
x D
a
k
m
ns s
S
S
510 . 4
50 . 4
2
1
) 50 . 4 ( 0 , max
2
1
=
+
=
+
The value of the peclet number at the control volume face is given by
62
( )
( ) b
y D
x F
Pe
a
y D
x F
Pe
e
e
e
e
51 . 4
2
51 . 4
2
*
*
=
=

( ) c
y D
x F
Pe
w
w
51 . 4
2
=
( )
( )
( ) f
x D
y F
Pe
e
x D
y F
Pe
d
y D
x F
Pe
S s
s
N n
n
w
w
51 . 4
51 . 4
51 . 4
2
*
*
=
=
=

The volume flow rates are given by:-
( ) a F
ne e
52 . 4
int
*
=
( )
( )
( ) d F
c F
b F
sw w
nw w
se e
52 . 4
52 . 4
52 . 4
int
int
*
int

=
=
=

Therefore the coefficient
P
a becomes
( ) ( )
s e w n e w
m m
S N W E P
F F F N F F F a a Na a a a a + + + + + =
* * 2 1
( 4.53)
The last term in equation (4.53) represents the volume flow rate balance of the two half
control volumes. Through the interface there is no convective exchange, so each of the
balances in the corresponding phases fulfills the continuity equation. Applying continuity
equation
( ) a F F F
n e w
54 . 4 0
* *
=
( ) b F F F
s e w
54 . 4 0 =
63
( ) 55 . 4
1
+ + + + =
m
S N W E P
a Na a a a a
At the interface the transport equation is coupled with the amount of substance generated
by the chemical reaction. Hence we should calculate the amount of substance generated at
the interface ( )
int
J . For the upper phase it is expressed as follows:-
( ) 56 . 4
*
int
* *
1
n e w
m
P
m
P
J J J J y x
t
C C
+ =

Solve for
int
J
( ) 57 . 4
* *
1
int n e w
m
P
m
P
J J J y x
t
C C
J + +

4.2.7 Heat transfer equation at the interface
With the same approach applied to mass transfer, we can formulate the discretised equation
for the heat transfer at the interface. The only difference is the presence of the source
term( )
P
Q . According to the explanation at the end of chapter (3.3.2) the reaction term at
the interface should be approximated through a mass flux dependent heat source.
( ) 58 . 4
int
hJ l Q
T P
=
h
T
is the specific amount of enthalpy releasing during the mass transfer process from the
donating to the receiving phase. It is negative for exothermic and positive for endothermic
reaction. Under the assumption that the solvent of both phases are immiscible, it is possible
to calculate the value with the mixing enthalpies of the transfer component in both phases.
The factor l shows the direction of mass transport. It has the value one for mass transport to
the upper phase and negative one to the lower phase.
64
The heat balance at the control volume face of figure (4.4) from equation (3.61) can be
discretised as follows
( ) T T
Z
U
r H
y
T
y x
T
y
T
V c
x
T
u
t
T
c
S
o
v R p o p o
+
|
|
\
|
+
]
]
]
2
2
2
(4.59)
With the same analogy as that of mass transfer, the heat fluxes for each control volume
face are given below
( )
( )
( ) ( ) [ ] ( ) a F T F T c
x
T T y
J
x
T T y
T F c J
x
T y y
T u c J
e e e P P o
P e
e
P e
e e P o e
e
e e P o e
60 . 4 0 , max 0 , max
2
2
2 2
* * * * * *
* * *
*
* * *
*
* * * *
*
*
* * * *
+

Since the system at the interface are in equilibrium, unlike the mass transfer the heat transfer has
equal interface temperature. One can use the temperature of the lower phase for this particular work.
With the same formulation as above the remaining flux are given below
( ) ( ) ( ) [ ] ( ) b F T Fe T c Pe A
x
T T y
J
e e P P o e
P e
e
60 . 4 0 , max 0 , max
2
+

( ) ( ) ( ) [ ] ( )
( ) ( ) ( ) [ ] ( ) d F T F T c Pe A
y
T T
x J
c F T F T c Pe A
y
T T
x J
s P s s P o s
S
s p
s
n n n P P o n
N
P n
n
60 . 4 0 , max 0 , max
60 . 4 0 , max 0 , max
* * * *
+

=
+

The integral value of the time function in the control volume is given by
( ) 61 . 4
2
1
* *
y x
t
T T
c c
dxdy
t
T
c
m
P
m
P
p o p o
n
s
e
w
m
p o

The heat lost to the surrounding is given by
65
( ) ( ) ( ) 62 . 4
2 2
y x T T
Z
U
dxdy T T
Z
U
S
o
n
s
e
w
u
o

Therefore equation (3.61) has the form
( ) ( ) 63 . 4
2
2
int
1
* *
y x T T
Z
U
hJ l J J J J y x
t
T T
c c
m
P S
o
T n s e w
m
P
m
P
p o p o

+ + =
+

Substituting equation (4.60to 62) in equation (4.51) and rearranging all the terms as shown
in appendix B: 5, one can get the following equation
( ) 64 . 4
1 1
b T a T a T a T a T a T a
m
P
m m
S S
m
N N
m
W W
m
E E
m
P P
+ + + + + =

Where the coefficients are given as follows
( ) ( ) [ ] ( ) ( ) ( )
( ) ( ) [ ] ( ) ( ) ( ) b F c F c Pe A Pe A
x
y
a
a F c F c Pe A Pe A
x
y
a
w p o w p o w w W
e p o e p o e e E
65 . 4 0 , max 0 , max
2
65 . 4 0 , max 0 , max
2
* * * * *
* * * * *

+ + + =
+ + + =
( ) ( ) ( )
( ) ( ) ( )
( ) f y x
t
c c
a
d Pe A
y
x
F c a
c Pe A
y
x
F c a
p o p o
m
p
s
S
s p o S
n
N
n p o N
65 . 4
2
65 . 4 0 , max
65 . 4 0 , max
* *
1
*
* * *

+
=
+ =
+ =

( )
( ) g hJ l yT x
Z
U
b
f y x
Z
U
a a a a a a
T S
o
o m
S N W E p
65 . 4
2
65 . 4
2
int
1
=
+ + + + + =

4.2.8 The vorticity equation at the interface
The horizontal grid lines are distributed over the calculation area in such away that the two
lines are forming the horizontal boundaries of the concentration - temperature control
volume at the interface. The interface itself is in between these lines. For the calculation of
66
the velocity field it is necessary to solve the vorticity transport equation at the interface to
get the two vorticity fields
*
and . Therefore an additional grid point is implemented at
the interface. The vorticity transport equation has to be discretised at the new grid point,
figure 4.5. The temperature and concentration values at the grid points are available which
allows us to calculate the x - differential of density and interfacial tension with out
interpolation.
Around the interface the vorticity transport equation is discretised for two phases for the
horizontal grid points,

Figure 4. 5 grid points at the interface
From the correlation for tension balance equation (3.34), we get the vorticity force for the
lower part of the interface.

( )
( ) b
x
a
x
W W W
WW WW WW
66 . 4
1
66 . 4
1
*
*
*
*
=
+
=

( )
( )
( ) e
x
d
x
c
x
EE EE EE
E E E
P P P
66 . 4
1
66 . 4
1
66 . 4
1
*
*
*
*
*
*
=
+
=
+
=

67
The main equation for vorticity transport at the interface as derived in chapter three is given
by equation (3.37)

x
g
Z y y x x
u
t
y o o
2 2
2
12
5
6
(4.67)
Each terms of the vorticity transport equation (4.67) are discretised with the help of
equation (4.4), (4.5), (4.6), (4.7) and (4.9).The discrete value of the lower phase
(
P EE E W WW
, , , ,
) are replaced with the above relations, equation (4.66).
( ) 68 . 4
2 2
1
2
1 12
2
1
2
1
2
1
2
1
5
6
2
1
2
1
*
* *
2
2
* 2
*
2
2 *
*
*
*
x x
g
Z
y y x x x x
u
t t
y
o o o o

Each terms of equation (4.68) is discretised one by one using finite difference and finally the
result is reassembled.
The time function is discretised as follows
t t t t
m
P
m
P
P
m
P
m
P
o
m
p o o
1 * *
*
1 *
*
2
1
2
1
2
1
2
1

(4.69a)
Substituting the discrete value of the lower phase by equation (4.66)
( ) 69 . 4
1
4
3
2
1
2
1
*
*
1 *
*
*
*
*
+ =

x t t t t t
w e m
P
o m
P
o
P o o
o
o o

For the convection term we have only the x-component.
68
( )
( ) b
x
u
x
u
x
u
a
x
u
x
u
x
u
EE E P
o P
WW W P
o P o P
EE E P
o P
WW W P
o P o P
70 . 4
2
3
10
6
2
3
10
6
10
6
70 . 4
2
4 3
10
6
2
4 3
10
6
10
6
* * *
* *
* * *
* *
*
+
+
=
]
]
]
+ +
+
=
]
]
]

Substituting for the lower part of the interface by equation (4.66), equation (4.70) becomes
as shown in appendix B: 6.
The diffusion term is discretised by finite difference
( ) a
x x
w
x x
E P W E P W
72 . 4
2
2
1 2
2
1
2
1
2
1
2
* * *
*
2 2
* 2
*
2
2
+
+
+
=

n correlatio the by parts lower the for ng Substituti . For x - component
( ) b
x x x x
x x x
x x
e ee
E
w e
P
ww w
W
72 . 4
2
1 1
2
2
1
2
1
2
1
*
2
*
2
*
2
*
*
2
*
2
* 2
*
2
2
+ +
+
=

n correlatio the by parts lower the for ng Substituti for y - component
( )
( ) b
y y x y y y y y y y y
a
y y y y y y y y y y
S
s
w e
S
P
S n
N
n
S
s
P
S
P
n
N
n
73 . 4
1
73 . 4
*
* *
*
* *
=
+ =

The source term is discretised at the grid point p.
( )
( ) 75 . 4
2 2
74 . 4
12 6
2
1
2
1 12
* * *
* *
2 2
* *
2
+
x x
g
x x
g
Z x Z Z
w e w e
y y
P
w e

69
Substituting equation (69, 71, 72, 73, 74 & 75 in equation (4.68) and rearranging all the
terms one can get
( ) 76 . 4
1 * 1 * 1 2 1 1
* * * * *
b a a a
a a a a a a a
m
p
m m
p
m m
p
m
m
S S
m
N N
m
WW WW
m
EE EE
m
W W
m
E E
m
P P
+ + +
+ + + + + + =

The coefficients of the discretised equations are
( ) a u
x x
a
P
o o
E
77 . 4 ) 0 , max(
5
6
*
*
2
*
+
+ =

( )
( ) c
y y
a
b u
x x
a
N
N
P
o o
W
77 . 4
77 . 4 ) 0 , max(
5
6
*
*
*
2
*

=
+
+ =

( )
( )
( ) f u
x
a
e u
x
a
d
y y
a
P
o o
WW
P
o o
EE
S
S
77 . 4 ) 0 , max(
10
3
77 . 4 ) 0 , max(
10
3
77 . 4
*
*
*
*
+
=
+
=
=

( ) ( ) i
Z
a a a a a a a a a
h
t
a
g
t
a
m m
WW EE S N W E P
o m
o m
77 . 4
12
) 77 . 4 (
) 77 . 4 (
2
*
1
*
1 *
*
*
1 *
1
+ + + + + + + + =
=
=

70
( )
( ) ( ) 0 , max
10
3
0 , max
10
3
77 . 4 ) 0 , max(
5
6
2
1
) 0 , max(
5
6
2
1
10
9 6 1 1
4
3
2
2 2
2 2
* *
p
www ww o
p
ee eee o
p
o ww w
p
o e ee
p
o
S
o w e w e w e
y
u
x x
u
x x
j u
x x x
u
x x x
u
x Z y y x t x x x
g
b

]
]
]
+
]
]
]
+
|
|
\
|
+ + + +
|
|
\
|
+
=

The Poisson equation (3.20) does not have to be solved at the interface, because the normal
velocity is zero at the interface. The interface can be represented by a stream line which is
given by any constant stream function values
int
and get the boundary conditions at the
interface.
4.3 Discretisation of boundary and initial conditions
Once the physical principle involved in the problem have been stated in the form of partial
differential equations, the next step is to lay down the boundary and / or initial condition
applying to the specific physical problem at hand [9]. The formulations of the boundary
conditions require a clear concept of the physical problem to be solved, in order to have
some assurance that a sensible solution exists.
4.3.1 Horizontal boundary
For the stream function and the transport properties
T and C ,
, we have to formulate
the condition at the boundaries. Like the phase boundary it is also possible to describe the
horizontal boundaries because the normal velocity component is zero. At the point of the
boarder the value of the stream function is constant.
= = =
int
*

HR HR
Constant (4.78)
The vorticity force is not as such easy to fix at the boundaries. If we use the Poisson
equation, it can happen stability problem and the result it self unreliable. But for free spaces
71
or surface far from the interface of the stream, we can assume that it is free of rotation or
spinning. In case of capillary flow, the horizontal boundaries are given by
HR HR
=
*
(4.79)
For mass transfer, there is no mass flux at the horizontal boundaries.
0 =

HR HR
y
C
y
C
(4.80a)
Besides the normal velocity component is zero, so that there is no convective transport
through the boundaries. To release this condition in the discretisation equations, we set the
coefficients of the boundary nodes to zero. For example, the coefficient (
N
a
) of the
upper boundary is zero. The other coefficients are the same as the bulk phase.
For heat transfer, the heat flux through the wall at the horizontal boundaries can be
neglected and taken as adiabatic boundaries as follows.
0 =

HR HR
y
T
y
T
(4.80b)
4.3.2 Interface Boundaries
At the interface we already have the transport equation except the stream function. Under
the condition that 0 = V , the values of the stream function along the interface is to be
constant. Hence the Poisson equation at the interface does not have to be solved.

4.3.3 Vertical boundaries
At the vertical boundaries symmetrical boundary conditions are assumed. Symmetrical
boundary conditions are very easy to formulate. A grid point at the left boundaries shall
72
have 0 = i and right boundary M i = . The distance to each of these boundaries shall be x
2
1
.
For the vorticity property this symmetrical pattern can be described
( )
( )
( )
( ) d
c
b
a
j j M
j j M
j M j
j M j
81 . 4
81 . 4
81 . 4
81 . 4
, 1 , 2
, 0 , 1
, 1 , 2
, , 1

=
=
=
=
+
+

and for the stream function as follows
( )
( ) b
a
j j M
j m j
82 . 4
82 . 4
, 0 , 1
, , 1

=
=
+

The boundary points ( ) ( ) j M i , & , 0 can be treated like any other point in the middle of the
calculation field because the neighbor points have the necessary w and values.
The half control volume for concentration and temperature distribution at the boundary of
the calculation field is united to the complete control volume.

( )
( ) b T T
a C C
j j M
j j M
83 . 4
83 . 4
, 0 , 1
, 0 , 1
=
=
+
+

( )
( ) b T T
a C C
j M j
j M j
84 . 4
84 . 4
, , 1
, , 1
=
=

The discretisation of the concentration and temperature equations has to be solved for the
control volume in the range of M i <= <= 0 .

73
4.3.4 Initial conditions
For the start of the simulation initial conditions are required which already fulfill the
differential equation. Initially it is assumed that both phases are at rest. Thus initial
distributions of the stream function and vorticity are given by
( ) ( )
( ) 86 . 4 0 ) 0 , , (
85 . 4 tan 0 , ,
=
=
y x
t cons y x

The initial distribution of the concentration and temperature are the result of a one
dimensional diffusion equation. The mass transport equation for one dimension is given by

2
2
y
C
D
t
C
(4.87)
The following boundary conditions are considered.
1. At 0 = t in both phases , one can have the bulk concentration
*

C and C ( ) 0 y
2. At the interface 0 = y , for all 0 t the continuity of mass transfer is granted. i.e.

y
C
D
y
C
D

*
(4.88)
3. The transport resistance of the interface is neglected. At the interface the phases are
in equilibrium( )
*
int int
NC C = .Applying the above conditions in equation (4.87) one
can obtain the following solutions.
0 y for
( ) a
Dt
y
Dt
NC C
Dt
y
Dt
C C
y
C
89 . 4
4
exp
4
exp
2
int
2
int

74
0 y for
( ) b
t D
y
t D
NC C
D
D
t D
y
Dt
C C
y
C
89 . 4
4
exp
4
exp
2
int
*
2 *
int

Integrating equation (4.89) for the lower phase gives
( ) ( )
Dt
y
erf NC C NC t y C
2
,
*
int
*
int
=

(4.90a)

and for the upper phase
( ) ( )
t D
y
erf NC C
D
D
C t y C
*
*
int
*
int
2
,
(4.90b)
The error function is defined as:-
dt e
x erf x erfc
x
t

=
=
0
2 2
1
1
(4.91)
Away from the interface the initial distribution of both phases is taken to be the bulk
concentration of the diffusing component. Applying the above condition and equation
(4.90) one can obtain a correlation for the interface concentration
*
int
C of the diffusing
component.
( ) ( ) 92 . 4
*
int int
NC C
D
D
C C

After rearranging it will be
( ) 93 . 4
1
*
int
N
D
D
C
D
D
C
C

75
Equation (4.93) is implicit in
int
C because the distribution coefficient itself depends on

int
C .
The interface concentration has determined through iteration of equation (4.93) using an
equation for ( ) C f N = .
To obtain the initial temperature distribution, the heat conduction equation in the capillary
space should be solved
( ) ( ) a T T A
y
T
a
t
T
94 . 4
0
2
2

( ) b
Z c
U
A
p
o
94 . 4
2
0
=
In deriving equation (4.94) the convective, reaction and the second derivative of differential
equation in x direction are neglected and the surrounding and the initial temperature of
the system are the same.
) 95 . 4 ( 0 , 0 , = = y t T T
o

To obtain the initial temperature distribution from equation (4.94), let us find the solution
for the following equation.
( ) 96 . 4
2
2
y
T
a
t
T

This equation describes the one dimensional heat conduction equation in y direction.
Using equation (4.89a) gives for the mass flow rate expressed in concentration of the lower
phase.
( ) ( ) 97 . 4
int 0 int
C C
t
D
t
C
D m
y
=
=
=

According to the explanation in section (4.2.7), the heat flux can be related as follows
76

( )
( ) ( ) b C C
D
h l B
Where
a
t
B
m h l q
T
T
98 . 4
98 . 4
int
int int
=
= =

The heat generated at the interface ( )
int
q is distributed in to two streams
*
int
q and
int
q for
the upper and lower phases. The heat flow rate of the lower phase is given by
( ) a
t
B
f q 99 . 4 =
and the upper phase
( ) ( ) b
t
B
f q 99 . 4 1
*
= D
The weighting factor (f) ranges between zero and one. The boundary condition at the
interface is therefore

( )
( ) ( ) b y
y
T
t
B
f
a y
y
T
t
B
f
100 . 4 0 , 1
100 . 4 0 ,
*
*
+ =
=
=

at the bulk phase
= = y T T
o
, (4.100c)
Under consideration of these boundary conditions one can obtain the result of equation
(4.96) with the help of Laplace transformation for the two phases as follows
( ) ( ) a y T
at
y
erfc
a B
f t y T
o
101 . 4 0 ,
2
, + =

( ) ( ) ( ) b y T
t a
y
erfc
a B
f t y T
o
101 . 4 0 ,
2
1 ,
*
*
*
*
+ =

77
Through multiplication of the first term on the right side by
At
e
, equation (4.101) is
modified in such way that the heat loss to the surrounding through the wall is considered.
Assuming that the coefficient which describes the intensity of the heat flow through the
wall be constant, one can obtain

( ) ( ) ( )
( ) ( ) ( ) ( ) b y T
t a
y
erfc At
a B
f t y T
and
a y T
at
y
erfc At
a B
f t y T
o
o
102 . 4 0 ,
2
1 ,
102 . 4 0 ,
2
exp ,
*
*
*
*
+ =
+ =

The average value for A is
( )Z c c
U
A
p o p o
o
* *
4
+
= (4.103)
Equation (4.102a) and (4.102b) are the required result for the initial equation (4.94a).The
temperature profile in both phases is correlated through the condition
*
T T = which allows
calculating the weight factor f. With y = 0, equate equation (4.102a) with equation
(4.102b), the result will be

1
1
*
*
+
=
a
a
f
(4.104)
If one uses a certain time
o
t in equation (4.90) and (4.102) for the start of the simulation,
then initial distribution of concentration and temperature can be obtained. Depending on
o
t different concentration gradients at the interface are resulting.

78
4.3.5 Algorithm
The Algorithm for the solution of transient problems combined mass, heat and momentum
transport equations has described below.
4.3.6 Solution of the discretised equation
In the previous section the governing equations of fluid flow, mass and heat transfer have
been discretised using finite volume and finite difference methods. These result in system
of linear algebraic equations which needs to be solved. The complexity and size of the set
of equations depends on the dimensionality of the problem, the number of grid points and
the discretisation practice [9]. There are two families of solution techniques for linear
algebraic equations: direct method and indirect or iterative methods. The equation system
for the calculation of the distribution ( ) y x
m
, based on the discretisation coefficients is
solved numerically through the inner iteration process.

79

Time iteration

Outer iteration

No

No

Yes

No Yes

Figure 4. 6 Algorithms for the simulation of mass and heat transport discretisation
equations using implicit scheme.
Start
Properties, geometry and discretising Data
0 := t
Mesh generation, Guess the initial
values of T C , ,
t t t + = :
{ } T C, ,

m m
=
:
1

Estimated value for &
m
distribution
Calculate the coefficient of mass transfer according to Eqn. (4.29), (4.24e), (4.27), (4.50)
Inner Iteration: ) 49 . 4 ( ), 23 . 4 ( . ), , ( Eqn y x C
m
and ) 57 . 4 ( . Eqn J
in

Calculate the coefficient of heat transfer according to Eqn. (4.40), (4.65)
Inner Iteration: ) 64 . 4 ( ), 39 . 4 ( . ), , ( Eqn y x T
m

) , ( ), , ( y x y x
Calculate the coefficient vorticity transport equation according to Eqn. (4.11), (4.77)
Inner Iteration: ) 76 . 4 ( ), 10 . 4 ( . ), , ( Eqn y x
m

Inner Iteration: ) 13 . 4 ( ) , ( Eqn y x , Coefficients Eqn (4.14)
Convergence
{ } , ,
m m m
T C
Print out the out put: ) , ( y x T
m

) , ( ), , ( ), , ( y x C y x y x
m m m

?
end
t t = = End
80

Iterative methods are based on the repeated application of a relative simple algorithm
leading to eventual convergence after some- time a large number of repetitions. The main
advantage of iterative solution methods are that only non zero coefficients of the equation
need to be stored in core memory.
Jacobean and Gauss - seidel iterative methods are easy to implement in simple computer
programs, but they can be slow to converge when the system of equations are large. Hence
they are not suitable for general CFD procedures. Thomas (1949) developed a technique for
rapid solving tri - diagonal systems that is now called the Thomas Algorithm or the Tri -
diagonal Matrix Algorithm (TDMA) [10]. The tri-diagonal matrix algorithm is actually a
direct method for one dimensional equation, but it can be applied iteratively, in a line-by-
line fashion, to solve multi-dimensional problems and is widely used in CFD program.
Generally the discretisation equations are rearranged so that the equation system along the
horizontal and vertical grid lines have the following form. For instance for the calculation
of the vorticity transport equation
m
j i,
, where ( ) M i , ,......... 2 , 1 , 0 = is shown blow.

The general vorticity transport equation in the discretised form is rearranged along the
horizontal grid line.
d C Bw A D E
b a a a
a a a a a a a a
m
EE
m
E
m
P
m
W
m
WW
m
P
m m
P
m m
SS SS
m
NN NN
m
S S
m
N N
m
EE EE
m
E E
m
P P
m
W W
m
WW WW
= +
+ + +
+ + + = +

) 105 . 4 (
2 1 1

81

j M
j M
j M
j M
j i
j
j
j
j
m
j M
m
j M
m
j M
m
j M
m
j i
m
j
m
j
m
j
m
j
M M M
M M M M
M M M M M
M M M M M
i i i i i
O O O
d
d
d
d
d
d
d
d
d
A D E
B A D E
C B A D E
C B A D E
C B A D E
C B A D E
C B A D E
C B A D
C B A
,
, 1
, 2
, 3
,
, 3
, 2
, 1
, 0
,
, 1
, 2
, 3
,
, 3
, 2
, 1
, 0
1 1 1 1
2 2 2 2 2
3 3 3 3 3
3 3 3 3 3
2 2 2 2 2
1 1 1 1
.
.
.
.
.
.
.
.
.
.
.
.
0 ...... .......... .......... .......... 0
0 .......... .......... .......... 0
0 .... .......... .......... 0
0 0 0
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
. ... 0 0 ........ 0
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
0 ......... .......... ..... .......... .......... 0 0
0 .......... .......... ........ .......... .......... 0
0 . ........ .......... .... .......... .......... .......... 0
0 ....... .......... ........ .......... .......... .......... 0
(4.106)
The element of the coefficient matrix is given below
( )
( )
( )
( )
( ) e a E
d a D
c a C
b a B
a a A
j i WW i
j i W i
j i EE i
j i E i
j i p i
107 . 4
107 . 4
107 . 4
107 . 4
107 . 4
, ,
, ,
, ,
, ,
, ,
=
=
=
=
=

And the element of the resultant vector

( ) f
a a
a a a a b
d
m
j i
j i m m
j i
j i m
m
j i j i SS
m
j i j i S
m
j i j i NN
m
j i j i N i
i
107 . 4
2
,
, , 2 1
,
, , 1
2 , , , 1 , , , 2 , , , 1 , . ,
+ +
+ + +
=

+ +

The elements ( ) M M i , 1 , 1 , 0 = of the resultant vector contains the boundary conditions
) 113 . 4 ( :
, 2 , 0 , , 1 , 0 ,
g a a d d
m
j j WW
m
j j W o o
+ + =

82
( )
( )
) 107 . 4 ( :
107 . 4 :
107 . 4 :
1 , , , 1 , ,
, 1 , 1 , 1 1
, 2 , 1 , 1 1
j a a d d
i a d d
h a d d
m
M j M EE
m
j M j M E M M
m
j M j M EE M M
m
j j WW
+ +
+
+ + =
+ =
+ =

The coefficient matrix of the vorticity equation has penta - diagonal shape because of the
number of neighbor points considered per coordination directions. At the discretisation
point of the Poisson, mass and heat equations the immediate neighbors have been involved.
Therefore tri-diagonal matrixes are resulted. The discretised equation of the Poisson, mass
and heat equations have the following forms
d B A C
b a a a a a a a
m
N
m
P
m
S
m
P
m m
E E
m
P P
m
W W
m
N N
m
P
m m
S S
= + +
+ + + + = +

) 108 . 4 (
2 1 1

The matrix is shown below for general function

m m
m m m
m m m
i i
O O
A C
B A C
B A C
B A C
B A C
B A C
B A
i
0 . . . . . . . 0
0 0
0 0 0
. . . . . . 0
. . . . . . .
0 0 0 . . 0
. . . . . . .
. . . . . . .
0 . . . . . 0 0
0 . . . . . . 0
0 . . . . . . . 0
1 1 1
2 2 2
2 2 2
1 1 1

m
m j
m
m j
m
m j
m
i j
m
j
m
j
m
j
,
1 ,
2 ,
,
2 ,
1 ,
0 ,
.
.
.
.
m
m j
m
m j
m
m j
m
i j
m
j
m
j
m
j
d
d
d
d
d
d
d
,
1 ,
2 ,
,
2 ,
1 ,
0 ,
.
.
.
.
(4.109)

83

The coefficients are
( )
( )
( ) ) 110 . 4
110 . 4
110 . 4
,
,
,
c a C
b a B
a a A
i j S
i j N
i j p
=
=
=

The resultant vector is given by
b a a a d
m
P
m m
W W
m
E E
+ + + =
1 1

(4.111)
To solve the penta-diagonal coefficient matrix in an effective way it is possible to use
Guess elimination.
In practice, the iterative process is terminated when some arbitrary convergence criterion is
satisfied [9]. An appropriate convergence criterion depends on the nature of the problem
and on the objective of the computation, A common procedure is to examine the most
significant quantities given by the solution (such as the maximum velocity, total shear
force, a certain pressure drop or overall heat flux) and to require that the iterations be
continued only until the relative change in these quantities between two successive
iterations is greater than a certain small number often the relative change in the grid-point
values of all the dependent variables is used to formulate the convergence criterion . This
type of criterion can sometimes be misleading when heavy under relaxation is used the
change in the dependent variables between successive iterations is intentionally slowed
down; this may create an illusion of convergence although the computed solution may be
far from being converged. A more meaningful method of equations is satisfied by the
current values of the dependent variables.

84

For each grid point, a residual R can be calculated from
nb nb nb nb
a b a R
+ = (4.112)
Obviously, when the discretisation equation is satisfied, R will be zero. A suitable
convergence criterion is to require that largest value of /R/ be less than a certain small
number.

85

5. Results and discussion
The mathematical models developed in the previous chapter have been solved using
MATLAB programming computer code. The code has been written for both one and two
dimensional diffusion equation, and two dimensional diffusion convection equations. The
results have been discussed in the following section. The model has been validated using
analytical solutions of one dimensional diffusion equations and other results from literature
[13].
The stream function vorticity method has some attractive features. The pressure term is
eliminated from the momentum equation by cross differentiation, and instead of dealing
with the continuity equation, and two momentum equation, we need to solve only two
equations to obtain the stream function and the vorticity. Although it has attractive
features, it has also short comings. The vorticity and vorticity potential vectors involve
concepts that are hard to visualize and interpret than the meaning of the velocity component
and pressure. For this reason the vorticity potential has used here only to calculate the
coefficient of the convective term in the discretisation equations.
The solutions of the discretised equations can be obtained for increasing time. Starting with
the given initial concentration and temperature distributions, the values of the concentration
and temperature distribution are obtained at the next time step. The results thus, obtained
are then used to evaluate the concentration and temperature at the end of the second time
step. Thus, the solution proceeds for increasing time until results are obtained over a
specified time or until a particular concentration and temperature level or the steady state is
attained [14].
86

The parameters used in this study have been taken from literature. Some of them are
experimental data [15] and some of them have been calculated using empirical correlations
[16]. For detail information see appendix A.
Table 5. 1 Parameter used for the simulation

Component Density
(m
3
kg
-1
)
Diffusivity
(m
2
s
-1
)
Thermal
conductivity
(w/m.k)
Heat
capacity
(J/kg.k)
Viscosity
(Ns/m
2
)
Water solution 1041
9
10 88 . 0

0.609 4186
3
10 9 . 0

Cyclohexane 779
9
10 17 . 1

0.135 1263
3
10 7 . 1

In addition to the parameters given in table (5.1) the following parameters are also used.
The value of distribution coefficient (N) has taken the value 168. The heat of reaction of the
system has the value
1
1067

= kg kJ H [13].
As it has been discussed in section (4.1.2), the solution of numerical methods depends on
the size of the mesh. Hence the optimal grid point used for the simulation of concentration
and temperature distributions in this thesis are 51 by 51 grid points. The discussions of the
results are based on those values of the grid points.

87

5.1 Simulation of Concentration Profile
5.1.1 Mass transfer with out chemical reaction
The simulation result for mass transfer with out chemical reaction is described below both
for one and two dimensional diffusion, and two dimension diffusion convection equations.
The results have been presented in the subsequent sections in the form of graphs both for
analytical and numerical solutions.
The concentration profile of acetic acid for both organic and water phases as a function of
position from the interface are plotted for different times as shown in figure 5.2. Initially it
has been assumed that there is no acetic acid in the water phase. Due to molecular motion
of the diffusing component however, acetic acid transfers from the interface to the water
phase. The concentration of the diffusing component (Acetic acid) decreases from its initial
concentration ( )
o
C in the bulk phase of cyclohexane to the interface and starts to develop
its concentration distribution in the water phase.
The analytical and numerical solutions for one dimensional diffusion equations are
presented in figure 5.1 and figure 5.2 respectively.

88

-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
0
10
20
30
40
50
60
y, cm
C
,

g
/
l
t1 = 5 s
t2 = 30 s
t3 = 55 s
t4 = 80 s
t5 = 105 s

function of distance from the interface, in the water phase negative, in the Cyclohexane
phase positive, Analytical Solution

To validate the result of the numerical method used, analytical method has been used for
one dimensional diffusion equations. The analytical equation has been solved using Laplace
transformation of one dimensional diffusion equation. It has been solved by implementing
two point boundary conditions and one initial condition [6]. As it has been presented in
figure 5.1 the highest concentration gradient occurs near the interface of the two phases.
Away from the interface the concentration distribution attains its bulk concentration.
89
The result obtained from the numerical discretisation is presented in figure 5.2. The
numerical solutions are compared with the analytical solutions to check the validity of the
numerical method used.
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
0
10
20
30
40
50
60
y, cm
C
,

g
/
l
t1 = 5 s
t2 = 30 s
t3 = 55 s
t4 = 80 s
t5 = 105 s

a function of distance from the interface, in the water phase negative, in the Cyclohexane
phase positive, Numerical solutions.

As it has been shown in figure 5.2 the result obtained from the numerical discretisation
equations is in good agreement with the analytical solution of one dimensional diffusion
equation. The comparison is presented in section 5.2.

90
Similarly, concentration distribution for two dimensional diffusion equations has been
developed and solved using numerical discretisation methods. The solutions of two
dimensional equations are validated using data from literature [13].

In the discretisation of two dimensional diffusion equations, the value of the required
parameter (temperature or concentration) takes the third dimension. In this sense, the
concentration and temperature distribution of the discretised equations are interpreted in
three dimensional cartitian coordinate system. The result of two dimensional plots for
concentration distribution is shown in figure 5.3. As it has been presented in figure 5.3, the
variation of concentration along the horizontal direction as compared to along the vertical
direction is very small. Since the major variation of concentration is along the vertical
direction emphasis has been given to the variation along the vertical direction for our
discussion. However, the variation of concentration along the horizontal direction is small;
its variation hasnt been ignored. Instead, the average value of the concentration along the
vertical direction has been considered through out our discussion.

91
0
0.5
1
-1
-0.5
0
0
10
20
30
40
50
x,cm
y, cm
C
,

g
/
l
0
0.5
1
0
0.5
1
0
10
20
30
40
x, cm
y, cm
C
,

g
/
l

a). Organic phase b). Water phase
Figure 5. 3 Two dimensional Concentration profile of the diffusing component.

Taking this in to consideration the concentration variation along the horizontal direction is
small and in order to visualize the system, the coordinate system has been changed in to
one dimensional coordinate system by taking the average value of concentration along the
vertical direction.
Thus, through out this thesis the discussion is based on the average value of the
concentration along the vertical direction.
92
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
0
5
10
15
20
25
30
35
40
45
50
y, cm
C
,

g
/
l
t1 =10 s
t2 = 35 s
t3 = 65 s
t4 = 85 s
t5 = 110 s

distance from the interface, in the water phase negative, in the Cyclohexane phase positive,
average value along the horizontal direction for two dimension.

When the numerical solutions of one dimensional diffusion equation is compared with two
dimensional diffusion equations, there is some significant difference in the result of two
dimensional discretisation equation from the analytical solution of one dimensional
diffusion equation. The concentration profile for one dimensional discretisation equations
are relatively in good agreement with the analytical solution than two dimensional
discretisation equations. In two dimensional diffusion equations, there is some significant
effect of the lateral diffusion of the diffusing component on the concentration distribution.
Due to this, the concentration distribution becomes flat in two dimensional discretisation
equations. The effect is more pronounced in the organic phase. This may be due to the
solubility difference of acetic acid in cyclohexane and water phases.
93

For pure diffusion processes, the diffusing component is dominantly transferred
perpendicular to the interface. The lateral diffusion (diffusion in the second direction) can
be neglected compare to diffusions perpendicular to the interface. This is conformed from
the result obtained for both one and two dimensional discretisation equations. I.e. for
physical mass transfer both dimension have similar concentration distribution of the
diffusing component. Of course it has been taken for two dimensional discretisation
equations, the average value of the concentration along the horizontal direction.

5.1.2 Mass transfer with chemical reaction
As it has been discussed in section (3.3.2), the reaction has been taken place at the interface
of the two fluids. Due to this the reaction term is not considered in the bulk phases of the
two liquids. Instead it has been considered only at the interface of the two liquids and used
as a source term in the discretisation of mass and heat transport equations.
Reactions that have Hatta number greater than two (Ha > 2) are considered to be fast
reactions. For the reaction considered in this study, the value of the Hatta number is 10.
Hence the reaction can be considered as fast reaction. Since the reaction that has been
considered is fast reaction and it has been taken place at the interface of the two liquids, the
diffusing component is consumed immediately as it reaches the interface. Hence, the
possibility of the diffusing component to penetrate the second phase compared to mass
transfer with out chemical reaction is very small. As a result its distribution in the second
phase is very small. The result of the distribution is shown in figure 5.5. Compared with the
distribution of mass transfer with out chemical reaction, it can be concluded that
94
concentration distribution of the diffusing component grows at slower rate to transfer to the
second phase. However, its possibility to penetrate the second phase is small, once it passes
the interface its transfer mechanism is not affected by chemical reaction. Because the
reaction has been taken place only at the interface. The transfer mechanism is simply
physical mass transfer. This is clearly shown in figure 5.5.

-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
0
5
10
15
20
25
30
35
y, cm
C
,
g
/
l
t1 = 5 s
t2 = 30 s
t3 = 55 s
t4 = 80 s
t5 = 105 s


The simulation result obtained for diffusion - convection discretisation equations are some
what different from the result obtained for diffusion equations. This is due to the
incorporation of the convective terms in the discretisation equations. As it has been shown
95
in figure 5.6, the profile is not as smooth as the profile obtained from the discretisation of
two dimensional diffusion equations. The contribution of the convective term in the
transport process is small as compared to the contribution of diffusion term. For both
phases the highest concentration gradient occurs at the interface of the two fluids. This is in
good agreement with the explanation of the two - Film theory.

-1 -0.5 0 0.5 1
0
5
10
15
20
25
30
35
t1 = 5 s
t2 = 30 s
t3 = 55 s
t4 = 80 s
t5 = 105 s

Figure 5.6 Concentration profiles during mass transfer at the interface as a function of

As it has been shown in the above figures 5.1, 5.2, 5.4, 5.5, and 5.6 for both dimensions and
for all cases there is a common characteristic on the distribution of the diffusing
component. The concentration distribution of the diffusing component decreases from the
bulk phase to the interface for organic phase. But it increases from the bulk phase to the
interface for water phase. With respect to time, the distribution of the diffusing component
decreases from its initial concentration C
o
to the specified or required concentration in the
96
organic (Cyclohexane) phase and its distribution increases with time in receiving (water)
phase. Since the source of the diffusing component is cyclohexane, the concentration of the
diffusing component decreases with time as it transfers to the second (water) phase.

5.2 Simulation of temperature Profile
Similarly, the temperature distribution of the system has been discussed for both one and
two dimensional discretisation equations. The temperature distribution is obtained due to
the heat generated at the interface of the two liquids by the chemical reaction. The heat
generated has been transported to the two bulk phases by diffusion as well as convection
mode of heat transfer.

The simulation result of one dimensional diffusion / conduction/ equation shows that the
temperature gradient is higher at the interface. This temperature gradient decreases as one
goes towards the bulk Phases of the two liquids. This clearly shows that the heat source
occurs only at the interface of the two liquids.

The temperature distribution is calculated for different times. The temperature profile
increases with increasing time. This will proceed until the required temperature distribution
is obtained or the specified time is attained. This is because the heat generated by the
reaction is greater than the heat lost to the surrounding. The result of one dimensional
temperature distribution is presented in figure 5.7.

97
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8 1
20
20.5
21
21.5
22
22.5
23
y, cm
T
,

0
C
t1 = 5 s
t2 = 30 s
t3 = 55 s
t4 = 80 s
t5 = 105 s

Figure 5. 7 One dimensional temperatures profile at the interface as function of distance
from the interface, in the water phase negative, in the Cyclohexane phase positive ,for U
o
=
5 w m
-1
k
-1

As it has been shown in figure 5.7 the temperature distribution decreases from the interface
to the two bulk phases. For this particular model the temperature distribution of the phases
are nearly symmetrical to the interface, because the thermal diffusivity coefficients of the
two fluids are nearly equal. But thoroughly observing the distribution there is still a slight
difference on the growth rate of the temperature distribution on two phases. The
symmetricity disappeared as the thermal diffusivity coefficients differences of the two
liquids become higher and higher.
The temperature distribution of two dimensional discretisation equation is presented in
figure 5.8. From the temperature distribution one can infer that the temperature variation is
98
not the same for the two coordinate systems. I.e. the temperature variation along the
vertical direction is higher than the temperature variation along the horizontal direction.
0
0.2
0.4
0.6
0.8
1
-1
-0.5
0
0.5
1
19
20
21
22
23
24
25
x, cm
y, cm
T
,

o
C
t1 = 75 s

Figure 5. 8 Two dimensional temperature distribution of the system, for U
o
= 5 w m
-1
k
-1

Considering that the temperature variation along the horizontal direction is small and in
order to visualize the system, the coordinate system has been changed in to one coordinate
system. Accordingly, the temperature variation along the horizontal direction has been
averaged for each raw along the vertical direction. Thus, through out this thesis the
discussion has been based on the average value of the temperature along the vertical
direction.
After averaging the values of the temperature distribution along the horizontal direction, for
two dimensional discretisation equations, similar result has been obtained for the
temperature distribution as that of one dimensional discretisation equation.
99
20.0
20.5
21.0
21.5
22.0
22.5
23.0
-1.00 -0.80 -0.60 -0.40 -0.20 0.00 0.20 0.40 0.60 0.80 1.00
y , cm
T
,

o
C
t4 = 100 s
t3 = 55 s
t2 = 30 s
t1 = 5 s

Figure 5. 9 Temperatures profile at the interface as function of distance from the interface,
in the water phase negative, in the Cyclohexane phase positive for k m w U
o
/ 5 = , Average
value of temperature along the horizontal direction for two dimensions.

As it has been shown in figure 5.9, the temperature distribution of two dimensional
discretised equations have similar trend as that of one dimensional discretised equation.
However, they have the same trend the gradient of the curves are different. The distribution
for one dimension is sharper than that of two dimensionional discretisation equations. On
the other hand, the temperature distribution of two dimensional discretisation equations is a
little bit flat compared to one dimensional discretisation equation. There are two
possibilities for the above explanation. The first one may be due to the information
(disturbance) transfer from one corner to the other corner in two dimensional discretisation
is very slow. The second one may be due to the convection heat transport of the fluid
particle. In this case, the heat that has been generated at the interface of the two liquids is
100
conveyed to the bulk phases by the convection motion of the fluid particles and in some
extent by molecular motion of the fluid particles. i.e. convective mode of heat transport is
very fast than conductive transport. Consequently the heat has been distributed to the two
bulk phases immediately it generates at the interface. Due to this the temperature
distribution in two dimensional discretisation equation becomes flat.
The maximum temperature occurs at interface of the two liquids for both one and two
dimensional discretised equations. This is because the heat that has been generated due to
chemical reaction occurs only at the interface of the two liquids. From the temperature
profile one can infer that the temperature decreases from the interface to the two bulk
phases at different rates. This is due to different in heat conductivity of the two liquids.

5.3 Validation of the simulation result
Up to now it has been discussed about the results that have been obtained from the
numerical discretisation of this work. But, whether the results are valid or not the results
should be checked with other similar works. Based on this, the results that have been
obtained in this study are compared with other results obtained from literature [13].
Moreover the numerical solutions for one dimensional diffusion equations are compared
with analytical solutions. Validation of one dimensional model is shown in figure 5.10 and
two dimensional models are shown in figure 5.11.
The comparison result of one dimension is presented in figure 5.8. It can be seen that the
numerical solution is in good agreement with the analytical solution. In validating the result
the error analysis technique has been employed. The average error calculated is two percent
(2%).
101
0
5
10
15
20
25
30
35
40
45
50
55
60
-1 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
y, cm
C
,

g
/
l
Analytical solution phase1
Numerical solution phase1
Analytical solution phase2
Numerical solution phase2
t = 105 s

Figure 5. 10 Concentration profile as a function of distance from the interface, Comparison
of numerical solution with analytical solution

The comparison of the temperature distributions is shown in figure 5.11. Some discrete
data has been taken from the literature [13]. The data that has been taken from the literature
are plotted together with the result obtained for this study on the same chart. Comparisons
of the two results show that there is some significant difference between the two results.
The deviation has been calculated using error analysis technique. The average absolute
error obtained is around two percent (1.887%).

102
20
20.5
21
21.5
22
22.5
23
-1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y ,c m
T
,

o
C
Literature result
Numerical solution
t = 75 s

Figure 5. 11 Temperature distributions as function of distance from the interface,
Comparison of numerical solution with other literature [13]

From the error obtained both for concentration distribution and temperature distribution it
has been concluded that the models that have been developed in thesis simulates the
concentration and temperature distribution satisfactorily.

103

6. Conclusion and Recommendation
6.1 Conclusion
In this study a numerical simulation code has been developed that can be used to analyze
the concentration and temperature distribution of a diffusing component at the interface of
two immiscible liquids. Two dimensional capillary space was considered to develop the
mathematical models for mass, heat and momentum equations. The mathematical model
has been developed for both the bulk phases of the two liquids and at their interface. The
analysis has made using numerical discretised techniques; the Finite Volume Method
(FVM) and Finite difference method. The discretised equations are converted in to
computer code using MATLAB software. The code has been developed for both one and
two dimensional diffusion equations as well as for two dimensional convection diffusion
equations.
Based on the result obtained, the following specific conclusions can be concluded
1. The concentration profile of the diffusing component (Acetic acid) obtained from
the numerical solution is in good agreement with the analytical solution of one
dimensional diffusion equation.
2. The concentration of acetic acid decreases in the cyclohexane and increases in the
water phase with time as it is expected from mass transfer theory.
3. The concentration profile of acetic acid shows similar result for both dimensions of
conduction equations. This leads to the conclusion that the diffusing component is
dominantly transferred in the direction perpendicular to the interface.
104
4. Since the heat has been generated at the interface, the maximum temperature occurs
at the interface of the two fluids.
5. The temperature gradient of one dimensional discretisation equation is sharper than
two dimensional discretisation equations.

As a general conclusion the selected numerical discretisation technique (finite volume
method) give a good result for both concentration and temperature distributions. This
method is widely used in CFD code development, because it considers the conservation of
species in the discretisation processes. As a main conclusion interface mass transfer with
chemical reaction can be simulated with the numerical solution method presented in this
study. By comparing the model result with data obtained from other similar work, it has
been concluded that the model developed for both one and two dimensional diffusion
equations, and two dimensional diffusion convection equations simulate the concentration
and temperature distribution satisfactorily. Moreover from the comparison of the numerical
results with analytical solutions and literature result, it can be conclude that the error is in
the reasonable range.

6.2 Recommendation
As it has been discussed in chapter three, it has been considered that the reaction occurs at
the interface of the two immiscible liquids. Based on this the reaction term is considered as
a source term in the discretisation of mass and heat transport equations. Considering all the
above explanations the following points are recommended as a future work.

105
1. One can include the reaction term in the bulk phases in the discretisation of mass
and heat transport equation.
2. The model can be extended for different reaction schemes with known reaction
kinetics.
3. Experiment is required to determine the accuracy of the model developed provided
that the experimental set up is available.
4. As it has been described in section 3.3.2, the interface is assumed to be flat and
stagnant. Therefore one can extend the model for movable interface and different
shapes of the interface. For example curved interface.
5. The model developed in this study was based on the natural convection generated
by buoyancy force. Therefore one can extend the model for flow generated by
forced convection.
6. The model can be extended to three dimensional discretisation equations

106

Symbols
A Arial,
2
m
C Concentration, g l
-1

D Diffusion coefficient, m
2
s
-1

F Volumetric flow rate, m
-2

s
-1
, Constant factor for mesh size
H Height, m
R
H Molar reaction enthalpy, J/mol
J Mass flux
K Over all mass transfer coefficients, m s
-1

M Molecular mass,
1
mol g
N Distribution coefficient, Molar flux, mol m
-2
s
-1
Pe Peclet number
T Temperature k,
O
C
T
b
Boiling temperature k,
O
C
T
s
Surrounding temperature k,
O
C
U Perimeter, m
V Volume, m
3
U
o
Over all heat transfer coefficient, w m
-2
s
-1
Z Length, m
a Temperature coefficient, m
2
s
-1
Coefficient of discretisation equations.
b Source term (Constant term in discretisation equation)
107
p
c
Heat Capacity, kJ/ Kg k
erf, ercf error function and complementary error function
g Gravity, m
2
s
-1
h Height., m
h
T
Specific enthalpy due to mass transfer,
kg
kJ

h
D
Individual mass transfer Coefficient, m s
-1
io
h Individual heat transfer coefficient, w m
-2
k
-1
l Mass transfer direction
mC Mass flow rate, kg m
-2
s
-1
p Pressure, Pa
q Heat flux, w m
-2

r
v
reaction rate per unit volume,
1 3
s m kmol
S thickness, m
t Time, s
u Horizontal Velocity component, m s
-1

v Vertical Velocity Component, m s
-1

V Velocity Vector, ms
-1

x Horizontal orthogonal coordinate, m
y Vertical orthogonal coordinate, m
z Normal orthogonal coordination, m

108

Greece symbols
Film thickness, m
Dissipation energy, J
General representation of transport Variable
Vorticity-component vector, s
-1

Stream function, m
2
s
-1

Volume expansion, m
3
mol
-1

Thermal expansion, k
-1
Interface shear viscosity, kg s
-1

Dynamic viscosity, Pa s
Interfacial dilatation viscosity, kg s
-1

Thermal conductivity, W m
-1
k
-1

Kinematics viscosity, m
2
s
-1

K
Stoichiometry coefficient for component K
Density, kg m
-3
Surface tension, N m
-1

Viscous force /shear force/, Pa
Index
k Component index
i, j vector representation
O initial value
Infinitive
109
E, .N, W, S, EE, NN, WW, SS location of nodal point (gird point)
e, n, w, s Location of control volume face
ne, nw, sw, se Edge of the control volume
P Central grid point
int. Interface
Equ. Equilibrium
Eqn Equation
Upper phase
m time indices
HR Horizontal boundary

110

Reference
1. G. Astarita. Elsevier, 1976, Mass transfer with chemical reaction, Amsterdam,
London.
2. Seader.J.D. Ernest Henley.J., (1998), Separation process principles, John Wiley
and Sons, Inc.
3. Robert E. Treybal, 1981, Mass Transfer operations, McGraw-Hill Book Company-
Singapore
4. Barbara Elvars, 1992, Principles of chemical reaction engineering and plant design,
ULLMans Encyclopedia of Industrial chemistry, Volume B
4
.
5. W. D. Deekwer, 1985, Bubble Column Reactors, John Wiley and Sons, New York
6. J.M. Coulson, J.F. Richardsons, J.R.Backhurst and J,H. Harker,1999, Coulson &
Richardsons, Fluid flow, heat transfer and mass transfer. Chemical Engineering,
volume 1, Sixth edition,
7. D. Avnir and M.L. Kagan, 1994, The Evaluation of chemical patterns in reactive
liquids, driven by hydrodynamic instabilities, American Institute of Physics,
CHAOS,Vol. 5, No.3, PP - 589-601
8. Khalid H.Javed, John D.Thornton, Tarry J.Anderson, 1989, Surface phenomena and
Mass transfer rate in Liquid Liquid systems: Part 2, AIChE Journal, Vol. 35,
No.7,PP-1125-1135
9. Suhas V. Patankar, 1980, Numerical Heat transfer and Fluid flow, Hemisphere
Publishing Corporation, Washington, New York, London
10. H.K Versteeg and W. Malalsekera, 1995, An introduction to computational fluid
dynamics, The finite volume method, Addison Wesley Longman Limited.
111
11. William M. Deen, 1998, Analysis of Transport phenomena, Oxford university
press, New York.
12. Alexander G. Volkov, David W. Deamer, Darrell L. Tanelian, Vladislav S. Markin,
1998, Liquid interface in Chemistry and Biology, John Willey and Sons, Inc., New
York.
13. Alexander Grahn, 2003, Stroemungs instabilitaeten bei Stoffuebergang und
chemischer Reaktion aneder ebenen Grenzflaeche zwischen zweinicht mischbaren
Fluessigkeiten, PhD thesis, German
14. Yogash Jaluria, Kannaeth E. Torrance, 1986, Computational heat transfer, Edward
Brothers Inc., USA
15. Robert C. Reid, John M. Prausnitz, Bruce E. Poling, The properties of Gasses and
Liquids, Fourth Edition
16. R.K. Sinnott, 1999, Coulson and Richardsons, Chemical Engineering Design,
Chemical Engineering Volume 6, third edition, Butterworth-Heinemann, USA.
17. Stanley M. Walas, 1991, Modeling with differential equations in chemical
engineering, Butterworth-Heinemann, USA.
18. John C. Berbg and Carl R.Morig, 1969, Density effects in interfacial convection,
Chemical engineering science, Vol. 24,pp 937 - 946
19. Jack Winnick, Chemical Engineering Thermodynamics, John Wiley and Sons, Inc.

112

APPENDICES

Appendix A: Prediction of physical Properties of substances

When ever possible, experimental determines Values of Physical Properties should be used.
If reliable values can not be found in the literature and if time or facilities are not available
for their determination then in order to proceed with the design the designer must restore to
estimation.

1. Thermal conductivity of liquids
The temperature dependency of
L
is weak, and usually
L
decreases with an increase in
temperature. Empirical Equation for thermal conductivity

2
CT BT A
L
+ + =

Component A B C [w/m.k] T[k] Temp Rang
Water -3.838e
-1
5.254e
-3
-6.369e
-8
6.09e
-1
293 273-623
Cyclohexane 2.031e
-1
-2.254e
-4
-2470e
-8
1-35e
-1
293 178-581

2. Diffusivity: most liquid-diffusion coefficient equation result from empirical modification
of the stokes Einteine equation, which predicates for the diffusion of a large spherical
molecule A through a dilute solution B. a widely used correlation for
o
AB
D is the Wilke -
Chang technique

( )
6 . 0
5 . 0
8
10 4 . 7
A B
B o
AB
T M
D

=

Where
o
Ab
D = Mutual diffusion Coefficient of Solute at very low concentration in solvent B,
sec
2
cm

113
M
B
= Molecular weight of solvent B
T = Assault temperature, K

B
= viscosity of solvent B, cp
048 .. 1
285 . 0
c A
V = V

A
V
= Molar volume of solute A at its normal boiling temperature,
mol g
cm
.
3

= Association factor for solvent B, dimensionless
Wilke and Chang recommended that be chosen as follows
=
edsolvent unassociat for
Methanol for
Ethanol for
water is solvent the if
1
9 . 1
5 . 1
6 . 2

3. Liquid Heat Capacity
To determine heat capacities of organic liquids over wide temperature ranges,
corresponding states methods are normally used and the difference between the heat
capacity of liquids of in the ideate gas state is correlated with the eccentric factor of the
reduced temperature.
( ) ( ) ( ) { } [ ]
1 4
1 634 . 0 1 64 . 11 67 . 3 2 . 2 5 . 0

+ + + =
r r
o
p pL
T T R C C

c
r
T
T
T =
Reduced temperature
= Acentric factor
3 2
dT cT bT a C
o
p
+ + + =

=
o
p
C
Ideal gas heat capacity at the same temperature to evaluate
pL
C

114
The values of the constants are given below.

Component H
2
O Water C
2
H
4
O
2

Acetic Acid
C
6
H
12

Cyclohexane
a 32.243 4.846 -54.541
b 19.238x10
-4
25.485x10
-2
61.127x10
-2

c 10.555x10
-6
-1.753x10
-4
-2.523x10
-4

d 3.596x10
-9
49.488x10
-4
13.214x10
-9

M
w
(g/mol) 18.015 60.052 84.162
T
b
(
O
C) 100 117.9 82.9/80.7
T
c
(
O
C) 647.3 592.7 553.4
P
c
(bar) 220.5 57.9 40.7
(kg/m
3
) 998 1049 779
V
A
658.25 600.94 653.62
V
B
283.13 306.21 290.84
V
c
(cm
3
/mol) 57 172 308

0.344 0.447 0.212

4. Viscosity Of liquids Experimental Value
Empirical Equation for Viscosity

C T
B
A
L
+
+ = ln

Where A, B and C are constants, T is in
0
C
Compound A B C T Rang,
0
C
,cp,(T,
0
C) Ref
Water -2.471e
1
4.209e
3
4.577e
2
0-370 0.90 (25) 224
Acetic Acid -4.515 1.384e
3
- 15-120 1.30 (18) 212
Cyclohexane -4.398 1.380e
3
-1.55e
3
7-280 0.88 (25) 224

115
Appendix B: Mathematical manipulation of the Discretisation Equations

1. Discretisation equation for vorticity equation

( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
( )
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
\
|
+
+
|
|
\
|
+
+
+
+
|
|
\
|
+
+
+
+ |
\
|
+
+ |
\
|
+
=
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
]
+
+
+
+
+
+
+
+ + +
+
+
+
+
+ +
1 .
1
) 0 , max(
) 0 , max(
) 0 , max(
5
3
) 0 , max(
5
3
2
0 , max
2
0 , max
) 0 , max(
5
12
) 0 , max(
5
12
12 2
2
0 , max
2
5
6
0 , max
2
5
6
0 , max
5
9
0 , max
5
9 1
1
2
2
2
2 2
B
x
g
w
t
V w
y y y
y
V w
y y y
y
u w
x
u w
x
w
y y y
V
y y
y y
w
y y y
V
y y
y y
w u
x x
w u
x x
w
Z y y y
y y y
V
y y y
y y
y
x x
V
y y y
y y
u
x
u
x t
w e
o
P
m
P P NN
NN N NN
N
P SS
SS S SS
S
P EE P WW
N
N S N
P
NN N
NN N
S
N S S
P
SS S
SS S
W P
E P
P
SS S S
NN N N
P
NN N N
NN N
N
P
SS S S
S S
P
P

2. Discretisation equation for mass transport equation

( )
( ) ( )
( )
( ) ( )
( ) ( )
( )
]
]
]
]
]
]
]
]
]
]
+
|
|
\
|
+ +
|
|
\
|
+
+ |
\
|
+ + |
\
|
+
=
]
]
]
]
]
]
]
]
]
+
+ +
+ + + +
+ + +
2 .
0 , max 0 , max
0 , max 0 , max
0 , max
0 , max 0 , max
0 , max
1
B C
t
y x
C F
y
x D
C F
y
x D
C F
x
y D
C F
x
y D
C
K M F
F F
F
y
x D
y
x D
x
y D
x
y D
t
y x
m
P
S s
s
N n
n
W w E e
P
k k s
n w
e
s n

116
3. Discretisation equation for Heat transport equation

( ) ( )
( ) ( )
( ) ( )
( ) ( )
( )
]
]
]
]
]
]
]
]
]
]
+
+
|
|
\
|
+ +
|
|
\
|
+
+
|
\
|
+ +
|
\
|
+
=
]
]
]
]
]
]
]
]
]
+ + +
+ +
+ + + + +
3 .
2
0 , max 0 , max
0 , max 0 , max
2
0 , max 0 , max
0 , max 0 , max
1
B T
c
y x U
T
t
y x
T F
y
x a
T F
y
x a
T F
x
y a
T F
x
y a
T
Z c
y x U
F F
F F
y
x a
y
x a
x
y a
x
y a
t
y x
S
P o
o m
P
S s
S
N n
N
W w E e
P
P o
o
s n
w e
N S

4. Discretisation equation for mass transport equation at the interface

( )
( )
( )
( )
( )
( ) ( )
( ) ( )
( ) ( )
( ) ( )
( )
( )

+
+
+ +
+
+
+ + +
+
+ + +
=
+ + +
+ +
+ +
+ +
+ + +
+
4 . .
2
1
0 , max 0 , max
0 , max 0 , max
2 2
0 , max 0 , max
2 2
0 , max 0 , max
0 , max
0 , max
2
0 , max
2
0 , max
2 2
1
1
*
*
*
*
*
*
B C
t
y x N
C F
y
x D
C F
y
x D
C F F N
x
y D
N
x
y D
C F F N
x
y D
N
x
y D
C
F
y
x D
F
y
x D
F
y
x D
F N N
y
x D
F
x
y D
F N N
x
y D
t
y x N
m
P
S s N n
W w w
E e e
P
s n
w
w
n
e
e

117
5. Discretisation equation for Heat transport equation

( )
( )
( ) ( )
( )
( )
( )
( ) ( )
( ) ( )
( )
( )
( )
( ) ( )
( )
( )
( ) ( )
( ) ( )
( ) ( )
( )
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+
+
+
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+ +
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=
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+
+ +
+ +
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+
+
|
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\
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+
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5 .
2
2
0 , max
0 , max
0 , max 0 , max
2
0 , max 0 , max
2
2
0 , max
0 , max
0 , max
0 , max
2
0 , max 0 , max
2 2
int
1
* *
*
* * *
* * *
* *
* * *
* *
* *
*
* * *
* *
* * *
* *
* *
B hJ l yT x
Z
U
yT x
t
c c
T Pe A
y
x
F c
T Pe A
y
x
F c
T
F c F c
Pe A
Pe A
x
y
T
F c F c
Pe A
Pe A
x
y
T
y x
Z
U
F c
Pe A
y
x
F c
Pe A
y
x
F c
F c
Pe A
Pe A
x
y
F c F c
Pe A
Pe A
x
y
t
y x
c c
T S
o
m
p
p o p o
m
S s
S
s p o
m
N n
N
n p o
m
W
w p o w p o
w
w
m
E
e p o e p o
e
e
m
P
o
s p o
s
S
n p o
n
N
w p o
w p o
w
w
e p o e p o
e
e
p o p o

6. Discretisation equation for Vorticity transport equation at the interface.

( )
( )
( )
( )
( ) 6 .
0 , max
5
6
10
3
0 , max
5
6
5
6
0 , max
5
6
10
3
0 , max
5
6
5
6
10
9
10
9
10
6
10
6
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
B
u
x x x
u
x x x
u
x x x
u
x x x
u
x x
u
x
x
u
x
u
P
ee eee o
EE o o
P
e ee o
E o o
P
ww ww o
WW o o
P
ww w o
W o o
P
w e o
P P o o
o P
o P
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Modeling and Simulation of Interface Mass Transfor With Chemical Reaction

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Modeling and Simulation of Interface Mass Transfor With Chemical Reaction

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Addis Ababa University

School of Graduate Studies

= Mass transfer coefficient.

at the interface. The rate of mass transfer can be lumped in the

Hence it is possible to use equation (3.1)

) from equation (3.20) the final equation becomes

can be eliminated using the continuity equation (3.7), and

, the x - differentiation of dynamic interfacial tension given in equation (3.26) is

. In the convective term, the

smaller than the heat flow that is expected; hence it

based on the time

can be discretised using first order back ward differentiation

through the stream up ward differentiation. The horizontal second order

, where ( ) M i , ,......... 2 , 1 , 0 = is shown blow.

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