Mass Transfer and Mass Transfer Operations

MASS TRANSFER and MASS TRANSFER OPERATIONS
Erden ALPAY Mustafa DEMİRCİOĞLU
Ege University-Engineering Faculty-Chemical Engineering Department

Bornova-İzmir-TURKEY
September-2006
TABLE OF CONTENTS
(You can click subject name in order to reach the related page)
Preface vii
Introduction 1
Chapter-1 : MASS TRANSFER BY MOLECULAR DIFFUSION 7
1.1 Introduction 7
1.2 Mass Transfer by Molecular Diffusion in the Gases 9
Integration of the General Flux Equation 9
Equimolar Counter Transfers of A and B 9
A Transfers through Non-Transferring B 10
The Relationship between NA and NB is Fixed by Reaction Stoichiometry 11
The Relationship between NA and NB is Given by the Latent Heats of Vaporization 12
Mass Transfer with Varying Cross-Sectional Area 12
Mass Transfer by Molecular Diffusion in Multi-Component Gas Mixtures 14
Determination of Binary Diffusivities of Gases 14
Experimental Determination 14
Prediction of Binary Gas Diffusivities 18
Estimation of Binary Gas Diffusivities 20
Effect of Temperature and Pressure on Gas Diffusivity 22
1.3 Mass Transfer by Molecular Diffusion in Liquids 22
Determination of Molecular Diffusivities in Liquids 23
Experimental Method 23
Estimation of Liquid Diffusivities 25
Molecular Diffusivity in Concentrated Liquid Solutions 29

Molecular Diffusivities in Electrolytic Solutions 29
Effect of Temperature on Molecular Diffusivity in Liquids 30
Molecular Diffusivity in Multi-Component Liquid Solutions 30
1.4 Continuity Equation for a Binary Mixture 30
1.5 Mass Transfer by Molecular Diffusion in Solids 33
Diffusion that is Independent of the Nature of the Solid 33
Steady-State Diffusion 33
Unsteady-State Diffusion 34
Diffusion that is Dependent on the Nature of the Solid 37
Diffusion of Liquids in Solids 37
Diffusion of Gases in Solids 38
The Relationship between the Fluxes at the Diffusion of Gases in Solids 42
Molecular Diffusivity of Gases in Solids and the Permeability 42
Chapter-2 : MASS TRANSFER BY TURBULENT DIFFUSION and

MASS TRANSFER COEFFIENTS 46
2.1 Introduction 46
2.2 A and B Transfer under Equimolar Counter Transfer Conditions 48
2.3 A Transfers through Non-Transferring B 49
2.4 Mass Transfer Coefficients in Laminar Flow 49
Mass Transfer from a Gas into a Liquid Film in Laminar Flow 51
2.5 Mass Transfer Correlations 56
2.6 Mass Transfer Theories 59
Film Theory 59
Penetration Theory 60
2.7 Determination of Effective Concentration Difference for
Calculation of Average Flux 61
Chapter-3 : MASS TRANSFER BETWEEN TWO PHASES 68
3.1 Introduction 68
3.2 Equilibrium between Phases 68
3.3 Mass Transfer between Two Phases 69
3.4 Mass Transfer Flux 70
3.5 Overall Mass Transfer Coefficients and Overall Driving Forces 72
3.6 The Relationships between Individual and Overall Mass Transfer 73

Coefficients
Chapter-4 : GAS ABSORPTION 78
4.1 Introduction 78
4.2 Gas-Liquid Equilibrium 79
Ideal Solutions 80
Real Solutions 81
4.3 Selection of Solvent 83
4.4 Absorption Operations 85
Gas Absorption in Continuous Contact Type of Equipment 85
Wetted-Wall Column 85
Spray Column 88
Packed Column 88
Gas Absorption in Packed Column 95
Calculation of Number of Transfer Units 100
Calculation of Individual Heights of Transfer Units 104

Determination of Diameter of a Packed Column 106
Stage-Wise Contact Type of Absorption 110
Gas Absorption in Plate Columns 110
4.5 Non isothermal Absorption 126
4.6 Gas Absorption with Chemical Reaction 130
Gas Absorption with Instantaneous Chemical Reaction 133
Calculation of Height of Packing when Chemical Reaction is Instantaneous 135
Calculation of Height of Packing when Chemical Reaction is Slow 138
Calculation of Height of Packing when Rates of Diffusion and Chemical Reaction are
Comparable 141
Chapter-5 : DISTILLATION 150
5.1 Introduction 150
5.2 Liquid-Vapor Equilibria 150
Ideal Solutions 153
Deviation from Ideality: Real and Azeotropic Solutions 155
Partial Solubility and Insolubility of the Components in Liquid Phase 158
Volatility and Relative Volatility 161
K-Values 162
Bubble Point Temperature 164
Dew Point Temperature 164
Enthalpy-Composition Diagrams 166
5.3 Methods of Distillation 168
Equilibrium or Flash Distillation 168
Equilibrium or Flash Distillation under Constant Pressure 168

Flash Distillation by Reducing the Pressure of the Heated Liquid 171
Simple or Differential Distillation 175
Rectification or Fractionation 182
Continuous Rectification in a Plate Column 185
Rectification in Batch Operation 219
Rectification in Packed Column 229
Rectification of Azeotropic Solutions 233
5.4 Internal Design of Plate Columns for Liquid-Gas (Vapor) Contact 237
Column Diameter 239
Plate Spacing (P.S.) 240
Liquid Entrainment 241
The Holes 241
Weir 242
Pressure Drop in the Gas along the Plate 242
Design Steps 245
Chapter-6 : LIQUID-LIQUID EXTRACTION 254
6.1 Introduction 254
6.2 Liquid-Liquid Equilibria 255
6.3 Selection of Solvent 258
6.4 Extraction Operations 259
Stage-Wise Operations 259
Single Stage Extraction 260
Cross-Current Multi-Stage Extraction 262

Counter-Current Multi-Stage Extraction 265
Counter-Current Multi-Stage Extraction under Reflux 269
Design of Mixer-Settler Units 272
Appendices 276
References 284
Preface
This CD-book covers the subject-matter on mass transfer and mass transfer
operations. The text is primarily intended for undergraduate students in chemical
engineering, however the first three chapters may also be used by biochemical, food
and environmental engineering students. Practicing process engineers may find the
book useful to refresh themselves.
The first three chapters of the book provide the students with background necessary to
understand the mass transfer operations, dealt with in the subsequent three chapters.
In Chapter1, molecular diffusion in gases , liquids and solids is discussed in some
details, including determination and prediction of diffusion coeffients. Chapter 2
covers the mass transfer by turbulent diffusion and introduces the student to mass
transfer coefficients and to their use. In Chapter 3, mas transfer between two insoluble
phases is dealt with and concept of mass transfer resistance is emphasized. The
following three chapters deal with macroscopic separation operations based on
interface mass transfer, which are gas absorption, distillation and liquid-liquid
extraction. Operations are discussed in both plate and packed columns including their
internals and sizing.
This CD-book was first published in 2004 and corrected and expanded in the years
2005 and 2006.
Another CD, prepared for the teachers, contains the animated power point
presentations of the topics and solved problems of this CD book. It is consisted of
1387 slides ( 695 in English, 692 in Turkish) and is sent to the interested colleagues.
Erden Alpay Mustafa Demircioğlu

erden.alpay@ege.edu.tr mustafa.demircioglu@ege.edu.tr
September, 2006-İZMİR
VI
Introduction
MASS TRANSFER and MASS TRANSFER OPERATIONS
Mass transfer and mass transfer operations play important roles in chemical
engineering practice. These are also important for bioengineering, environmental
engineering and food engineering practices. What is mass transfer and how does it
take place? In order to understand this, let us take a glass of water. Although the water
in the glass looks stagnant to us, it is well known that individual water molecules are
not stagnant but move randomly in all directions (Brownian motion). During motions,
molecules collide with each other and change directions. Nevertheless, these motions
of the molecules do not result in net transfer of mass, because of the fact that, the
number of the molecules leaving a region is balanced with the number of the
molecules coming to this region. Hence, we cannot mention of mass transfer in a
medium consisting of single type of molecules (pure components). Now, let us hang a
potassium permanganate (KMO4) crystal into the glass as shown in Fig.1. As we
know, potassium permanganate can dissolve in water and has a violet colour. Within a
very short time period, we notice that the water surrounding the crystal turns into
purple colour. This is the indication of the dissolution of crystal. As the time passes,
purple coloured water expands showing the movement of KMO4 molecules. We
understand from this that dissolved KMO4 molecules (in reality ions rather than
molecules) do not remain stagnant but diffuse from dissolved region to the regions,
which do not contain these molecules. After a very long time, a uniform purple colour
throughout the whole glass is finally obtained. Uniform colour means that number of
the KMO4 molecules in each ml of the solution (concentration of the solution)) at
every point of the glass is the same. We understand from this experiment that a net
transfer of mass (KMO4) had taken place: the dissolved KMO4 molecules moved from
the dissolved region to the regions where they did not exist. This phenomenon is
named as mass transfer. As the mass transfer resulted from the movement of the
individual molecules, this type of mass transfer is known as mass transfer by
KMO4
Fig.1 Dissolution of KMO4 crystal and mass transfer by molecular diffusion
molecular diffusion. In reality, we cannot follow the movements of the individual

molecules by blank eye, as they are very tiny particles. But in this experiment, because
of the colour associated with molecules, we can realise the mass transfer by noticing
the colour change. If we repeat this experiment, for example with table salt (NaCl), we
No part of this CD-book may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu 1
cannot realise mass transfer with blank eye, although we may follow the dissolution of
colourless crystal. Normally, we follow and understand mass transfer by measuring the
concentration of the solution at different points. If we return back to KMO4
experiment, we can say that KMO4 molecules transferred from higher concentration
regions to the lower concentration regions (how can we say that?). It follows from this
that the reason or driving force for a mass transfer is the concentration difference or
concentration gradient. Since, because of concentration difference mass transfer takes
place, mass transfer can only be met in the solutions. If at two different points of a
solution, a concentration difference exists for a component (in the example this
component is KMO4), this component transfers from higher concentration region to
the lower concentration region to remove this difference. As long as this difference
prevails, the mass transfer continues. When the concentration uniformity is obtained,
transfer of mass stops, although the movements of the molecules of both water and
KMO4 do not stop. But these movements do not bring about net transfer of mass. This
is an example of mass transfer by molecular diffusion in a liquid phase.
Now, look at another example: Suppose a teacher has a perfume can and by pressing
the knob at the top of the can he lets the perfume liquid to vaporize into air of a class-
room whose door and windows are closed. Students, sitting in the immediate vicinity
of the teacher, smell the nice smell almost instantaneously, but the students, sitting at
the back seats, smell the perfume much later. Here, vaporized perfume molecules mix
with the molecules of still air near the teacher. Now, the concentration of perfume
molecules in the gaseous mixture near the teacher is higher than in the gas at the rest
of the room. Thus, reason for mass transfer has been created. Under this concentration
difference, perfume molecules start transferring from teacher’s vicinity towards the
students. As the air in the room is still, mass transfer is affected by molecular
diffusion. This is an example of mass transfer by molecular diffusion in a gas phase.
It follows from these two experiments that, rate of mass transfer is rather slow,
because the times required for the glass to obtain uniform colour and for the students
sitting at the back seats to smell the perfume are both rather long.
Now, if we repeat the first experiment by stirring the content of the glass by a stirrer as
soon as we hang the KMO4 crystal, we see that the time required for uniform colour
attainment is very short. The answer to the question: “what has happened?” is:
“stirring has created turbulence”. Turbulence is characteristic of creating molecule
groups, called Eddy. These eddies contain large number of both solvent and solute
molecules (in the smallest eddy this is higher than 1016) and move rapidly. This type of
mass transfer is known as mass transfer by turbulent diffusion. The rate of mass
transfer by turbulent diffusion, which depends largely on the intensity of the
turbulence, is much greater than the rate of mass transfer by molecular diffusion. In the
second experiment mass transfer by turbulent diffusion is affected by switching on a
fan as soon as the can’s knob is pressed. As expected, in this case the time required for
the students to smell the scent of the perfume is much shorter compared with the
experiment without fan.
The creation of turbulence can be accomplished by various ways. For example
consider a solid horizontal plate as shown in Fig.2, made of a soluble solid or coated
with it, along which a liquid flows parallel to the plate (e.g. solid is benzoic acid,
liquid is water). If the average velocity of flow u x is small, the liquid flows as layers
slipping one on the other. The velocity of the first layer adjacent to solid is zero and
liquid B
x
solute A
solid plate
(a) (b)
Fig.2 Mass transfer (a) in laminar, (b) in turbulent flow
other layers have different velocities, which increase in z-direction. This type of flow
is known as streamline or laminar flow. In this type of flow, there is not velocity
component in the z-direction (uz=0), and only individual molecules can pass from one
layer to another. If the velocity of liquid is increased, after a critical velocity, liquid
loses its orderly flow, and an appreciable velocity component in z-direction forms.
This type of flow is known as turbulent flow. Disorderly flow is due to the formation
of eddies, which are characteristic of turbulent flow. The eddies move rapidly in both
x- and z-directions. As the plate is coated with dissolving solid A, a concentration
gradient for component A in z-direction sets up, as soon as the flow of liquid B starts.
The concentration of solute A in the first liquid layer adjacent to solid plate
corresponds to its solubility at the prevailing temperature and this is the highest
concentration. Due to this concentration change in z-direction, mass transfer in z-
direction must take place. In the laminar flow, since only the movement of single
molecules in z-direction is possible, molecules of solute A diffuse from one layer to
the next layer in z-direction. In other words, mass transfer can only take place by
molecular diffusion. In the turbulent flow, since the movement of group of molecules
(eddy) is permissible, transfer of solute A from liquid next to solid surface to the bulk
liquid is by turbulent or eddy diffusion.
So, whenever a concentration gradient exists for a component of a solution, mass
transfer takes place. The transfer mechanism depends on the condition of medium: if
the medium is stagnant or flows in laminar regime, transfer of mass is by molecular
diffusion. On the other hand, if the medium is mixed or flows in turbulent regime,
transfer of mass is by turbulent or eddy diffusion. Although the mass transfer by
turbulent diffusion is much more rapid than the mass transfer by molecular diffusion,
this is not an instantaneous process but it is a rate process.
Interphase mass transfer and mass transfer operations: So far, we have seen mass
transfer within a single phase. We consider now the mass transfer between two phases.
These two phases may be: liquid-liquid, liquid-gas, liquid-solid and gas-solid. Gas-gas
system is not possible, as gases mix with each other in any proportion. As an example,
take liquid-gas system. Suppose we contact a gaseous mixture of ammonia (A)-
nitrogen (C) with water (S) at room conditions. At these conditions, only ammonia
dissolves in water and water does not evaporate into gas. As soon as we have the
contact, some of the ammonia molecules in the gas phase next to the interface pass the
interface and dissolve in water. As a result of this, a concentration difference for the
ammonia molecules in z- direction sets up, as the
number of the ammonia molecules in the unit gas
interface
volume next to the interface is less than the number Gas phase Liquid phase
A+C S
of the ammonia molecules in unit volume in the
A
bulk gas. Under this concentration difference,
ammonia transfers from bulk gas to the interface Bulk gas Bulk liquid
and from there into the liquid phase. Now, look at
the liquid phase. At the beginning, water does not
contain any ammonia. As soon as the ammonia
z
molecules cross the interface, the liquid next to the
interface contains more ammonia molecules than
the bulk liquid. So, in the liquid phase a concentration gradient for the ammonia in z-
direction sets up as well. As a result of this concentration difference, ammonia
transfers from liquid interface to the bulk liquid. If we look at the whole process, we
see that ammonia is transferring from the gas phase into the liquid phase. This transfer
can proceed until the two phases reach in equilibrium. The equilibrium concentration
of ammonia in the liquid phase is the solubility of ammonia in water under the
prevailing partial pressure of ammonia and temperature. Once the equilibrium is
attained, mass transfer stops and concentration in both phases are uniform throughout.
At the equilibrium, concentrations of ammonia in two phases are not equal.
This interphase mass transfer can be by molecular or turbulent diffusion depending
upon the conditions and the flow characteristics of the phases. If both phases are
stagnant or flow in laminar regimes, then the mass transfer is by molecular diffusion in
both phases. If both phases are mixed thoroughly by stirrers or they flow in turbulent
flow regimes, then the mass transfer in both phases is by turbulent diffusion. Of
course, depending upon hydrodynamics of the phases, mass transfer in one phase may
be by molecular diffusion and in the other by turbulent diffusion.
Look at the net result of this interphase mass transfer. What has happened? With
interphase mass transfer we make changes in the concentrations of the phases. Take
the gas phase: at the beginning we have a gaseous mixture rich in ammonia, by
transferring part of the ammonia to the water we obtained a gaseous mixture lean in
ammonia. We can even transfer all the ammonia in the gas into liquid phase by taking
necessary measures, leaving almost pure nitrogen behind. So, by applying interphase
mass transfer we can separate or even purify a phase. In the example, ammonia is
separated from nitrogen by contacting gaseous mixture with water. This operation is
known as gas absorption. Gas absorption is used to separate or purify gaseous
mixtures. For the separation or purification of liquid mixtures, distillation or
extraction or both are used. To all these operations and to some more are given a
general name: Mass transfer operations. So, mass transfer operations are the
separation or purification operations that depend on interphase mass transfer.
What is the importance of separation or purification in chemical process
industries? In the chemical process industries, separation is very important. Almost in
all the chemical reactions, mixtures, not pure substances are obtained. For sale or
subsequent use of a product, certain degree of purity is required. Thus separation of
any reactor exit is almost dictated upon us. In some cases, even the reactants
themselves must be purified prior to the entry to a reactor. As an example, consider the
production of benzoic acid from toluene by oxidation with air oxygen.
Toluene + O2 Benzoic acid
Although the reaction can be written in this simple way, industrial production is rather
complicated, as it requires large number of separation steps: Reactant toluene, which
is a petro-chemical, is generally found mixed with benzene and xylenes and is
separated from these by using a series of distillation operation, before pumping it to
the reactor. Other reactant oxygen is again obtained by liquefaction and distillation of
air. The reactor outlet contains not only the main product benzoic acid, but also un-
reacted toluene (conversion is kept at 35-40 %), and the side-products benzaldehyde,
acetic acid, benzylbenzoate, etc. This mixture is then sent to a train of separation units,
which contains distillation and stripping columns, to separate and purify the benzoic
acid. The separation and purification operations used in this production are all mass
transfer operations. In the total investment cost of the plant, the investment cost of the
reactor is much smaller than the investment cost of the separation units. From this, we
may understand the importance of mass transfer operations in chemical engineering
practices.
Are all the separation operations mass transfer operations? In chemical process
industry, various separation operations are used. Not all these separation operations are
mass transfer operations. Only the separation operations based on interphase mass
transfer are the mass transfer operations. For example, filtration, which is a separation
operation, is not a mass transfer operation, since it does not involve interphase mass
transfer. It is based on physical separation of a solid from a solid-liquid mixture with
the help of a media, such as filter paper or cloth. Sieving is also a separation operation
but it is not a mass transfer operation. Because, in the sieving a solid mixture having
different sizes of material, is separated into uniform size fractions by using a sieve set.
Again repeating, mass transfer operations are the separation operations based on mass
transfer between the phases. Here are some industrially important mass transfer
operations: gas absorption, stripping or desorption, distillation, liquid-liquid extraction,
leaching, adsorption, membrane separation, etc.
Almost all the separation operations, used in chemical industry, whether are based on
interphase mass transfer or not, are physical in nature and hence they are unit
operations.
Don’t we use mass transfer in processes other than separation operations? We
also make use of mass transfer knowledge in various processes other than mass
transfer operations; for example, at the production of ammonia or hydrochloric acid
solution. In these cases, we contact the gas ammonia or gas hydrogen chloride with
water and by taking the necessary measures we can produce ammonia or hydrochloric
acid solution at the desired concentrations. In a fermentation process, substrate
dissolved in the solution, diffuses to the microorganism to react there. Here, the rate of
mass transfer directly affects the fermentation process. In a catalytic chemical reaction,
the reactants diffuse from the bulk of gas phase to the catalyst surface, where reaction
takes place. Gaseous products diffuse from the surface of the catalyst to the bulk gas.
In this case, rate of mass transfer to or away from the surface affects the production
rate. In drying processes, the moisture in the bulk solid, first diffuses through the solid
phase to the surface of the solid, there it evaporates into hot gas at solid-gas interface
and continues its diffusion in the gas phase from interface gas to the bulk gas. The rate
of drying of the solid may depend on the rate of mass transfer in solid or in gas phase
or both.
Chapter-1
MASS TRANSFER BY MOLECULAR DIFFUSION
1.1 Introduction: It was shown in the introduction that mass transfer takes place by
molecular diffusion in stagnant media or laminar flow regimes. In any mass transfer
process, it is very important to calculate the rate of mass transfer. Now, we will try to
write this rate equation. Concentration difference causing mass transfer and the rate
can be expressed in molar or mass units. Throughout this chapter molar units will be
used. According to Fick, when a concentration gradient exists for component A in z-
direction in a binary mixture of A+B, molar diffusional flux of A JAz,is written as:
JAz= -DAB dc A (1-1)
dz
This is known as Fick’s first law equation. Since the flux is defined as quantity of A
transferring per unit time per unit area normal to the transfer direction, in SI unit
system this is then: k-molA/m2s. dcA/dz is the concentration gradient causing the mass
transfer as k-molA/m3 m. (-) sign emphasizes that diffusion always occurs in the
direction of decreasing concentration. DAB is called as molecular diffusivity or
diffusion coefficient of component A in component B (m2/s). This is a true physical
property of the system and hence is characteristic of A-B pair and depends on
pressure, temperature and concentration of the mixture.
If a concentration gradient exists for the other component B of the mixture, similar
equation for this component is written as:
JBz= -DBA dc B (1-2)
dz
Rate of molecular diffusion, J A z (k-molA/s) can be related to the diffusional
flux, J Az by :
J
J Az = Az (1-3)
Sm
where, Sm (m2) is the mass transfer area which is normal to the transfer direction.
If mass units instead of molar units are used, diffusional flux of component A, jAz (kg
A/m2s) is written as:
jAz=-DAB
dρ A (1-4)
dz
where ρ A (kgA/m3 ) is the mass concentration of component A.
As it has been stated above, these fluxes are the fluxes of molecules. At some cases,
the mixture itself moves in the diffusion direction of the components, which is known
as bulk or convective flow. In reality, when a concentration gradient exists for one
component of a binary mixture in any direction, there must be a concentration
difference for the other component of the mixture in the opposite direction. As a result
of these concentration differences, both components of the mixture diffuse in the
opposite directions. If the rates of these diffusions are not equal in molar units, then
the mixture itself drifts in the direction of the component whose molar diffusional rate
7
No part of this CD-book may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
is greater. So, it is obvious that total molar flux of each component for a fixed observer
will be different than the diffusional fluxes of the components. Let us consider this in
more details: Let us show the velocities of each type of molecules in z-direction as uAz
and uBz. Then, the total molar flux of each component relative to the fixed coordinates
are NAz= cA uAz and NBz= cB uBz, where cA and cB are molar concentrations of A and B
(k-mol/m3) . On the other hand, since the total molar concentration of the mixture is
c=cA+cB, the molar average velocity of the mixture, u& z (m/s) is then:
c A u Az + c B u Bz N Az + N Bz
u& z = = (1-5)
c c
As the molar diffusional flux of component A is due to the movement of the molecules
relative to the molar average velocity of the mixture, then;
JAz= cA(uAz- u& z ) = cA uAz - c A u& z (1-6)

can be written. After substitutions from the equations above finally,
cA
NAz= JAz + ( NAz + NBz ) (1-7)
c
is obtained. This equation is known as general flux equation and it relates the molar
diffusional flux to total molar flux. As it is seen, total molar flux of a component is the
sum of the molar diffusional flux of this component and the flux of this component
due to the bulk flow of the mixture.
Repeating once more, diffusional flux of a component in a mixture is the flux, which is
relative to the average velocity of the mixture, if any. Total flux of the same
component is the flux of this component with respect to fixed coordinate system. If
there is no bulk flow of the mixture in the direction of diffusion, then total and
diffusional fluxes will be the same. Total flux is very important in the design of the
equipment in which mass transfer occurs.
Similar equation for the other component B will be:
cB
NBz = JBz + ( NAz + NBz ) (1-8)
c
The relationship between total molar flux and total molar rate ( N Az ) (k-mol A/s)
can be written as:
N
N Az = Az (1-9)
Sm
Similarly, if instead of molar units, the mass units are used; total mass flux of
component A, nAz (kgA/m2s) is written as:
ρA
nAz = j Az + ρ A u z = j Az + (nAz + nBz ) (1-10)
ρ
where uz is the mass average velocity of the mixture and given as:
u z = ( ρAu Az + ρBuBz ) / ρ =( nAz + nBz )/ ρ (1-11)
8
1.2 MASS TRANSFER BY MOLECULAR DIFFUSION IN THE GASES
1.2.1. Integration of the General Flux Equation: Equation (1-7) can be integrated
under various conditions. Let us consider its integration at steady-state with DAB and
Sm are constant. First, substitute JAz from equation (1-1) and then separate the
variables. With the limits of the integrals: at z=z1 cA= cA1 and at z = z2 cA=cA2 ;
c
⌠
A2
1 z2 dc A
cD AB ∫ z1
dz = − ⎮
⌡c A1 cN A − c A ( N A + N B )
is obtained. For the sake of simplicity
subscript z is omitted. Upon integration,

z 2 − z1 1 c N A − c A2 (N A + N B )
= ln is found. If both sides of this equation are
c D AB N A + N B c N A − c A1 ( N A + N B )
multiplied by NA and z = z2-z1 is taken, finally;
NA c
− A2
NA c D AB NA + NB c
NA = . ln (1-12)
NA + NB z NA c
− A1
NA + NB c
is obtained. This equation can also be written in different forms. From the ideal gas
n nA
law, P = RT = cRT and pA = RT = c A RT can be written, where P and
V V
pA are the total and partial pressure of component A, respectively. Substituting these
into equation (1-12),
NA p
− A2
NA D P NA + NB P
NA = . AB ln (1-13)
N A + N B RTz NA p
− A1
NA + NB P
is obtained. From Dalton’s law yA= pA/P, where yA is the mole fraction of component
A in the gas. Substituting this into the equation above, another form of equation (1-12)
is found as:
NA
− y A2
NA D P NA + NB
NA = . AB ln (1-14)
N A + N B RTz NA
− y A1
NA + NB
Any one of these three equations may be used to calculate the total molar flux of
component A. But, to use any one of these equations, the relationship between NA and
NB must be known. This can be easily obtained from the condition of the system. Let
us see below the most commonly encountered cases for the interrelationships of NA
and NB.
1.2.2 Equimolar Counter Transfers of A and B: This is a situation, which is
frequently met in distillation of binary solutions of equal latent heats of vaporization.
So, in this case, NA=-NB = constant and equation (1-12) is indeterminate. Then, we go
back to the equation (1-7), with NB=-NA this equation becomes:
9
N A = − D AB
dc A c A
+ [N A + (− N A )] = − D AB dc A + 0
dz c dz
if this equation is integrated under the conditions at which equation (1-7) was
integrated.
D AB
NA = (c A1 − c A 2 ) (1-15)
z
is obtained. This equation is the special solution of equation (1-12) for this case.
Similarly, the special solutions of equations (1-13) and (1-14) for this case are:
D AB
NA = ( p A1 − p A 2 ) (1-16)
RTz
and
D AB P
NA = ( y A1 − y A 2 ) (1-17)
RTz
As it is seen, at this special case NA = JA . It follows from this that there can’t be bulk
flow in the transfer direction, when equimolar counter transfer occurs. Since in this
case NA+NB=0, this case is also known as “mass transfer under zero-net-flux”. It is
obvious from the equations above that concentrations of the components change
linearly with transfer path as shown in Fig.1.1a.
1.2.3 A Transfers through Non-Transferring B: This occurs in gas absorption
operations. In this special case, since component B is not absorbed, NB=0 and then
equations (1-12), (1-13) and (1-14) simplify to:
c D AB c D AB P p D AB P y
NA = ln B2 , NA = ln B2 , NA = ln B2 (1-18)
z c B1 RTz p B1 RTz y B1
Although these equations can be used in these forms, we prefer to write them in the
form of “flux of a component is proportional to the concentration difference of the
same component”.
Since, cA1 – cA2 = cB2 – cB1, pA1 – pA2 = pB2 – pB1 and yA1 – yA2 = yB2 – yB1 ,
the right hand sides of the equations given in (1-18) are first multiplied with the
appropriate equation below,
c A1 − c A 2 p A1 − p A 2 y A1 − y A 2
=1, =1 =1
c B2 − c B1 p B2 − p B1 y B2 − y B1
then by definitions of logarithmic means, which are given below,
c B2 − c B1 p B2 − p B1 y B2 − y B1
= (c B )ln , = (p B )ln , = (y B )ln
c B2 p B2 y B2
ln ln ln
c B1 p B1 y B1
finally;
D AB c D AB P D AB P
NA = ( c A1 − c A 2 ) , N A = ( p A1 − p A 2 ) N A = ( y A1 − y A 2 )
z (c B ) ln RTz (p B )ln RTz (y B ) ln
(1-19)
are obtained. As it is seen, in this special case, relationships between concentrations
and transfer paths are not linear as shown in Fig.1.1b. Furthermore, it is seen from the
figure that (-dpB/dz ) is not zero, and under this concentration gradient component B
10
diffuses also in the opposite direction of component A. But its diffusional flux is
exactly balanced with the bulk flow flux of B. As a result of this, to a fixed observer,
component B looks non-transferring. So, when only one component of a binary gas
mixture is absorbed into a liquid, there is always a bulk flow of the mixture in the
transfer direction. This increases the flux of the absorbed component.
P P P P
A A
pressures,pA,pB,P
pB2 pB2
pressures,pA,pB,P
B
pA1
pB1
pA1
pB1 pA2
pA2
z1 distance,z z2 z1 distance,z z2
(a) (b)
Fig.1.1 Concentration profiles (a) in equimolar counter transfer and (b) in A

transfers through non-transferring B
1.2.4. The Relationship between NA and NB is Fixed by Reaction Stoichiometry: In

some cases, relationship between the fluxes is fixed by the chemical reaction, taking
place nearby. Consider the gas phase reaction below taking place on a solid catalyst
surface,
m A→ n B
According to the stoichiometry of the reaction, when m moles of component A

transfer towards catalyst surface at the same time n moles of component B transfer
from the catalyst surface to the bulk gas. So, n NA = - m NB can be written. Hence,
substituting NB = - (n/m) NA into any one of the equations (1-12), (1-13) and (1-14) NA
is calculated.
Example-1.1) Calculation of Molar Fluxes
A gaseous chemical reaction is taking place on a solid catalyst surface at 2 bars and 25 oC according
to the stoichiometry given below:
2A B
Across a gas film of 2 mm thickness adjacent to the solid, partial pressures of component A are
measured as 0.40 and 0.10 bars.
Calculate total molar fluxes of component A and B.
At the operating temperature and pressure DAB= 4.10-5 m2/s.
11
Solution :
Equation(1-13) can be used.
A
t
catalyst
NA NA 1
= = =2
N A + N B N A − 0.5 N A 1 − 0.5 B z
1 2
( 4 *10−5 m 2 / s)(2 bar ) 2 − (0.1 / 2)

N A = ( 2) ln
(0.083 bar m / k − mol K )(273 + 25 K )(2 *10 m)
3 −3
2 − (0.4 / 2)
NA = (3.23 * 10-3) ln (1.083) = 2.58 *10-4 k-mol A/m2s
NB = - (0.5) NA = - 1.29*10-4 k-mol B/m2s
1.2.5 The Relationship between NA and NB is Given by the Latent Heats of

Vaporization: In the rectification of a binary liquid solution, mass transfer takes place
both in liquid and vapor phases. The more volatile component transfers from liquid to
vapor and the less volatile from vapor to liquid. As the vapor and liquid are both
saturated at the operating conditions, an energy equal to the latent heat of vaporization
is needed for the vaporization of more volatile component. This energy is given by the
condensation of less volatile component. Thus, the quantities of more and less volatile
components that will vaporize and condense are interrelated by λA NA = - λB NB,
where λA and λB are latent heats of vaporization of the corresponding components
(kJ/k-mol). In this case substituting NB = - (λA/λB ) NA into one of the equations (1-
12), (1-13) and (1-14) the fluxes can easily be calculated. Note that if λA = λB,
equimolar counter transfers of A and B occurs.
1.2.6 Mass Transfer with Varying Cross-Sectional Area: If the mass transfer area
Sm does not remain constant and changes with z, the fluxes in the equation (1-7) do not
remain constant even at steady-state. Since, in this case N Az and N Bz are constant, NA
N Az N
and NB in the equation (1-7) are first replaced with and Bz and Sm is
Sm Sm
expressed as function of z and then the integral is performed. By dividing so-obtained
( N Az ) with the Sm value calculated at the specified z, NA at this z is obtained.
Example-1.2) Calculation of Molar Flux in Varying Cross-Section
SO2 (A) is transferring at steady-state through non-transferring O2 (B) in a metal conduit, 2.0 meter
long, at 10 bars and 598 K. The cross-section of the conduit is rectangular and tapers uniformly from
an area of 300 mm by 400 mm to an area of 300 mm by 200 mm. The partial pressure of SO2 is
measured as 0.22 bar and 0.055 bar at two ends.
12
Calculate the total molar flux of SO2 at mid-point of the conduit.
The molecular diffusivity of SO2 in O2 at 1 bar and 25 oC is 2.25*10-5 m2/s.
Solution :
b=300 mm
a2 =200 mm
Sm1 NA Sm2
S a
(S pA2
a1 =400 mm NB= 0
pA1
b=300 mm
l/2
z
Sm = b * a = 0.3 * a (m2)
a1 − a 2 0.4 − 0.2
a = a1 − z = 0. 4 − z = 0.4 − 0.1 z (m)
l 2
Sm = 0.3(0.4 - 0.1 z) = 0.12 - 0.03 z (m2) From eqn.(1-7) for NB=0 and J A = − D AB dp a
RT dz
pA D dp A
N A (1 − ) = − AB
P RT dz
NA D P dp A
dz = − AB After substituting for Sm and separating the variables,
Sm RT P − p A
l dz D AB P p A2 dp A
NA ∫o 0.12 − 0.03 z = −
RT ∫p A1 P − pA
ln [0.12 − 0.03 z ]02 = AB ln [P − p A ]00..22

NA D P
− 055
0.03 RT
1.75
⎛ 1 ⎞ ⎛ 598 ⎞
D AB = 2.25 *10 ⎜ ⎟ ⎜
−5
⎟ = 7.61*10 −6 m 2 / s
⎝ 10 ⎠ ⎝ 298 ⎠
Then from equation above, N A =1.11*10−9 k − mol A / s = cons tan t
At z = l / 2 (Sm)l /2= 0.12 – 0.03 (1.0) = 0.09 m2
NA 1.11 * 10 −9
(N A ) l / 2 = = = 1.23 * 10 −8 k − molA / m 2 s
(S m ) l / 2 0.09
13
1.2.7 Mass Transfer by Molecular Diffusion in Multi-Component Gas Mixtures:
In many engineering applications of mass transfer, the mixture contains more than two
components and all the components of the mixture may diffuse under the available
concentration gradients. The total molar flux of component A in this case can also be
calculated from equations (1-12, (1-13) and (1-14) by making two modifications in the
n
equations. First, all the NA+ NB terms in the equations are replaced with ∑ N i second,
i=A
an effective diffusivity defined by equation (1-20) is taken in the place of DAB.

n
NA − yA ∑ Ni
D Aef = i=A
(1-20)
n 1
∑ ( yi N A − yA Ni )
i = A D Ai
With these changes, the equation (1-12) becomes:

NA cA2
n
−
∑ Ni c
N A c D Aef
NA = n
ln i=A
(1-21)
∑ N z NA c
i=A
i
n
− A1
∑ Ni c
i =A
As it is seen from equation (1-20), effective diffusivity DAef, which can be synthesized
from its binary diffusivities with each of the other components, depends on the
concentration and hence may vary considerably from one end of the diffusion path to
the other, and a linear variation with distance can be usually assumed. In some cases
all N’s except NA is zero. In this case equation (1-20) simplifies to:
1− yA
D Aef = n y
(1-22)
∑ i
i = B D Ai
1.2.8 Determination of Binary Diffusivities of Gases: It is obvious from the

equations above that to use any one of these, binary diffusivity, DAB must be known at
the operating conditions. It was shown that effect of concentration on the diffusivity is
negligible. The diffusivities can be determined experimentally or may be predicted
from the kinetic theory of gases or can be estimated from various empirical
correlations. Depending upon the physical state of the components at the
experimentation conditions, one of the three experimental techniques given below, can
be used.
1.2.8.1 Experimental Determination: Three main methods are available. Depending
upon the state of the components at experimental conditions, one of these can be used.
Two-Bulb Method: This method is used when both components are gas at the
experimentation conditions. The experimental set-up as shown in Fig.1.2, consists of
two chambers with V1, V2 volumes, connected with a capillary tube whose length and
cross-section are l and S. This set-up can be made of glass or metal depending upon
experimental pressure. The chambers are first completely evacuated, then the valve on
the capillary tube is closed and chamber-1 is charged with pure A and the chamber-2
with pure B at the same pressure. At θ = 0, the valve on the capillary tube is opened
and mass transfer is allowed to take place. After a certain time, the valve is closed and
14
1 c oA1 2 c oA 2
Sm
V1 V2
cA1 l
cA2
z
Fig.1.2 Experimental set-up for two bulb method
chamber-2 is thoroughly mixed and analysed for component A. By ignoring the

volume of the capillary tube and assuming uniform concentrations in both chambers at
any time of the diffusion, equation
dc D (c − c )
J A = −D AB A = − AB A 2 A1 (1-23)
dz l
can be written. The accumulation of component A in chamber-2 is due to the mass
transfer of this component from chamber-1. Thus,
dc S m D AB (c A1 − c A2 )
V2 A2 = S m J A = (1-24)
dθ l
is written. On the other hand, the average concentration of component A (c A ) in the
system is found from any one of the equations below, where
c oA1 , c oA 2 , c A1 , c A 2 are molar concentrations of component A in chamber-1 and
(V1 + V2 ) cA = V1 c oA1 + V2 c oA 2 (1-25)
(V1 + V2 ) c A = V1 c A1 + V2 c A 2 (1-26)
chamber-2 at the beginning and at the end of the experiment. If cA1 is solved from
equation (1-26) and substituted into equation (1-24) ,
D (V + V2 )
c
⌠
A2
dc A 2 θ
⎮ = ∫o dθ is obtained. Where, p is defined as p = AB 1

⌡c p ( cA − c A 2 )
o
A2
(l/S m )V1 V2
After performing integral, substituting p and solving for DAB finally,

l V1 V2 c − co
D AB = ln A A2 (1-27)
S m (V1 + V2 ) θ c A − c A2
is obtained. Since V1 , V2 , Sm , l are all known, and c A can be found from equation
(1-25), by measuring the cA2 after an experimentation time of θ, DAB is calculated from
equation (1-27).
Winkelmann Method: This method is used when one of the components is liquid at
the experimentation conditions. As shown in Fig.1.3, a narrow tube is filled with liquid
A to a certain depth and the gas component B is made to flow through a large diameter
channel attached to the tube mouth. During this flow, liquid A vaporizes and transfers
in the gas in z-direction by molecular diffusion, as its concentration at the liquid-gas
interface (point-1) is higher than that at the tube mouth (point-2). Mass transfer takes
15
place under the conditions of “A transfers through non-transferring B”, as component
B is not absorbed into liquid A. So, any one of the
gas B equations (1-19) can be written.
2 D AB P
NA = ( p A1 − p A 2 ) (1-19)
pA2≈0 RTz (p B ) ln
NA Here, pA1 is the partial pressure of component A at the
z liquid-gas interface and hence equals the vapor
l pA1= p oA pressure of the liquid ( p oA ) at the experimentation
1
temperature. The partial pressure of A at the tube
mouth (pA2) can be taken zero, by making volumetric
Liquid A
flow rate of the gas in the channel very high. By
measuring the decrease in the liquid level in the tube
after an experimentation time of θ, the evaporation flux
Fig.1.3 Winkelmann experiment of A, which is equal to the mass transfer flux of A in
the z-direction, can be written as:
ρ A dVA
NA = − , where VA, MA and ρA are volume, molecular weight and
M A S m dθ
density of the liquid respectively. On the other hand, Sm being the cross-sectional area
of the tube,VA= Sm(l -z) and dVA = -Sm dz can be written. If all these are substituted
ρ A dz D AB P
into equation (1-19): = p oA
M A dt RTz (p B ) ln
zθ D AB M A P p oA θ
and ∫ z0
z dz =
ρ A RT ( p B ) ln ∫ o
dθ and finally,
2 D AB M A P p oA
θ
z θ2 − z 02 = (1-28)
ρ A R T (p B ) ln
is obtained. By measuring the liquid levels at the beginning (z0) and at the end (zθ ) of
the experimentation time θ, DAB can be calculated from this equation.
Example-1.3) Measurement of Molecular Diffusivity
The molecular diffusivity of carbon tetrachloride (A) in air (B) will be measured by using
Winkelmann’s method at 1 atm. and 50 oC. The tube filled with liquid carbon tetrachloride till 10 mm
below its mouth is subjected to air flow. After 55 hours and 29 minutes the level of the liquid in the
tube falls 73.8 mm. What is the value of molecular diffusivity? At 50 oC, vapor pressure and the
density of carbon tetrachloride are 282 mmHg and 1 500 kg/m3. MA= 154.
Solution:
From the givens, zo=10 mm and zt =10 +73.8 = 83.8 mm.

760 − (760 − 282)
(p B ) ln = = 608.1 mmHg
ln[760 /(760 − 282)]
θ = (55)(3 600) + (29)(60) = 199 740 sec. Then, from equation (1-28),
[(83.8) 2 − (10) 2 ] *10 −6 (1 500)(0.083)(273 + 50)(608.1)

D AB = = 9.63 *10 −6 m 2 / s
2(154)(1.013)(282)(199 740)
is found.
16
Vaporization of Liquid Drops or Sublimation of Solid Spheres: For the application
of this experiment, one of the components must be either liquid or sublimable solid at
the experimentation conditions. As shown in Fig.1.4 component A, either as liquid
drop or solid sphere in rp diameter, is hanged in a large diameter channel through
which gas B flows at low velocity at the
2 experimentation temperature and pressure.
B A Liquid drop or solid sphere vaporizes or
1 sublimes into the gas at liquid (solid)-gas
interface (point-1) and from there it transfers
into the bulk gas (point-2), because of the
concentration difference exists in radial
Fig.1.4 Vaporization of liquid drops direction. Here, again mass transfer takes place
under the conditions of “A transfers through
non-transferring B”, and hence flux equation,
D AB P
NA = ( p A1 − p A 2 ) (1-19a)
RT r (p B ) ln
is written. Again here, pA1 is the partial pressure of A at liquid (solid)-gas interface,
which is equal to the vapor pressure of A at operating temperature. pA2 is the partial
pressure of A at bulk gas, which can be assumed zero, as the volumetric flow rate of
gas B is large. Vaporization or sublimation flux of component A, which is also equal
to the mass transfer flux of component A in radial direction, can be written as,
ρ A dVA
NA = − , where VA, MA and ρA are volume, molecular weight and density
M A S m dθ
of the liquid drop or solid sphere respectively. From the sphere geometry, Sm = 4π r2
4 3
and VA = π r can be written. If the flow of gas B continues until the drop or sphere
3
evaporates completely, by inserting all the above equations into equation (1-19a), the
equations;
M A D AB P p oA θ M A D AB P p oA rp2
ρ A RT (p B ) ln ∫o
dθ = − ∫r r dr
o
and θ=
p
ρ A RT (p B ) ln 2
are obtained. On the other hand, from the definition of logarithmic mean,
p B2 − p B1 p oA
(p B ) ln =
ln
p B2
=
[
ln P / (P − p oA ) ]
p B1
is written. Substituting this into equation above and by rearranging, finally
ρ A rp2 RT
D AB = (1-29)
2 M A θ P ln[P /( P − p oA )]
is found. By measuring the time θ for complete vaporization or sublimation, DAB is
calculated from the equation above.
In Table.1.1, experimentally measured values of molecular diffusivities of some gas
pairs at 1 atm. pressure and at various temperatures are given. It follows from the table
that the values for most gas pairs are at the order of 10-4 m2/s. It can easily be shown
that for gaseous mixtures DAB = DBA.
17
Example-1.4) Measurement of Molecular Diffusivity
Molecular diffusivity of iodine (A) in air (B) will be measured at 760 mmHg and 25 oC. For this, solid
iodine cast in spherical shape with 4 mm diameter is suspended in a duct through which air flows.
After 22 hours and 54 minutes, iodine sphere completely disappears. What is the value of molecular
diffusivity?
Vapor pressure and density of solid iodine at 25 oC are 1.07 mmHg and 4 930 kg/m3. MA=254.
Solution:
θ = (22)(3 600) + (54)(60) = 82 440 sec.

From equation (1-29),
4 930 * (2 *10 −3 ) 2 * 0.083 * (273 + 25)
D AB = = 8.16 *10−6 m 2 / s
2 * 254 * 82 440 *1.013 * ln[760 /(760 − 1.07)]
is found. It is seen that this value, after temperature correction, is identical with the value given in
Table.1.1.
1.2.8.2 Prediction of Binary Gas Diffusivities: The kinetic theory of the gases is
fairly well developed. Starting from the kinetic theory of the gases, Hirschfelder-
Bird-Spotz derived the theoretical equation below, which can be used to predict the
binary diffusivities of non-polar gas pairs or of a polar gas with a non-polar gas, at the
absence of experimentally found value.
⎛ ⎛ ⎞
0.5 ⎞
10 −4
3
⎜
T 2 1.084 − 0.249 ⎜⎜
1
+
1
⎟⎟ ⎟
⎜ ⎝ M A M B ⎠ ⎟⎠ ⎛ 1 0.5
⎝ 1 ⎞
D AB = ⎜⎜ + ⎟⎟ (1-30)
2
P rAB Ω D,AB ⎝ MA MB ⎠
In the equation above, DAB is molecular diffusivity in m2/s. T and P are absolute
temperature in K, and pressure in N/m2 respectively. MA and MB are molecular
weights of A and B in kg/k-mol. rAB, which is defined as rAB=(rA+rB)/2 , is collision
radius in nm. Ω D,AB , which is given as function of (kT/ ε AB ) in Fig.1.5, is known as
collision function, where k is very well known Boltzmann constant. ε AB , which is
obtained from the force constants (ε/k) of the components by ε AB / k = ε A ε B / k , is
known as energy of molecular attraction. The collision radius and force constants for
some molecules are given in Table.1.2.
Example-1.5) Prediction of Molecular Diffusivity
Predict molecular diffusivity of methane in air at 1 atm. and 0 oC from Hirschfelder-Bird-Spotz

Equation:
From Table.1-2.
ε/k r (nm) M
Methane 148.6 0.3758 A 16
Air 78.6 0.3711 B 29
18
Table 1-1. Experimentally determined binary gas diffusivities at 1 atm. pressure
Temp. Temp.
Gas (Vapor) Pair D *104 m2/s Gas (Vapor) Pair DAB*104 m2/s
(oC) AB (oC)
Acetic acid-Air 0 0.1064 Ethyl formate-Air 0 0.337
Acetic acid-CO2 0 0.0716 Ethylene-H2 0 0.486
Acetic acid-H2 0 0.416 Formic acid-Air 0 0.131
Acetone-Air 0 0.109 H2-SO2 200 1.23
Air-n-Butanol 59 0.104 H2-Su 55.5 1.121
Air-n-Butanol 25.9 0.087 Helium-Nitrogen 20 0.705
Ammonia-Air 0 0.198 n-Heptane-CH4 38 0.066
Ammonia-H2 25 0.784 n-Hexane-H2 15 0.290
Ammonia-H2 85 1.093 Iodine-Air 0 0.07
Ammonia-N2 85 0.328 Mercury-Air 0 0.07
Ammonia-N2 25 0.230 Methanol-Air 0 0.132
Aniline-Air 0 0.061 Methyl acetate-H2 0 0.303
Aniline-Air 25.9 0.074 Methyl formate-Air 0 0.0872
Aniline-Air 59 0.09 Naphthalene-Air 0 0.0513
Argon-Nitrogen 20 0.194 Nitrogen-H2 25 0.784
Benzene-Air 0 0.077 Nitrogen-SO2 -10 0.104
Benzene-CO2 0 0.0528 Nitrogen-Water 34.5 0.256
Benzen-H2 0 0.306 Nitrogen-CO2 25 0.165
CH4-H2 15 0.694 O2-Air 0 0.178
CH4-O2 500 1.1 O2-H2 0 0.697
CO2-Air 44 0.177 O2-Nitrogen 0 0.181
CO2-Air 0 0.138 n-Octane-H2 30 0.271
CO2-H2 0 0.55 n-Octane-O2 30 0.0705
CO2-Helium 25 0.612 Phosgene-Air 0 0.095
CO2-O2 0 0.139 n-Propanol-Air 0 0.085
CO2-SO2 70 0.108 n-Propanol-CO2 0 0.0577
CO2-Water 55.4 0.211 n-Propanol-H2 0 0.315
CO2-Water 34.4 0.202 Toluene-Air 0 0.076
CO-Nitrogen 100 0.318 Toluene-Air 30 0.088
n-Decane-H2 90 0.306 i-Valeric acid-H2 0 0.212
Ethanol-Air 0 0.102 Water-Air 25.9 0.258
Ethanol-CO2 0 0.0685 Water-O2 59 0.305
Ethanol-CO2 67 0.106 Water-O2 450 1.3
19
1.4 0.5
1.2
1 0.4
Ω D ,AB
0.8
Ω D ,AB
0.6 0.3
0.4
0.2 0.2
0.1 1 10 100 1000
kT/ ε AB
Fig. 1.5 Collision function
rA + rB 0.3758 + 0.3711 ε AB εA εB
rAB = = = 0.37345 (nm) = = (148.6)(78.6) = 108.074 (K )
2 2 k k k
kT 273 ΩD,AB = 0.5 is read.
= = 2.53 From Fig.1.5
ε AB 108.074
0.5
⎡ 1 1 ⎤
0.5
⎡1 1⎤
⎢ + ⎥ =⎢ + ⎥ = 0.311
⎣MA MB ⎦ ⎣16 29 ⎦
By substituting all these into equation(1-30)
10 −4 ( 273) 3 / 2 [1.084 − (0.249)(0.311)](0.311)

D AB = = 2 * 10 −5 m 2 / s
(1)(1.013 * 10 5 )(0.37345) 2 (0.5)
is obtained
1.2.8.3 Estimation of Binary Gas Diffusivities: There is large number of empirical

equations developed by analysing large number of experimental results. In the absence
of experimentally obtained values, the suitable ones of these may be used to estimate
the binary gas diffusivities. In using these equations, one must be very careful with the
units of the terms contained in the equations and with the application range of the
equations. The equation given by Fuller-Schettler-Giddings can be successfully used
to estimate the binary diffusivities of polar and non-polar gas pairs with ± % 10
deviation.
1.0 ∗ 10−9 T1.75

1/ 2
⎛ 1 1 ⎞
D AB = ⎜ + ⎟ (1-31)
2 ⎜⎝ M A M B ⎟⎠
P ⎡(∑ v )1A/ 3 + (∑ v )1B/ 3 ⎤
⎢⎣ ⎥⎦
20
Table 1-2. The collision radius and force constants for some molecules
Gas (Vapor) r (nm) ε/k (K) Gas (Vapor) r (nm) ε/k (K)
Acetone 0.4600 560.2 Hydrogen iodide 0.4211 288.7
Acetylene 0.4033 231.8 Hydrogen peroxide 0.4196 289.3
Air 0.3711 78.6 Hydrogen sulfide 0.3623 301.1
Ammonia 0.2900 558.3 Iodine 0.5160 474.2
Argon 0.3542 93.3 Krypton 0.3655 178.9
Arsine 0.4145 259.8 Mercury 0.2969 750.0
Benzene 0.5349 412.3 Mercury dibromide 0.5080 686.2
bi-Butane 0.5278 330.1 Mercury dichloride 0.4550 750.0
bn-Butane 0.4687 531.4 Mercury diiodide 0.5625 695.6
Boron trichloride 0.5127 337.7 Methane 0.3758 148.6
Boron trifluoride 0.4198 186.3 Methanol 0.3626 481.8
Bromine 0.4296 507.9 Methyl acetate 0.4936 469.8
Carbon dioxide 0.3941 195.2 Methyl acetylene 0.4761 251.8
Carbon monoxide 0.3690 91.7 Methyl bromide 0.4118 449.2
Carbon sulfide 0.4483 467.0 Methyl chloride 0.4182 350.0
Carbon tetrachloride 0.5947 322.7 Methyl ether 0.4307 395.0
Carbon tetrafluoride 0.4662 134.0 Methylene chloride 0.4898 356.3
Chlorine 0.4217 316.0 Neon 0.2820 32.8
Chloroform 0.5389 340.2 Nitrogen 0.3798 71.4
Cyanogen 0.4361 348.6 Nitrogen monoxide 0.3492 116.7
Cyclo –propane 0.4807 248.9 Nitrogen oxidul 0.3828 232.4
Cyclo-hexane 0.6182 297.1 n-Pentane 0.5784 341.1
2,2 Dimethylpropane 0.6464 193.4 n-Propyl alcohol 0.4549 576.7
Ethane 0.4443 215.7 Oxygen 0.3467 106.7
Ethanol 0.4530 362.6 Phosphine 0.3981 251.5
Ethyl acetate 0.5205 521.3 Propane 0.5118 237.1
Ethyl chloride 0.4898 300.0 Propylene 0.4678 298.9
Ethyl ether 0.5678 313.8 Silicon hydride 0.4084 207.6
Ethylene 0.4163 224.7 Silicon tetrafluoride 0.4880 171.9
Fluorine 0.3357 112.6 Stannous bromide 0.6388 563.7
Helium 0.2551 10.2 Sulfur dioxide 0.4112 335.4
n-Hexane 0.5949 399.3 Sulfur hexafluoride 0.5128 222.1
Hydrogen 0.2827 59.7 Trimethyl borate 0.5503 396.7
Hydrogen bromide 0.3353 449.0 Uranium hexafluoride 0.5967 207.6
Hydrogen chloride 0.3339 344.7 Water 0.2641 809.1
Hydrogen cyanide 0.3630 569.1 Xenon 0.4047 231.0
Hydrogen fluoride 0.3148 330.0
In the equation above, DAB is molecular diffusivity in m2/s, T and P are absolute
temperature in K and pressure in atm., Σv is the diffusional volume of the molecule in
m3/k-mol, which can be synthesized from the atomic diffusional volumes and the
structural contribution of the molecule, in the absence of the value for the molecule.
Table1.3 gives the diffusional volumes of some atoms and molecules.
21
Chen and Othmer derived an equation using critical volumes and critical
temperatures instead of diffusional volumes.
1/ 2
1.5 ∗ 10 −6 T1.81 ⎛ 1 1 ⎞
D AB = ⎜⎜ + ⎟⎟ (1-32)
P (TcA TcB ) 0.1405
(V
cA
0.4 0.4 2
+ VcB ) ⎝ MA MB ⎠
Here again, temperature, pressure and volumes should be taken in K, in atm. and in
m3/k-mol respectively. DAB will be obtained in m2/s.
1.2.9 Effect of Temperature and Pressure on Gas Diffusivity: In the gases,

molecular diffusivity increases with temperature but decreases with pressure. This is
understandable as the kinetic energy hence the mobility of the molecules raises with
the increasing temperature, and the number of the molecules per unit volume increases
with rising pressure. These dependences are expressed as;
1.75
⎛ P ⎞⎛ T ⎞
(D AB )P ,T = (D AB )P ,T ⎜⎜ 1 ⎟⎟⎜⎜ 2 ⎟⎟ (1-33)
⎝ P2 ⎠⎝ T1 ⎠
2 2 1 1
So, if molecular diffusivity at one temperature and pressure is known, its value at
another temperature and pressure can easily be calculated from the equation above. In
the equation, temperature T is taken in K.
1.3 MASS TRANSFER BY MOLECULAR DIFFUSION IN LIQUIDS:
The integration of general flux equation (1-7) requires that DAB and c are constant.
This is almost so for binary gas mixtures but not so for binary liquids, where both may
vary considerably with concentration. Nevertheless, due to the lack of knowledge of
these changes, equation (1-7) is also used in liquids with average values of DAB and c.
So, the integration of equation (1-7) at steady-state, with constant S results in :
NA D AB c x − N A /( N A + N B )
NA = ln A 2 (1-34)
NA + NB z x A1 − N A /( N A + N B )
where DAB and c are the arithmetic means of the molecular diffusivities and total
molar concentrations evaluated at the two ends of diffusional path. xA, which is
defined as x A = c A / c , is the mole fraction of component A in the liquid .
When mass transfer takes place under the condition of “equimolar counter transfer of
A and B”, equation (1-34) simplifies to:
D AB c D
NA = ( x A1 − x A 2 ) = AB (c A1 − c A 2 ) (1-35)
z z
On the other hand, if the transfer is under the conditions of “A transfers through non-
transferring B”, equation (1-34) simplifies to:
D AB c 1 − x A2 D AB c
NA = ln = ( x A1 − x A 2 ) (1-36)
z 1 − x A1 z( x B ) ln
x − x B1
where, xB is given as ( x B ) ln = B2
ln(x B2 / x B1 )
22
Table 1-3. Diffusional volumes of some atoms and molecules
Atom Diffusional volume,v Atom Diffusional volume,v

m3/kg atom *103 m3/kg atom *103
Carbon 16.5 Oxygen 5.48
Chlorine 19.5 Sulfur 17.0
Hydrogen 1.98 Aromatic ring -20.2
Nitrogen 5.69 Heterocyclic ring -20.2
Molecule Diffusional volume,∑ v Molecule Diffusional volume, ∑v

m3/k-mol *103 m3/k-mol *103
Air 20.1 He 2.88
Ar 16.1 Kr 22.8
Br2 67.2 N2 17.9
Cl2 37.7 Ne 5.59
CO 18.9 NH3 14.9
CO2 26.9 N2O 35.9
CCl2F2 14.8 O2 16.6
D2 6.70 SF2 69.7
H2 7.07 SO2 41.1
H2O 12.7 Xe 37.9
1.3.1 Determination of Molecular Diffusivities in Liquids: Molecular interactions in

a liquid are much greater than that of a gas and the formulation of these interactions is
very difficult and as a result of this, the kinetic theory of the liquids is not so
developed as the gases. Hence, there is no reliable theoretical equation for the
prediction of binary diffusivities in liquids.
1.3.1.1 Experimental Method: For the experimental determination of binary
diffusivities of liquids, two-cell method is frequently used. As it is shown in Fig.1.6,
this equipment consists of two cells of volume V each, separated with a porous disc of
thickness δ, and equipped with stirrers. Two different strengths of dilute binary
solutions are prepared and put in each cell, and then the stirrers are set on motion. If
c oA 2 > c oA1 , component A transfers by molecular diffusion from cell-2 to cell-1 through
the stagnant liquid filled the porous disc. Assuming steady-state, the concentration
∂c c − c A1
gradient at any moment can be written as: A = A2 , where constant K, which
∂z Kδ
is greater than 1, emphasizes the fact that diffusion path is always greater than δ. Since
the solutions are dilute, by neglecting bulk flow contribution,
dc A c − c A1
N A = J A = − ε D AB = ε D AB A2 (1-37)
K dz Kδ
can be written, where ε shows the fraction of the area which is open to mass transfer
in the porous disc.
23
No part of this e-book may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
V
cA1
1
stirrer
z δ
2 porous
disc
V cA2
Fig.1.6 Experimental set-up for two-cell method
The component A transferring from cell-2 to cell-1 causes an accumulation in this cell.
Hence,
dc ε Sm D AB
V A1 = (c A2 − c A1 ) (1-38)
dθ Kδ
is written, where Sm is the cross-sectional area of the disc. Similarly, component A
leaving the cell-2 causes a depletion in this cell and hence, equation,
dc ε Sm D AB
− V A2 = (c A2 − c A1 ) (1-39)
dθ Kδ
is also written. If we add equation (1-38) to the equation (1-39),
dc − dc A2 d(c A2 − c A1 ) 2 ε S m D AB
V A1 = −V = (c A2 − c A1 ) (1-40)
dθ dθ Kδ
is obtained. If the variables are separated and integrated,
c θA2 −cθA1
⌠ d (c A2 − c A1 ) 2 ε S m D AB θ
−⎮
⌡c c A2 − c A1
=
KδV ∫o dθ and finally,
o
A2
−c A1
o
KδV c oA2 − c oA1

D AB = ln (1-41)
2 ε Sm θ c θA2 − c θA1
is obtained, where c oA1 , c oA 2 , c A1 , c A 2 are molar concentrations of component A in
the cells at the beginning (θ =0) and at the end (θ = θ) of the experiment. The constants
of the experimental set-up can be collected under one constant, α = (K δ V/2 ε S m ) , and
this constant can easily be determined by conducting an experiment with a liquid pair
whose molecular diffusivity is already known.
Experimentally measured diffusivities of some binary liquids are given in Table.1.4.
As it was stated before, molecular diffusivities in liquids are also dependant on the
concentration of solution. By comparing Table.1.4 with Table.1.1, it can be realized
that values of molecular diffusivities of binary gases are about ten thousand times
higher than the values of molecular diffusivities in binary liquids.
24
Example-1.6) Measurement of Molecular Diffusivity in Liquids
Molecular diffusivity of methanol (A) in water (B) will be measured at 25 oC in a two-cell

experimental set-up whose cell constant is not known. To the cell-1 and cell-2 pure water and
methanol solution with 0.085 k-molA/m3 strength are charged. After 63 hours and 36 minutes,
methanol concentrations in cell-1 and cell-2 are measured as 0.0195 k-molA/m3 and 0.0655 k-
molA/m3 respectively.
In order to find the cell constant, an experiment with formic acid(A)- water(B) system whose
molecular diffusivity at 25 oC is known as DAB=1.52*10-9 m2/s is conducted with initial concentrations
of formic acid in cell-1 and cell-2 being as 0.0 and 0.12 k-molA/m3 and these changing to 0.025 k-
molA/m3 and to 0.095 k-molA/m3 after 48 hours and 28 minutes experimentation time.
What is the molecular diffusivity of methanol in water at 25 oC and within the concentration range
used?
Solution:
First, find the cell constant α. From the givens: θ = (48)(3 600) + (28)(60) = 174 480 sec.
c A1 = 0.0 ; c A 2 = 0.12 k − molA / m 3 ; c θA1 = 0.025 k − molA / m 3 ; c θA 2 = 0.095 k − molA / m 3
o o
Then, from equation (1-41);

(1.52 * 10 −9 )(174 480)
α= = 4.92 * 10 −4 m 2
ln[(0.12 − 0.0) /(0.095 − 0.025)]
is found. Now this constant can be used to calculate the molecular diffusivity of methanol in water.
From the givens : θ = (63)(3 600) + (36)(60) = 228 960 sec.
c oA1 = 0.0 ; c oA 2 = 0.085 k − molA / m 3 ; c θA1 = 0.0195 k − molA / m 3 ; c θA 2 = 0.0655 k − molA / m 3
Then, from equation (1-41) ;
4.92 * 10 −4 0.085 − 0.0
D AB = ln = 1.32 * 10 −9 m 2 / s
228 960 0.0655 − 0.0195
is obtained. As it is seen this value is only 6.5% greater than the value given in Table.1.4.
1.3.1.2 Estimation of Liquid Diffusivities: There is large number of empirical

equations derived by various scientists in terms of physical variables of the
components and the mixture. Most of them are for dilute solutions and have
application limitations.
The equation given by Wilke and Chang can be used to estimate the binary
diffusivities in liquids at a temperature range of 5-40 oC, when the solution is dilute for
solute A.
1.17 ∗10 −16 (φ B M B ) 0.5 T
D oAB = (1-42)
VA0.6 µ
In the equation, µ is the viscosity of the solution in kg/m s, T is absolute temperature
in K, VA is the molar volume of solute A at normal boiling temperature in m3/k-molA,
DAB is molecular diffusivity of solute A in solvent B in m2/s, MB is the molecular
weight of solvent B in kg/k-mol B, φ B is the association factor of solvent B, which is
2.6 for water, 1.9 for methanol, 1.5 for ethanol, 1 for benzene, ether and non-polar
solvents such as aliphatic hydro-carbons. Superscript (o) on DAB means that solution is
dilute for solute A. Molar and atomic volumes of some components at normal boiling
temperature are given in Table.1.5. The equation above gives the molecular
diffusivities of the solutions whose solvent is water, with ± % 10-15 deviation, and
with up to ± % 25 deviation for other solutions. This equation is recommended for
25
solutes whose molar volumes are below 400*103 m3/k-molA. When solute A is water
the value obtained from the equation must be multiplied with 0.453.
Reddy and Doraiswamy obtained a pair of equations, which can be used when the
association factor of the solvent is not available.
10 ∗ 10 −17 M 0B.5 T
For (VB/VA) < 1.5 D oAB = (1-43)
µ (VA VB )1/ 3
8.5 ∗10 −17 M 0B.5 T

For (VB/VA) ≥ 1.5 D oAB = (1-44)
µ (VA VB )1 / 3
The accuracy of these equations is almost the same with equation (1-42).
Othmer and Thaker gave an equation which is very simple and used only when the
solvent B is water.
1.11 ∗ 10 −13
D oAB = (1-45)
µ1.1 VA0.6
In the equations (1-43), (1-44) and (1-45) , µ is the viscosity of the solution in kg/ms,
VA and VB are the molar volumes at normal boiling temperature in m3/k-mol, T is the
absolute temperature in K and D oAB is the molecular diffusivity of solute A in solvent
B, when the solution is dilute for solute A.
Example-1.7) Estimation of Liquid Diffusivities
Estimate the molecular diffusivity of dilute ethanol in water at 15 oC from;

a) Wilke-Chang Equation
b) Othmer-Thaker Equation
From Table.1-5 Atomic volumes of Carbon, Hydrogen and Oxygen are read as 0.0148, 0.0037, 0.0074
m3/kg atom.
Hence for ethanol (A) CH3-CH2-OH
VA =(2)(0.0148) + (6)(0.0037) + (1)(0.0074) = 0.0592 m3/k-mol A
For water φB = 2.6 and at 15 oC µB = 1.14 cP

From Wilke-Chang Equation;
(1.17 *10 −16 )[(2.6)(18)]0.5 (273 + 15)

D oAB = 0.6 −3
= 1.10 *10 −9 m 2 / s
(0.0592) (1)(1.14 *10 )
From Othmer-Thaker Equation;

1.11 * 10 −13
D oAB = = 1.05 * 10 −9 m 2 / s
[ −3 1.1
(1)(1.14 * 10 ) (0.0592)]0.6
are found. As it is seen both values are quite close to the value given in Table.1.4.
26
Table 1-4. Experimentally determined molecular diffusivities in liquids at 1 atm.
Solute (A) Solvent (B) Temperature(oC) Concentration DAB *109 m2/s

(k-mol A/m3)
Acetic acid Acetone 25 0 3.31
Acetic acid Benzene 25 0 2.09
Acetic acid Water 9.7 0.05 0.769
Acetic acid Water 25 0.05 1.26
Acetone Water 25 0 1.28
Acetylene Water 25 0 1.78
Ammonia Water 5 3.5 1.24
Benzene Chloroform 15 0 2.51
Benzene Water 25 0 1.0
Benzoic acid Acetone 25 0 2.62
Benzoic acid Benzene 25 0 1.38
Benzoic acid Water 25 0 1.21
n-Butanol Water 15 0 0.77
Butyric acid Water 25 0.05 0.92
Carbon dioxide Water 25 0 2.0
Chloroform Ethanol 20 2 1.25
Ethanol Benzene 15 0 2.25
Ethanol Chloroform 15 0 2.20
Ethanol Water 10 3.75 0.50
Ethanol Water 10 0.05 0.83
Ethanol Water 10 0 0.84
Ethanol Water 15 0 1.0
Formic acid Benzene 25 0 2.28
Formic acid Water 25 0 1.52
Glycerin Water 25 0 0.94
HCl Water 10 9 3.3
HCl Water 10 2.5 2.5
Hydrogen Water 25 0 6.3
Iodine Benzene 25 0 1.98
KCl Ethylene glycol 25 0.05 0.119
KCl Water 25 0.05 1.87
Methanol Water 25 0 1.24
Methanol Water 15 0 1.28
Oxalic acid Water 25 0 1.61
Oxygen Water 18 0 1.98
Oxygen Water 25 0 2.41
Phenol Ethanol 25 0 0.89
n-Propanol Water 15 0 0.87
Propionic acid Water 25 0.05 1.01
Tartaric acid Water 25 0 0.80
Toluene n-Hexane 25 0 4.21
Water Ethanol 25 0 1.13
Water Glycerin 25 0 0.021
27
Table 1.5 Molar and atomic volumes at normal boiling temperature
Atom AtomcicVVolume
Atomi olume
m33/100
m
3
0 atom×103
/kg atom*10
Bromine 27.0
Carbon 14.8
Chlorine (as R-CHCl-R) 24.6
(end as R-Cl) 21.6
Chromium 27.4
Fluorine 8.7
Hydrogen 3.7
Iodine 37.0
Lead 46.5-50.1
Mercury 19.0
Nitrogen
1 double bond 15.6
1 primary amine 10.5
1 secondary amine 12.0
Oxygen (outside below) 7.4
1 double bond in carbonyl 7.4
bonded to other elements
aldehyde and ketons 7.4
methyl esters 9.1
methyl ethers 9.9
ethyl esters and ethers 9.9
higher ester and ethers 11.0
acids (-OH) 12.0
bonded to S, P, N 8.3
Phosphorous 27.0
Rings
1 three members -6.0
1 four members -8.5
1 five members -11.5
1 six members -16.0
1 naphthalene -30.0
1 anthracene -47.5
Silicon 32.0
Sulfur 25.6
Tin 42.3
Titanium 35.7
Zinc 20.4
Molecule Molar Volume, V Molecule Molar Volume, V
m3/k-mol ×103 m3/k-mol ×103
Air 29.9 H2S 32.9
Br2 53.2 I2 71.5
Cl2 48.4 N2 31.2
CO 30.7 NH3 25.8
CO2 34.0 NO 23.6
COS 51.5 N2O 36.4
H2 14.3 SO2 44.8
H2O 18.8 O2 25.6
28
1.3.2 Molecular Diffusivity in Concentrated Liquid Solutions: The molecular
diffusivity in concentrated liquid solutions differs from that in dilute solutions, because
of the changes in viscosity with concentration and also because of the changes in the
degree of non-ideality of the solutions. Leffler and Cullinan proposed the following
empirical equation by analysing the experimentally measured diffusivities in
concentrated solutions.
⎛ ∂ lnδ A ⎞
D AB µ m = (D oAB µ B ) x B (D oBA µ A ) x A ⎜1 + ⎟ (1-46)
⎝ ∂lnx A ⎠
This equation is used to estimate the molecular diffusivity of solute A in concentrated
solutions whose solvent B does not associate. In the equation, D oAB is the molecular
diffusivity at infinite dilution in B and D oBA is the molecular diffusivity of B at infinite
dilution in A. µ m , µ A , µ B are viscosities of the solution, solute A and the solvent B
respectively.The activity coefficient δ A can be obtained from liquid-vapor
equilibrium data as the ratio of real to ideal partial pressure of A in vapor in
equilibrium with a liquid of concentration xA.
p = po x for ideal solutions (Raoult’s law)
A A A
p = δ po x for non-ideal solutions
A A A A
y P
δ A = oA
pA x A
A graph of log δ A versus logxA is first constructed, then the derivative dlog δ A /dlogxA
at any xA, is obtained from the slope of this graph.
1.3.3 Molecular Diffusivities in Electrolyte Solutions: As it is known, molecule

dissociates in cations and anions in the electrolyte solution. As the sizes of the ions are
smaller than the size of the molecule, mobility of the ions is quite different than the
molecule. It is expected that smaller ions will diffuse at higher rates than the larger
ions. But this is not so, because of the fact that electrical charge cannot be separable.
Nernst has given the following equation for molecular diffusivity of ionic solute A in
infinitely dilute solution with solvent B.
RT λ λ Z + Z o o
λ λ Z +Z o o
D = o + −
= 8.91*10 T
+ − −14 + −
(1-47) + −
F λ +λ λ +λ
AB 2 o o o o
+
ZZ − + −
ZZ + − + −
where F is the Faraday constant in A s/g-equiv., D oAB

is molecular diffusivity at
infinite dilution in m2/s, λ o+ and λ o− are conductances of anion and cation in
(A/cm2)(cm/V)(cm3/g-ekiv.), and Z+ and Z- are the valences of cation and anion, and
T is absolute temperature in K. Ionic conductances of some ions at infinite dilution are
given in Table.1.6.
Example-1.8) Molecular Diffusivity in Electrolyte Solution
Calculate the molecular diffusivity of sulphuric acid ( H2SO4) in water at 20 oC when the solution is
dilute for sulphuric acid.
.Remember that sulphuric acid is ionized in water as H+ and SO =4 . Hence Z+ = 1 and Z_= 2.
29
From Table.1.6 λ o+ = 349.8 and λ o− = 80. Substituting all these into equation (1-47),
(349.8)(80) (1 + 2)
D AB = (8.91 * 10 −14 )(293) .
(349.8 + 80) (1)(2)
DAB= 2.55*10-9 m2/s
is found.
Table 1-6. Ionic conductances of some ions at infinite dilution
Cation λo+Anion λo−

Ag+ 61.9 Br- 78.4
H+ 349.8 Cl- 76.35
Li+ 38.7 Cl O 3− 64.6
Na+ 50.1 ClO −4 67.6
K+ 73.5 F- 55.4
-
NH −4 73.6 I 76.8
Ca+2 −
59.5 NO 3 71.46
Cu+2 56.6 OH- 198.6
Mg+2 53.0 CO 3−2 69.6
Zn+2 52.8 SO −42 80.0
1.3.4 Effect of Temperature on Molecular Diffusivity in Liquids: The change of

molecular diffusivity in liquids with temperature is given by the equation below:
⎛ D AB µ ⎞ ⎛D µ⎞
⎜ ⎟ = ⎜ AB ⎟ (1-48)
⎝ T ⎠ T 2 ⎝ T ⎠ T1
Since the viscosity of the solution decreases with increasing temperature, nothing can
be said about the change of diffusivity with temperature.
1.3.5 Molecular Diffusivity in Multi-Component Liquid Solutions: Mass transfer
flux of solute A in liquid solutions containing more than two components can be
n
calculated from the flux equations derived for binary solution by using ∑ N i in place
i=A
of NA+ NB and by replacing DAB with effective diffusivity, DAef. Perkin and
Geankoplis have given the following equation for the effective diffusivity of solute A,
which is dilute in the strong solutions of B and C.
m = x B D AB µ B + x C D AC µ C
D oAef µ 0.8 o 0.8 o 0.8
(1-49)
µ m , µ B and µ C are the viscosities of solution, components B and C .
1.4 CONTINUITY EQUATION FOR A BINARY MIXTURE:
A general equation for mass transfer of a component of a binary mixture of A+B can
be derived by considering all the possible changes such as molecular diffusion, bulk
30
z
(nAx)x (nAx)x+∆x
∆z
y T
∆y
∆x
x
Fig.1.7 Differential volume in mixture
flow, chemical reaction at unsteady-state. Let us consider a differential volume, as

shown in Fig. 1.7, within a binary fluid mixture and write the mass balance for
component A for this differential volume:
Mass rate of inflow of A - mass rate of outflow of A + mass rate of formation of A

= mass rate of accumulation of A.
Let us find the mathematical equivalents of these expressions and substitute them into
equation. Assume that component A enters this differential volume through three faces
with a common corner at T and leaves it through other three faces. Hence, rate of mass
flow of A in:
(n Ax ) x ∆ y ∆ z + (n Ay ) y ∆ x ∆ z + (n Az ) z ∆ x ∆ y and rate of mass flow of A out:
(n Ax ) x + ∆x ∆ y ∆ z + (n Ay ) y + ∆y ∆ x ∆ z + ( n Az ) z + ∆z ∆ x ∆ y , where n Ax is the total mass
flux of A in x-direction and subscripts x and x + ∆x outside the brackets show its
values at points x and x + ∆x respectively. If component A forms from component B
with a chemical reaction and its mass formation rate in unit volume is rA (kg A/m3 s),
then its mass rate of formation is rA ∆x ∆y ∆z . On the other hand, since total mass of
component A in the volume is ∆ x ∆ y ∆ z ρ A , where ρ A (kg A/m3) is the mass
density of component A, mass rate of accumulation of component A in differential
volume is then, ∆ x ∆ y ∆ z ( ∂ρ A / ∂ θ) , where θ(s) shows the time. If all these values
are substituted into the above-given mass balance expression:
{[
(n
Ax
)
x + ∆x
− (n
Ax
)
x
]∆y ∆z + [(n Ay ) y + ∆y
− (n
Ay
)
y
] [
∆x ∆z + (n
Az
)
z + ∆z
− (n
Az
)
z
]∆x ∆y}+
∆x ∆y ∆z ( ∂ρ /∂t ) = r ∆x ∆y ∆z
A A
(1-50)
is obtained. If both sides of this equation are divided with ∆x ∆y ∆z and then limits of
each term is taken as ∆x, ∆y and ∆z go to zero;
31
⎛ ∂n Ax ∂n Ay ∂n Az ⎞ ∂ρ A
⎜⎜ + + ⎟+ = rA (1-51)
⎝ ∂x ∂y ∂z ⎟⎠ ∂θ
is obtained. Similar analyses for component B gives:
⎛ ∂n Bx ∂n By ∂n Bz ⎞ ∂ρ B
⎜⎜ + + ⎟⎟ + = rB (1-52)
⎝ ∂x ∂y ∂z ⎠ ∂θ
If these two equations are summed,
∂(n +n ) ∂(n + n ) ∂(n + n )
A B x + A B y
+ A B z + ∂ρ = 0 (1-53)
∂x ∂y ∂z ∂θ
is found. This gives total mass balance for the mixture. Note that ρ = ρ A + ρ B and
rA + rB = 0 , where ρ is the mass density of the mixture.
It follows from equation (1-11) that ( n A + n B )z = ρ u z . If the derivative of this with
respect to z is taken,
∂( n A + n B )z ∂u ∂ρ
= ρ z + uz is obtained. If similar equations for x- and y-directions
∂z ∂z ∂z
are written and then derivatives of these are taken with respect to y and z;
∂( n A + n B )x ∂u ∂ρ ∂( n A + n B )y ∂u y ∂ρ
= ρ x + ux and =ρ + uy are also obtained.
∂x ∂x ∂x ∂y ∂y ∂y
Now, if all these equations are substituted into equation (1-53) finally to,
⎛ ∂u ∂u ∂u ⎞ ∂ρ ∂ρ ∂ρ ∂ρ
ρ⎜⎜ x + y + z ⎟⎟ + u x + uy + uz + =0 (1-54)
⎝ ∂x ∂y ∂z ⎠ ∂x ∂y ∂z ∂θ
is reached. This equation is known as “continuity equation for the mixture”. All the
derivatives of ρ is zero, when ρ is constant, then equation (1-54) reduces to:
∂u x ∂u y ∂u z
+ + =0 (1-55)
∂x ∂y ∂z
This equation is known as “continuity equation for incompressible fluids”.
Now, return back to equation (1-51). From equation (1-10),
∂n Az ∂j Az ∂u ∂ρ A
= + ρ A z + uz is obtained. If similar equations to the equation (1-10)
∂z ∂z ∂z ∂z
are written for x- and y-directions and these equations are differentiated with respect to
x and y, and all these three equations are substituted into equation (1-51)
∂ρ ⎛ ∂u x ∂u y ∂u z ⎞ ∂ρ ∂ρ ∂ρ ⎛ ∂j
A ⎜ Ax
∂j ∂j ⎞
Az ⎟
+ρ ⎜ ⎟ =r
A A A Ay
+ + + ux + uy + uz + + + (1-56)
A⎜ ⎟ ⎜ ∂x ⎟ A
∂θ ⎝ ∂x ∂y ∂z ⎠ ∂x ∂y ∂z
⎝ ∂ y ∂ z
⎠
is finally obtained. When the density of the mixture is constant, this equation
simplifies to:
∂ρ A ∂ρ ∂ρ ∂ρ ⎛ ∂j ∂j ∂j ⎞
+ u x A + u y A + u z A + ⎜⎜ Ax + Ay + Az ⎟⎟ = rA (1-57)
∂θ ∂x ∂y ∂z ⎝ ∂x ∂y ∂z ⎠
By dividing both sides of this equation with MA, the molecular weight of component
A, and by noting that; ρ A / M A = c A , rA / M A = R A and j A / M A = J A ;
∂c A ∂c ∂c ∂c ⎛ ∂J ∂J ∂J ⎞
+ u x A + u y A + u z A + ⎜⎜ Ax + Ay + Az ⎟⎟ = R A (1-58)
∂θ ∂x ∂y ∂z ⎝ ∂x ∂y ∂z ⎠
32
is obtained. Since J Ax = −D AB (∂c A / ∂x ) then; ∂J Ax / ∂x = −D AB (∂ 2 c A / ∂x 2 ) . If this and
equivalents of ( ∂J Ay / ∂y ) and ( ∂J Az / ∂z ) are all substituted into equation (1-58)
finally,
∂c A ∂c ∂c ∂c ⎛ ∂ 2c ∂ 2cA ∂ 2cA ⎞
+ u x A + u y A + u z A = D AB ⎜⎜ 2A + + ⎟ + RA
2 ⎟
(1-59)
∂θ ∂x ∂y ∂z ⎝ ∂x ∂y 2
∂z ⎠
is found. This equation simplifies to the equation below, when the velocity of the
mixture is zero and no chemical reaction takes place:
∂c A ⎛ ∂ 2cA ∂ 2cA ∂ 2cA ⎞
= D AB ⎜⎜ 2 + + ⎟ (1-60)
∂θ ⎝ ∂x ∂y 2 ∂z 2 ⎟⎠
This equation is known as Fick’s second law equation.
Equation (1-59), which is continuity equation for component A in a mixture of A+B, is
also known as “general equation for mass transfer”. Solution of this equation for
any geometry under specified initial and boundary conditions gives the concentration
profile of component A, from which mass transfer flux of this component can easily be
calculated.
1.5 MASS TRANSFER BY MOLECULAR DIFFUSION IN SOLIDS:
Transfer of gas, liquid and solid by molecular diffusion in solids play important roles
in some engineering applications. As example leaching, adsorption, drying of solids,
separation of solutions by solid membranes and chemical reactions taking place in the
pores of solid catalysts can be cited. Transfers of solutes in solids proceed under
several ways. Although the transfer mechanisms in the solids are not simple as in the
solutions of gases and liquids, in the majority of them Fick’s law can still be used
successfully. While in some solids diffusion is independent of the structure of the
solid, at the others this is strongly influenced by the nature of the solid. So, these two
situations will be dealt with separately.
1.5.1 Diffusion that is Independent of the Nature of the Solid: This situation is met,
when the solute dissolves and forms a homogeneous solution with the solid. Although
diffusion mechanisms are quite different for many systems, Fick’s first law equation
can be written to calculate the flux of the solute A at steady-state operations.
1.5.1.1 Steady-State Diffusion: At the absence of bulk flow, and when the diffusivity
is independent of the concentration, which are realistic cases in many engineering
applications,
dc
N A = − D AB A (1-61)
dz
can be written. Integration of this equation under steady-state conditions with constant
S yields to:
D (c − c )
N A = AB A1 A2 (1-62)
z
When the mass transfer area changes with z, NA is first replaced with N A /S m and then
the integration is performed. As an example, at the transfer of solute A in radial
direction (z = r) through the wall of a cylindrical pipe,
33
2π l D AB
NA = (c A1 − c A2 ) (1-63)
ln (r2 /r1 )
is obtained, where r1, r2 are the inner and outer radii and l is the length of the pipe.
1.5.1.2 Unsteady-State Diffusion: Many mass transfer processes occurring in solids

proceed under unsteady-state conditions. In this case concentration of solute A not
only depends on location but also on the time. For that, Fick’s second law equation can
be used to determine the concentration profile of solute in the solid. This equation is
solved for various geometries with given initial and boundary conditions.
Diffusion through a slab of 2a, 2b, 2c dimensions: Let us first assume that small
surfaces of the slab, which are the surfaces normal to the x and y-directions, are
insulated against mass transfer. Assume that this solid, whose initial solute
concentration is uniform throughout at c Ao , is dropped into a solution that can dissolve
the solute A, at θ =0. The concentration of solute A at the surfaces of the solid remains
constant at cAs (this concentration is the concentration that the solid would have had, if
the solid had remained in the solution infinitely long time). Thus, c − c is the
Ao As
measure of the solute that can be removed from the solid at the operating conditions. If
the solid is kept in the solution for a θ time, the concentration of solute A in the solid
drops to the uniform concentration of c A . Thus, c A - cAs is the measure of the solute
that remained in the solid and potentially can still be removed, if the contact time is
A A
cAo
Concentration
cA
cA
cAs
z
-a o a
Distance from the
center
Fig.1.8 Concentration profiles in the slab at
unsteady-state mass transfer
prolonged. Hence, the ratio of ( c A - cAs)/( c −c ) shows the fraction of solute A

Ao As
that has not transferred and remained in the solid at the end of time θ. On the other
hand, subtraction of this ratio from 1, gives the fraction of solute A that has already
transferred from solid to the solution. With these, the equation (1-60) simplifies to:
34
∂c A ∂ 2cA
= D AB (1-64)
∂θ ∂z 2
This equation must be solved under the following initial and boundary conditions:
θ<0 -a < z < a cA= cAo = constant
0<θ<∞ z=±a cA = cAs = constant
θ>0 -a < z < a cA = cA
There are different techniques for the solution of partial differential equations such as
above. Method using Fourier transformations yields to:
c − c As ⎛D θ⎞ 8 1 1 −mβ
F = A = f ⎜ AB2 ⎟ = 2 (e −mβ + e −mβ + 1
e + .........) = Fa
1
(1-65)1
cAo − c As ⎝ a ⎠ π 9 25
where m and β1 are m = π2/4 and β1 = DABθ/a2. Function Fa is given in Fig.1.9.
If mass transfer is allowed from the small surfaces of the slab, equations similar to the
1
2a
Fa , Fb , Fc (slab)
2c
2b
Fr (cylinder)
0.1
2a
2c
Fa Fs (sphere)
Fb
Fc
Fr
Fs
0.01
x 2a
y
0.001
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
D AB θ D AB θ D AB θ
β1= β2= β 3=
a2 b2 c2
Fig.1.9 Values of Functions Fa, Fb, Fc, Fs and Fr
35
equation (1-65) are found for these surfaces. Finally, the equation for mass transfer
from all the surfaces of the slab becomes;
c − c As ⎛D θ⎞ ⎛D θ⎞ ⎛D θ⎞
F = A = f ⎜ AB2 ⎟ f ⎜ AB2 ⎟f ⎜ AB2 ⎟ = Fa Fb Fc (1-66)
cAo − c As ⎝ a ⎠ ⎝ b ⎠ ⎝ c ⎠
D θ D θ
where β2 = AB2 β 3 = AB2 . Functions Fb and Fc are also given in Fig.1.9
b c
Diffusion through a cylindrical solid: If the solute A diffuses through a cylindrical

solid of radius a, length 2c, to the solution surrounding the solid, Fick’s second law
equation is first written in the cylindrical coordinates and then solved with suitable
initial and boundary conditions. The function Fr, which gives the concentration profile
of solute A in radial direction is thus obtained. The profile in x-direction is given by
the same function obtained for the slab. Thus, for mass transfer from all the surfaces of
cylinder,
c − c As ⎛D θ⎞ ⎛ D θ⎞
F = A = f ⎜ AB2 ⎟ f ′ ⎜ AB2 ⎟ = Fc Fr (1-67)
cAo − c As ⎝ c ⎠ ⎝ a ⎠
is written. Function Fr was also added to Fig.1.9.
Diffusion through a solid sphere of radius a: When the solute A transfers from a
solid sphere into a solution surrounding the solid, Fick’s second law equation is first
written in the spherical coordinates and then solved with the appropriate initial and
boundary conditions. Result is;
c − c As ⎛D θ⎞
F = A = f ′′ ⎜ AB2 ⎟ = Fs (1-68)
cAo − c As ⎝ a ⎠
Function Fs is also plotted in Fig.1.9.

The equations given above can also be used, when solute A transfers from solution to
the solid.
In the slab and cylinder geometries mass transfer is assumed to take place from the
both faces in a direction. If this is not the case (mass transfer takes place from only one
of the faces in one direction), to the denominator of β in this direction 4 is added,
because length of the diffusion path, in this case, is twice.
Example-1.9) Unsteady-State Diffusion in Solid
Cotton seeds which contain 18 kg oil per m3 of solid and are pressed in the form of slabs with 12 mm
x 8 mm x 3 mm dimensions, are immersed in hexane to extract the oil. Calculate their oil content
after 1 hour of contact. The solution is well mixed so that resistance to mass transfer is only in the
solid phase. Molecular diffusivity of oil in solid at the operating conditions is 4.1*10-10 m2/s.
Givens : Asked :
c Ao = 18 kg oil / m 3 of solid cAs = 0 c Ao = ?
2a = 3 mm, 2b = 8 mm, 2c = 12 mm, DAB = 4.1*10-10 m2/s
θ = 1 hour
36
For mass transfer from all the surfaces of the slab,
c A − c As ⎛ D θ⎞ ⎛ D θ⎞ ⎛ D θ⎞
F = = f ⎜ AB2 ⎟ f ⎜ AB2 ⎟f ⎜ AB2 ⎟ = Fa Fb Fc (1-66)
c Ao − c As ⎝ a ⎠ ⎝ b ⎠ ⎝ c ⎠
D θ ( 4.1*10 −10 )(1)(3600) From Fig.1-9 Fa = 0.16
β 1 = AB2 = = 0.656
a (1.5 *10 −3 ) 2
D θ (4.1*10 −10 )(1)(3600) From Fig.1-9 Fb = 0.63
β 2 = AB2 = = 0.093
b (4 *10 −3 ) 2
D AB θ (4.1 *10 −10 )(1)(3600)

β3 = = = 0.041 From Fig.1-9 Fc = 0.78
c2 (6 *10 −3 ) 2
cA − 0
= (0.16)(0.63)(0.78) = 0.0786
18 − 0
c A = 1.42 kg oil / m 3 of solid is found.
1.5.2 Diffusion that is Dependent on the Nature of the Solid: As it has been seen,
the Fick’s first and second law equations can be used for the calculation of mass
transfer flux, when the diffusion is independent of the nature of the solid. On the other
hand, in some cases, the mass transfer is strongly influenced from the type and the size
of the pores in the solid, and the terms showing the effects of these appear in the flux
equations.
1.5.2.1 Diffusion of Liquids in Solids: Let us assume that the pores of a solid, as
shown in Fig.1.10, is filled with a binary liquid solution of A+B and molar
concentrations of solute A, which are cA1 and cA2, are different at two faces such as
(cA1> cA2). As a result of this, solute A transfers from face-1 to face-2, through the
A
A+B
A+B
A
z
1 2
Fig.1.10 Diffusion of liquids through porous solid
pores of the solid. It is obvious from the figure that the transfer path is greater than
z2-z1 and the mass transfer area is smaller than Sm, total area of each face of the solid.
With these facts in consideration, total molar flux of A, neglecting the bulk flow is
written as:
ε c −c
N A = 2 D AB A1 A2 (1-69)
kt z 2 − z1
37
where ε and kt, which must be found experimentally, are the void fraction of the solid
and the tortuousity factor. Notice that mass transfer area in this case, is εSm. One of
the tortuousity factors accounts for the fact that true mass transfer path is greater than
z2-z1 and corrects it, the other one emphasizes the fact that pores at the faces make
angle with the surfaces and corrects it. DAB, which is the molecular diffusivity of
solute A in solvent B, is not influenced from the solid. This DAB may be grouped with
ε and kt in a way given by equation (1-70) that the resultant diffusivity is known as
effective diffusivity for the system.
DAef=(ε/ k 2t ) DAB (1-70)
1.5.2.2 Diffusion of Gases in Solids: Depending upon the relationship between the
diameter of the pores in the solid and the mean free path of the gas molecules, transfer
of gases in the porous solids takes place at different mechanisms. The mean free path
of the gas molecules is given by;
0.5
3.2 µ A ⎛ RT ⎞
λA = ⎜⎜ ⎟⎟ (1-71)
P ⎝ 2π M A ⎠
where λA(m) is mean free path of the gas molecules, which is defined as the distance
the molecule travels before colliding with another molecule on its way, µA is the
viscosity of the gas(kg/m s), P (N/m2) is total pressure, T(K) is absolute temperature,
and R is the general gas constant, which is 8314 J/k-mol K. The mechanisms that
solute A molecules may encounter during their transfers in a gaseous mixture of A+B
through a porous solid under the concentration difference of (pA1 - pA2) at a constant
total pressure of P are shown schematically in Fig.1.11
Knudsen diffusion: If the mean free path of the molecules is much greater than the
diameter of the pores, the molecules collide with the wall of the pores rather than
colliding with each other. This type of diffusion is known as Knudsen diffusion and
Knudsen diffusion coefficient DKA(m2/s) is given as;
⎛ T ⎞
0.5
D KA = 48.5 d ⎜ ⎟ (1-72)
⎝ MA ⎠
where, d(m) is the diameter of the pore, which can be calculated from
pA1 pA2
NA
(a)
NA
(b)
NA
(c)
Fig.1.11 Mass transfer along the pore (a) by Knudsen diffusion, (b) by Molecular
diffusion, (c) by Transition diffusion
38
4ε
d= (1-73)
Sk ρ b
In the equation above, ρb (kg/m3), is the bulk density of the solid, Sk(m2/kg) is the
surface area in unit mass of solid and ε is the void fraction.
Hence at steady-state, total molar flux of solute A through a pore of length l (m), is
obtained from:
dc D dp A D P
N A = − D KA A = − KA = KA (y A1 − y A2 ) (1-74)
dz RT dz RTl
As it is seen, transfer of A through the pore is not influenced by the existence of B, as

molecules A collide with the wall of the pore rather than with the molecules of B.
Knudsen diffusion occurs when the Knudsen number, defined by
λ
NKn = (1-75)
d
is greater than 10.
Molecular diffusion: If the diameter of the pore is much greater than the mean free
path of the molecules, molecule-molecule collision rather than molecule-wall collision
dominates throughout the pores, and as a result of this, pores do not have any effects
on the transfer of solute A in a gas mixture of A+B through the pores of a solid.
Hence, in this case, for the total molar flux of A equation (1-7) can be used. This
equation can be written as,
D dy A
N A = − AB + y A (N A + N B ) (1-76)
RT dz
By defining NR=NA/(NA+NB) , the equation (1-76) can also be written as;
D AB P dy A D AB dp A
NA = − =− (1-77)
(1 − y A /N R ) dz (1 − y A /N R ) dz
Upon integration of this equation at steady-state with S=constant, finally;
D P N − y A2
N A = N R AB ln R (1-78)
RTl N R − y A1
is obtained. Equation (1-78) is valid, when Knudsen number < 0.01.
Transition (mixed) diffusion: If the Knudsen number is greater than 0.01 but smaller
than 10, both molecule-molecule and molecule-wall collisions are important in the
pores. This case is known as transition or mixed diffusion, and a flux equation for this
case can be derived as follows: The loss in the momentum of A molecules, when they
travel dz distance in the pores and collide with the walls of the pores is found by
multiplying dpA, obtained from equation (1-74) with Ac, which is cross-sectional area
of the pores;
RT
− (dp A ) K A c = N A dz A c (1-79)
D KA
Similarly, momentum loss due to the molecule-molecule collision is found from
equation (1-77) as;
RT
− (dp A ) M A c = N A (1 − y A /N R ) dz A c (1-80)
D AB
39
Hence, total momentum loss of the gas is obtained by summing the two equations
above,
RT RT
-(dpA) Ac = N A dz A c + N A (1 − y A /N R ) dz A c
D KA D AB
with rearranging,
⎡ 1 ⎤ P dy A
NA = − ⎢ ⎥ (1-81)
⎣ (1 − y A /N R )/D AB + 1/ D KA ⎦ RT dz
and upon integration of this equation at steady-state finally,
D AB P ⎡1 − y A2 /N R + D AB /D KA ⎤
NA = NR ln ⎢ ⎥ (1-82)
RTl ⎣1 − y A1
/N R
+ D AB
/D KA ⎦
is obtained. This equation reduces to the equation (1-74) at low pressures, and to the
equation (1-78) at high pressures.
Example-1.10) Diffusion of Gases in Solid
Oxygen (A) is diffusing in a mixture of oxygen+carbon monoxide at 0.05 atm. and 400 K in the pores
of a solid catalyst. The pores are cylindrical with 4 microns diameter and 80 mm length. At the two
ends of the pores mole fractions of oxygen are 0.10 and 0.02. The flux ratio is NA= - 2NB.
Calculate the total molar flux of oxygen.
Molecular diffusivity of oxygen in carbon monoxide at 1 atm. and 20 oC is 7.84*10-5 m2/s and
viscosity of oxygen at operating conditions is 0.026 cP.
From eqn.(1-71)
0 .5
(3.2)(0.026)(1*10 −3 ) ⎡ (8314)(400) ⎤
λA = = 2.11 *10 − 6 m
(0.05)(1.013 *10 5 ) ⎢⎣ (2π)(32) ⎥⎦
From eqn.(1-75)
(2.11*10 −6 )
N Kn = = 0.528
(4)(1 *10 − 6 )
As 0.01<NKn<10 , mass transfer takes place in the transition regime,
NA NA
NR = = =2
N A + N B N A + (−0.5) N A
0.5
⎛ 400 ⎞
D KA = (48.5)(4)(1*10 −6 )⎜ ⎟ = 6.86 *10 m / s
−4 2
⎝ 32 ⎠
1.75
⎛ 1 ⎞ ⎛ 400 ⎞
D AB = (7.84 * 10 ) ⎜
−5
⎟⎜ ⎟ = 2.71 * 10 m / s
−3 2
⎝ 0.05 ⎠⎝ 273 + 20 ⎠
D AB (2.71 *10 −3 )
= = 3.95
D Kn (6.86 *10 − 4 )
From equation(1-82)
(2)(2.71 *10 −3 )(0.05)(1.013) ⎡1 − (0.02 / 2) + (3.95) ⎤
NA = ln ⎢ ⎥ = 8.4 *10 k − molA / m s
−7 2
is obtained.
(0.083)(400)(80 *10 −3 ) ⎣1 − ( 0 . 10 / 2) + (3 . 95) ⎦
40
Table 1-7. Permeability and Diffusion Coefficients in Some Solids
Permeability
Solubility,s Molecular
Temp., PM
SoluteA Solid B cm 3 A( N.T.P) Diffusivity,DAB
o
C cm3 A( N.T.P)
cm 3 B atm. (m2/s)
cm 2 s (atm. / cm)
H2 Vulcanized rubber 25 0.342 10-6 0.040 8.55 10-10
O2 25 0.152 10-6 0.070 2.17 10-10
N2 25 0.054 10-6 0.035 1.54 10-10
CO2 25 1.003 10-6 0.900 1.11 10-10
H2 Vulcanized 0 - 0.065 0.37 10-10
neoprene
17 0.051 1.03 10-10
27 0.053 1.80 10-10
46.5 0.050 4.81 10-10
H2S Nylon 30 2.60 10-9 5.20 5.0 10-14
Cellulose 30 2.56 10-9 16.0 1.6 10-14
acetate
60 4.64 10-9 9.1 5.1 10-14
Polyvinyl butyral 0 2.25 10-8 15.0 1.5 10-13
30 5.04 10-8 8.0 6.3 10-13
Polyvinyl 30 2.04 10-9 0.3 6.8 10-13
trifluoroacetate
60 5.80 10-9 0.2 2.9 10-12
Mylar A 0 1.43 10-10 11.0 1.3 10-15
60 1.74 10-9 2.8 6.2 10-14
Saran 30 2.69 10-10 2.8 9.6 10-15
45 1.13 10-9 3.9 2.9 10-15
75 7.80 10-9 1.3 6.0 10-13
Air Newspaper 25 0.357
Air Leather 25 0.152-0.684
H2O Paraffin 23 0.160 10-6
H2O Cellophane 38 0.91-1.82 10-6
He Pyrex Glass 0 2.81 10-11
20 4.86 10-11
100 20.06 10-11
Air Porcelain 25 0.81 10-11
He SiO2 20 0.01 2.4-5.5 10-14
H2 Ni 85 0.202 1.16 10-12
125 0.194 3.4 10-12
165 0.192 10.5 10-12
H2 Fe 20 2.59 10-13
CO Ni 950 4.0 10-12
Bi Pb 20 1.1 10-20
Cd Cu 20 2.7 10-19
Al Cu 20 1.3 10-34
41
1.5.3 The Relationship between the Fluxes at the Diffusion of Gases in Solids: At
the transfer of gases through the pores of a solid in a system which is closed to
atmosphere and kept under constant pressure, there is always the relationship Σ Ni = 0.
This is because of the fact that at both ends of the pore total pressure is constant. For a
binary system this leads to: NA = - NB. Hence, it follows from this that in a closed
system at constant pressure mass transfer always takes place under “equimolar counter
transfer conditions”. On the other hand in an open system there is always the
following relationship between the fluxes, regardless of whether mass transfer takes
place by Knudsen, molecular or transition diffusion.
ΣNi √Mi = 0
For a binary system this gives NA√ MA = - NB √ MB. As stated before, different
effects in other cases may govern the relationships between the fluxes.
1.5.4 Molecular Diffusivity of Gases in Solids and the Permeability: Usually, in the
diffusion of gases through solids, the permeability, instead of molecular diffusivity, is
used. The permeability, PM is defined as the volume of the gas as cm3, measured at 1
atm. and 0 oC, that passes through 1 cm2 surface of the solid of 1 cm thick at 1 second
under a pressure difference of 1 atm. If the solubility of the gas in the solid is s (cm3
gas/cm3 solid atm.) the relationship among permeability, molecular diffusivity and the
solubility is given
as;
PM = 104 DAB s (1-83)
Hence, if the solubility of a gas in solid and the permeability of the solid for this gas
are known, the molecular diffusivity of this gas through this solid can easily be
calculated from the equation above. In Table.1.7, the solubilities, the permeabilities
and molecular diffusivities for some gas-solid pairs are given.
PROBLEMS
1.1 Across a gas film of thickness 0.2 mm, components A and B are diffusing in opposite directions at
2 bars and 25 oC. Under steady-state conditions, total molar flux of A is twice that of B. Partial
pressures of A at each side of the film are 0.40 bar and 0.10 bar. Calculate the total molar fluxes of A
and B. Molecular diffusivity of A in B at 0 oC and 1 bar is 2*10-5 m2/s.
[ Ans. NA= - NB =
1.2 Equimolar counter transfers of N2 and CO are occurring by molecular diffusion at steady-state in a
tube 0.11 m long. The partial pressures of N2 at each end are 80 mmHg and 10 mmHg.
a) Calculate the total fluxes of the components as kg/m2s at 298 K and 1 atm.
b) Repeat the calculations at 473 K and 1 atm. Do the fluxes increase?
c) Repeat the calculations at 298 K and 3 atm. Do the fluxes change?
[Ans. a) NA = 7.36*10-7 k-mol A/ m2s ]
1.3 In a binary laminar gas mixture, equimolar counter transfers of A and B occurs at 1 bar pressure.
The molar concentrations of A at point one and point two, which are 2 mm apart, are measured as 0.04
k-mol/m3 and 0.08 k-mol/m3 respectively. Temperature in the gas phase does not remain constant and
changes with distance as T = T1e-200z , where T1 is the temperature at point 1 and its value is 305 K, z
is distance in m.
Calculate the total molar flux of A. Molecular diffusivity at 1 bar and 305 K is 2.5*10-5 m2/s.
42
[Ans. NA = 1.4*10-4 k-mol A/m2s ]
o
1.4 Water at 25 C is flowing in a covered irrigation pipe below ground. In every 30 m there is a vent
line 25 mm inside diameter and 300 mm long to the atmosphere which is at 760 mmHg and 25 oC.
There are 10 vents in 300 m pipe. The outside air can be assumed to be dry.
Calculate daily water loss as kg. The vapor pressure of water at 25 oC is 23.8 mmHg.
[ Ans. 8.55*10-4 kg water / day ]
1.5 Water vapor is diffusing at steady-state through stagnant air in a conical channel at 54 oC and 1
bar. The height of channel is 10 meters and the diameter of it changes uniformly from 0.8 m at the
bottom to 0.4 m at the top. The partial pressures of water vapor at the bottom and at the top of channel
are 2 500 Pa and 500 Pa, respectively.
If air is non-transferring, calculate:
a) The molar rate of transfer of water vapor as kg/h,
b) The molar fluxes of water vapor at the top and at the bottom of the channel.
[Ans. a) N A = 4.29 *10 −5 kg water / h ]
1.6 A gaseous mixture consisting of A+B is contacted with a liquid solvent S, which can dissolve only
component A and itself does not evaporate into the liquid at the operating conditions. The two phases
flow counter-currently in laminar flow regimes. Considering molecular diffusions and bulk flows of
the components write the appropriate expressions on the arrows.
Interface
Gas phase(A+B) Liquid phase(S+A)
1.7 In a catalytic reactor, the dimerization reaction 2A A2 is being carried out. Each
catalyst particle is surrounded by a laminar gas film of 0.16 mm thickness through which gas A
diffuses in order to arrive at catalyst surface. Reaction occurs instantaneously on the catalyst surface
and product A2 diffuses back through the same gas film to the bulk gas composed of equimolar A and
A2.
a) Calculate the total molar fluxes of A and A2 at 140 oC and 1 bar pressure.
b) Find the distance from the catalyst surface where the mole fraction of A is 0.25.
Molecular diffusivity at the operating conditions is 2.4*10-5 m2/s.
[ Ans. a) NA = 2.55*10-3 k-mol A /m2s, b) 0.074 mm ]
1.8 Hydrogen is being oxidized on a solid catalyst surface according to the reaction below:
2H2+O2 2H2O
H2 and O2 diffuse through a laminar gas film of 0.2 mm thickness to the catalyst surface, react there
instantly with complete conversion, and H2O diffuses back through the same film into the bulk gas. At
the bulk gas at 300oC and 2 atm total pressure, the mole percents of the components are 50, 25, and 25
for H2(A), O2(B) and H2O(C) respectively.
43
Calculate:
a) The effective diffusivity of H2 in O2 - H2O mixture.
b) Total molar fluxes of H2 , O2 and H2O.
The binary diffusivities at 200 oC and 1 atm are DAB=1.8*10-4 m2/s, DAC=2.1*10-4 m2/s and
DBC=5.9*10-4 m2/s. [Ans. a) DAef =1.47*10-4 m2/s, b) NA = 0.018 k-mol/m2s ]
1.9 The following reaction takes place on a solid catalyst surface at 4.2 bar and 323 oC.
A(g) + 3 B(g) 4 C (g)

The mole fractions of the components at the left and right side of the gas film adjacent to the solid
catalyst surface are given as;
yA yB yC
Left side 0.20 0.60 0.20
Right side 0.05 0.15 0.80
Calculate the total molar fluxes of each component by assuming that thickness of the film is 0.1 mm.
Binary diffusivities at 1 bar and 25 oC are given as DAB =1*10-5 m2/s, DAC = 2*10-5 m2/s, DBC= 1.5*10-5
m2/s.
1.10 In the diffusion system shown on the Figure, pure liquid A evaporates into a gas B at constant
pressure and temperature. During an experiment under steady-state conditions, the position of liquid-
gas interface is kept fixed at z = z1, and the mole fraction of A is yA1, which corresponds to
equilibrium with the liquid at the interface. The solubility of B in A is negligible. At the tube mouth
(z = z2) mole fraction of A remains constant at yA2.
a) Derive the following equation for the total molar flux
of A at any z B A+B
cD AB 1 − y A
NA = ln 2 z2
z − z 1 1 − y A1
b) Derive the following equation for the concentration profile
of B in the gas phase. 1 z1
z − z1
y B ⎛ y B 2 ⎞ z 2 − z1 A
=⎜ ⎟
y B1 ⎜⎝ y B1 ⎟⎠
For the case t= 23 oC, P = 1 bar, DAB = 8.35*10-6m2/s, z2-z1= 150 mm and vapor pressure of A at 23 oC
100 mmHg, calculate:
c) The total molar flux of A,
d) The distance where the partial pressure of A is the half of that at the liquid-gas interface.
Due to the large flow rate of gas B, the partial pressure of A at the tube mouth may be taken zero.
1.11 Predict the molecular diffusivity of CO2 in Cl2 at 1 bar and 25 oC from Hirschfelder-Bird-Spotz
equation.
1.12 Calculate the molecular diffusivity of copper sulfate ( CuSO4) in water at 25 oC, when the
solution is dilute for copper sulfate. Remember that copper sulfate ionizes in water as Cu++ and SO =4 .
1.13 Prove that in a binary gas mixture DAB = DBA.
1.14 Derive equation (1-20). Hint : Write total molar flux equations for binary and multi-component
gas mixture.
1.15 Derive equation (1-22) starting with equation (1-20).
44
1.16 Starting with Fick’s first law equation show that for steady-state equimolar counter diffusion of
gas A through a non-isothermal medium consisting of A and B, in which T is proportional to zn, the
total molar flux of gas A is given by
(1 − n / 2)(p A1 − p A 2 )
N Az =
R[(Tz / D AB ) 2 − (Tz / D AB )1 ]
where pA is the partial pressure of component A, R is the gas constant, T is absolute temperature, z is
the distance in the direction of diffusion, n is a constant, and subscripts 1 and 2 refer to the two
boundaries between the diffusion takes place. Assume that DAB is proportional to T1.5 and n = 2.
1.17 a).Show that for steady-state diffusion of component A from a cylindrical surface through a non-
transferring gas film of B , the total molar flux of component A at the cylinder surface is given by
D AB P ln(p B 2 / p B1 )
N A1 =
RTa ln(1 + χ / a )
where P is the total pressure, a the radius of the cylinder, χ the thickness of the gas film, and pB1 and
pB2 the partial pressure of component B at the cylinder surface and at the other side of the gas film.
b) A cylindrical brass rod, 12 mm in diameter, is given a protective coat of lacquer. After application
in an acetone solvent, the lacquer is dried in a chamber through which acetone-free air is passed at 70
o
C and atmospheric pressure. If the temperature at the surface of the coating is assumed to remain
constant at the wet-bulb value of 10 oC until drying is complete and acetone is assumed to diffuse from
the rod through a stagnant gas film of 6 mm thick, how long does the lacquer take to dry?
The original lacquer coating contains 10 mg of acetone per cm2 of rod surface. The vapor pressure of
acetone at 10oC is 147 mbar and molecular diffusion coefficient of acetone through air may be taken
as 8.0*10-6 m2/s. Assume that flow rate of B is sufficiently high so that pA2 ≈ 0. [Ans.: b) 147 sec.]
45
Chapter-2
MASS TRANSFER BY TURBULENT DIFFUSION

and
MASS TRANSFER COEFFIENTS
2.1 Introduction: In the discussion of mass transfer, so far the emphasis has been on
molecular transport in fluids that were stagnant or in laminar flow. In much of the
mass transfer applications, the rate of mass transfer by molecular diffusion is too small
and more rapid transfer is necessary. To speed up the transfer, the fluid velocity is
increased so that flow regime changes from laminar to turbulent and as a result of this
mass transfer takes place by turbulent or eddy diffusion. To have a fluid in turbulent
flow requires this fluid to be flowing past another immiscible fluid or a solid surface.
An example of this was already given in Fig.2 in the introduction. When a fluid flows
past a surface under turbulent flow conditions, the actual velocity of small particles
(eddies) of fluid cannot be given mathematically as in laminar flow. In laminar flow
fluid flows in smooth streamlines whose behaviours can be described mathematically.
In turbulent flow there are no orderly streamlines and no equation to describe the
behaviour. There is large number of eddies which move rapidly and randomly in all
the directions.
When a solute is dissolving from a solid surface and being transferred into the fluid,
there is a high concentration of this solute in the fluid adjacent to the solid and its
concentration decreases as the distance from the surface increases.
A typical concentration profile, which is
cA
A explained below, is shown in Fig.2.1. Adjacent

Molar concentration of solute A,
Laminar sublayer
cA1 to the surface, a thin laminar film is present, in
Buffer layer which the mass transfer occurs by molecular
True turbulent core diffusion, since no eddies can penetrate into this
cA layer. Since mass transfer by molecular
cA2 diffusion is a slow process, large concentration
cA=f(z) change or drop in concentration occurs across
0 this laminar film. Adjacent to this layer is the
Distance from surface, z
transition or buffer layer to which some
Fig.2.1 Typical concentration profile eddies can penetrate and mass transfer is by the
in turbulently flowing fluids sum of the molecular diffusion and by turbulent
diffusion. In this layer there is a gradual change from almost pure molecular diffusion
at one end to the turbulent diffusion at the other end. For that, concentration decrease
is much less in this layer. In the true turbulent core adjacent to buffer layer most of
the transfer is by turbulent or eddy diffusion. Molecular diffusion still occurs, but its
contribution is little to the over-all mass transfer in this layer. The concentration
decrease is very small here, since the rapid movement of eddies evens out any gradient
tending to exist. As the average concentration of solute A, c A is very close to the
minimum concentration, cA2, the thickness of laminar sublayer is very small compared
to the thickness of the true turbulent core. Although the thickness of the laminar
sublayer decreases sharply with an increase in turbulence, this can never be made zero.
46No part of this CD-book may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu 46
It was stated that even the motions of the particles of a pure fluid in turbulent flow
cannot be described mathematically with today’s knowledge of us. It can then easily
be realized that the situation will be more complicated when a second component and
hence the mass transfer exist. For that reason, the flux equation for turbulent diffusion
can only be written by analogy to the flux equation for molecular diffusion.
dc A
J A = −(D AB + ε M ) (2-1)
dz
where JA is the molar diffusional flux of A in a turbulently flowing mixture of A+B as
(k-molA/m2s), (dcA/dz) is the concentration gradient causing this diffusion. ε M is
known as turbulent or eddy diffusion coefficient for mass transfer. Although it has
the same dimension with DAB and looks counter part of DAB in turbulent diffusion, it is
not a true physical property as it depends not only on the components but more than
this on the flow conditions of the fluid. Hence, ε M is strongly dependent on z, distance
from the surface of the solid. Although this dependence cannot be given by an
equation yet, it is obvious that ε M =0 at z=0, and it increases with increasing z. If the
mixture itself moves in the transfer direction (bulk flow) the flux given by equation
(2-1) is the flux of component A relative to the molar average velocity of the mixture
defined by equation (1-5). A question may be asked: “ why was DAB added to the
equation (2-1)?” The answer is very simple; “not only in the laminar and buffer layers
but also in the true turbulent core molecular diffusion still exist”.
For the integration of equation (2-1) ε M = f ( z ) is required. It was already said that this
is not known yet. By defining an average ε M , which is independent of z, integration
can easily be performed at constant Sm and at steady-state with boundary conditions; at
z = 0 cA=cA1 and at z = z cA=cA2;
D AB + εM
JA = (c A1 − c A 2 ) (2-2)
z
In general; cA1=cAi, which is equilibrium solubility of component A in B at the
prevailing conditions, and from the above-given explanations c A 2 ≅ c A . In the
equation (2-2) z and ε M are both influenced by the flow conditions and they must be
determined experimentally. Since DAB must also be found experimentally, then all
these three variables are collected under one coefficient, k ′c (m/s), which is known as
mass transfer coefficient and is determined experimentally.
D AB + ε M
k ′c ≡ (2-3)
z
It is obvious that all the parameters effecting DAB, ε M and z will effect the k ′c . So-
defined k ′c is only the mass transfer coefficient of the eddies and molecules diffusing
under the available concentration difference. If any bulk flow exists in the transfer
direction, flux arising from this flow is excluded from the flux obtained by using this
coefficient. Since we are normally interested in the total flux rather than diffusional
flux alone, in this case equation (1-7) can be written as;
dc A c A
N A = − (D AB + ε M ) + (N A + N B ) (2-4)
dz c
From the integration of this equation at steady-state with the same boundary conditions
used in the integration of equation (2-1) ;
N
A
cA 2
−
NA D
AB
+ εM N
A
+N
B
c
NA = c ln (2-5)
NA + NB Z N
A
cA1
−
N +N c
A B
is obtained. Substituting k ′c from equation (2-3) gives;
N
A
cA 2
−
NA N +N c
NA = k ′c c ln A B
(2-6)
NA + NB N
A
cA1
−
N +N c
A B
We prefer to write this equation in the form of “Flux equals the product of mass
transfer coefficient and concentration difference causing this transfer” and hence,
k ′c
NA = (c A1 − c A 2 ) (2-7)
β
is written. Here β accounts for the bulk flow contribution to the mass transfer and is
therefore known as bulk flow contribution term or drift factor. β is 1, when no bulk
flow in the transfer direction exists. By equating equations (2-6) and (2-7) an
expression is obtained for the calculation of β.
N R − c A 2 / c k ′c
N R k ′c c ln = (c A1 − c A 2 )
N R − c A1 / c β
β=
(N R − c A 2 / c) − (N R − c A1 / c) = (N R − c A / c)ln (2-8)
N R ln R
(N − c A 2 / c ) NR
(N R − c A1 / c)
where, NR is defined by NR=NA/(NA+NB).
Now, let us see what the β will be at some special cases, which were already
considered in Chapter-1. But before this, note that β is almost 1, when the solution is
dilute for component A (cA/c ≅ 0 ), whatever the relationship between the fluxes is.
2.2 A and B Transfer under Equimolar Counter Transfer Conditions: Since NA=
- NB, NR is indeterminate and then we go to equation (2-4). If NB is substituted with
-NA and then integrated with the boundary conditions at which equation (2-2) was
integrated,
NA= k ′c (c A1 − c A 2 ) (2-9)
is obtained. Comparing this equation with the equation (2-7) β=1 is seen. This is an
expected result, as it was already proved in Chapter-1 that there cannot be bulk flow in
“equimolar counter transfer of A and B”. It follows from this that; mass transfer
coefficient given by k ′c is the mass transfer coefficient for “ equimolar counter transfer
of A and B”.
As the concentrations in the solutions are expressed in different units, the mass transfer
coefficients have also different units, because NA has always the same unit. In the gas
phase, partial pressure and mole fraction are the most commonly used units next to the
molar concentration. Hence, for gas mixtures equation (2-9) can be written as:
N A = k ′c (c A1 − c A 2 ) = k ′G (p A1 − p A 2 ) = k ′y ( y A1 − y A 2 ) (2-10)
Interrelationships between three mass transfer coefficients can be found as
k ′G P = k ′y = k ′c c , by noting that yA= cA/c and cA= pA/P .
Similarly in the liquid solutions equation (2-9) is written as;
N A = k ′L (c A1 − c A 2 ) = k ′x ( x A1 − x A 2 ) (2-11)
where k ′x = k ′L c = k ′L (ρ / M ) can easily be proven. Here, ρ and M are density and
molecular weight of liquid solution.
2.3 A Transfers through Non-Transferring B: In this special case as NB=0 then

NR=1, and since from equation (2-8): β= (1-cA/c)ln = (1-xA)ln = (xB)ln veya =(1-yA)ln =
(yB)ln finally equation,
k ′c
NA = (c A1 − c A 2 ) = k c (c A1 − c A 2 ) (2-12)
( x B ) ln
is obtained.
In the gas mixtures this equation can also be written as;
N A = k G (p A1 − p A 2 ) = k c (c A1 − c A 2 ) = k y ( y A1 − y A 2 ) (2-13)
where, kG= k ′G P/(p B ) ln , k c = k ′c /(y B ) ln and k y = k ′y P/(p B ) ln
The relationships between three mass transfer coefficients are: kG P = ky = kc c
In liquid solutions the equation (2-12) is written as;
N A = k L (c A1 − c A 2 ) = k x ( x A1 − x A 2 ) (2-14)
where, kL= k ′L /(x B ) ln and k x = k ′x /(x B ) ln
It follows from the equations above that primless mass transfer coefficients are the
mass transfer coefficients for “A transfers through non-transferring B”. Furthermore,
while k ′c is independent of concentration, kc depends on concentration of the solution.
Mass transfer coefficient equals k ′c /β , when solutions are not dilute and when mass
transfer takes place under the conditions other than two special cases given above.
Often experimental determination of mass transfer coefficients is conducted when β is
not 1. To use this coefficient for other values of NR, it is first converted to k ′c and then
is corrected to the desired value of NR. If the mass transfer coefficient is determined
experimentally in a mixture, which is very dilute for component A, then regardless of
the value of NR used, the experimental value of (kc)exp. equals k ′c and kc, as the bulk
flow contribution is negligible.
The flux equations and the relationships between various mass transfer coefficients for
the two special cases mentioned above were all collected in Table.2.1
2.4 Mass Transfer Coefficients in Laminar Flow: In principle, mass transfer

coefficients are not required for laminar flow, since molecular diffusion prevails and
equations given in Chapter-1 can be used to calculate mass transfer rates. But, for
complex geometrical systems, it is either difficult to describe the laminar flow
mathematically or to solve the written equation without making many simplifying
assumptions. This then may lead to the oversimplification of the case. For that even for
laminar flow, mass transfer coefficients are measured experimentally and correlated.
Below, theoretical determination of mass transfer coefficient in laminar flow for a very
simple geometry will be described. As it will be seen, even the geometry is very
simple; many simplifying assumptions will be made to solve the complex
mathematical expressions.
Table 2-1. Mass transfer coefficients and Flux equations
General equations:
k ′c k′ k ′y
NA = (c A1 − c A 2 ) = x ( x A1 − x A 2 ) = ( y A1 − y A 2 )
β β β
( N R − x A 2 ) − ( N R − x A1 )
β= NR = NA/(NA+NB)
N R ln ( N R − x A 2 ) /( N R − x A1 )
Special cases:
A transfers through non-

Equimolar counter transfer transferring B Units of mass transfer coefficients
β=1 β=(1-xA)ln in SI
Gases:
N A = k ′G (p A1 − p A 2 ) N A = k G (p A1 − p A 2 ) k-mol A /m2 s bar
k-mol A /m2 s
N A = k ′y ( y A1 − y A 2 ) N A = k y ( y A1 − y A 2 )
N A = k ′c (c A1 − c A 2 ) N A = k c (c A1 − c A 2 ) k-mol A /m2 s (k-molA /m3)
N A = k Y ( YA1 − YA 2 )
k-molA/m2 s (k-mol A/k-mol B)
Liquids:
N A = k ′x ( x A1 − x A 2 ) N A = k x ( x A1 − x A 2 ) k-mol A/m2 s
k-mol A/m2 s (k-mol A/m3)

N A = k ′L (c A1 − c A 2 ) N A = k L (c A1 − c A 2 )
Conversions of mass transfer coefficients:
P (p ) (p )
Gas : k ′c c = k ′c = k c B ln = k G ( p B ) ln = ky B ln = k ′y
RT RT P
ρ
Liquid: k ′L c = k L ( x B ) ln c = k ′L = k ′x = k x ( x B ) ln
M
2.4.1 Mass Transfer from a Gas into a Liquid Film in Laminar Flow: Let us
consider the transfer of solute gas A into a liquid film B in laminar flow down a
vertical flat plate of length l, and width b. Our aim is to calculate the liquid phase
mass transfer coefficient kL theoretically, which in turn can be used to compute the
total flux or rate of the solute A dissolved in liquid B at any point of the plate. As it is
seen from Fig.2.2, the flow direction is x, mass transfer direction is z and thickness of
Liquid
z
y
x
Ac=b*δ
b
x=0
c A = c Ao dx
δ G
Liquid film
A
Solid plate
cA S
dSm=b*dx
l
ux,max
u x ux=f(z)
c Ax cAi
Ac
cAx=f(z)
c A = cAl
x=l
Liquid
Fig.2.2 Mass transfer from a gas into a laminar liquid film
the liquid film is constant at δ . The concentration of solute A in the inlet liquid is
uniform and shown with c Ao . The concentration of solute A in the first liquid layer
adjacent to the gas is cAi, which is the equilibrium solubility of solute A in liquid B at
the prevailing temperature and pressure. cAi does not change with x. The solution of
the problem is started by writing the continuity equation for component A, which was
derived in the previous chapter, and Navier-Stokes equation, which describes the
motion of the fluid in x-direction.
∂c A ∂c A ∂c A ∂c A ⎛ ∂ 2cA ∂ 2cA ∂ 2cA ⎞
+ ux + uy + uz = D AB ⎜⎜ 2 + + ⎟ + RA (1-58)
∂θ ∂x ∂y ∂z ⎝ ∂x ∂y 2 ∂z 2 ⎟⎠
⎛ ∂u x ∂u x ∂u x ∂u x ⎞ ⎛ ∂ 2 u x ∂ 2 u y ∂ 2 u z ⎞ ∂P
ρ⎜⎜ + ux + uy + uz ⎟ = µ⎜⎜ 2 + + ⎟− + ρg (2-15)
⎝ ∂θ ∂x ∂y ∂z ⎟⎠ ⎝ ∂x ∂y 2 ∂z 2 ⎟⎠ ∂x
These two equations must be solved simultaneously. First from equation (2-15)
velocity profile, ux=f(z) is obtained, then by substituting this into equation (1-58)
concentration profile is found. It is obvious that these equations cannot be solved in
these forms and hence some simplifications are required. These are: 1o) There is no
chemical reaction between A and B and hence RA = 0. 2o). There are no changes in the
conditions in y-direction, as a result of this, all the derivatives with respect to y are set
to zero. 3o) Steady-state prevails so that ∂c A /∂θ = 0 and ∂u x /∂θ = 0 . 4o) Rate of
absorption of solute A in liquid B is small, this leads to u z ≅ 0 . 5o) Rate of molecular
diffusion of solute A in x-direction is negligible compared to the rate of transfer by
bulk motion in this direction, so that D AB (∂ 2 c A / ∂x 2 ) = 0 can be written. 6o) Flow is
fully developed and hence ∂u x /∂x = 0 and ∂ 2 u x /∂x 2 = 0 . 7o) Pressure drop in flow
direction is negligible, then ∂P / ∂x = 0 . 8o) All the physical properties ( ρ, µ, D AB ) are
constant.
Under these assumptions equation (2-15) simplifies to:
d 2u x
µ + ρg = 0 (2-16)
dz 2
If this equation is integrated with boundary conditions of: at z = δ ux=0 and at z = 0
du x / dz = 0 ,
ρg δ 2 ⎡ ⎛ z ⎞2 ⎤ 3 ⎡ ⎛ z ⎞2 ⎤ ⎡ ⎛ z ⎞2 ⎤
ux = ⎢1 − ⎜ ⎟ ⎥ = u x ⎢1 − ⎜ ⎟ ⎥ = u x , max ⎢1 − ⎜ ⎟ ⎥ (2-17)
2µ ⎢⎣ ⎝ δ ⎠ ⎥⎦ 2 ⎢⎣ ⎝ δ ⎠ ⎥⎦ ⎢⎣ ⎝ δ ⎠ ⎥⎦
is obtained, where ux and u x are the local and average velocities. The average
velocity, which is written as u x = ρgδ 2 /3µ is found from the integration of local
velocity over the whole cross-section. ux,max is the maximum velocity which occurs at
gas-liquid interface and is obtained as u x , max = 3u x / 2 from the equation above by
inserting z = 0.
As for the equation (1-58), with the assumptions given above this equation also
simplifies to:
∂c A ⎛ ∂ 2c A ⎞
ux = D AB ⎜ ⎟ (2-18)
∂x ⎜ ∂z 2 ⎟
⎝ ⎠
If ux is substituted from equation (2-17), this equation becomes
⎡ ⎛ z ⎞ 2 ⎤ ∂c ∂ 2c A
u x , max ⎢1 − ⎜ ⎟ ⎥ A = D AB (2-19)
⎢⎣ ⎝ δ ⎠ ⎥⎦ ∂x ∂z 2
Equation (2-19) must be integrated with the following boundary conditions: at z=0 for
0 < x < l cA = cAi , at x = 0 for 0 < z < δ cA = cAo and at z = δ for 0 < x < l
∂c A / ∂z = 0 . The equation above is still complicated for integration and may be
integrated at two different conditions:
1o) Contact time and hence the length of plate is long: In this case solute A can
penetrate into all the liquid layers. This condition is met, when the liquid Reynolds
number, which is defined as Re = 4Γ/µ, is smaller than 100. Upon the integration
under these conditions first cA= f(x,z) is obtained , then by inserting x = l for all the
x’s in the equation, the concentration profile in the outlet liquid, cAl = f(z) is found.
The average concentration in the outlet liquid, which is independent of z, is then
obtained by performing the following integral;
1 δ
u x δ b ∫o
cAl = c Al u x b dz (2-20)
If all these steps are accomplished, finally the average concentration of the outlet
liquid is found as:
c Ai − cAl
= 0.7857 e −5.1213 η + 0.100 e −39.3 8 η + 0.03599 e −105.6 4 η + ..... (2-21)
c Ai − cAo
where η = 2D ABl/3δ 2 u x .
Consider the differential volume in the liquid as shown in Fig.2.2. Since solute A
transferring through the shaded area will cause an increase in the A content of the
solution,
u x δ b d cA = k L (c Ai − cA ) b dx can be written. By separating the
variables and integrating;
c Al
⌠ d cA l l
u xδ ⎮ = ∫o k L dx = k L ∫o dx
⌡ c c Ai − cA
Ao
ux δ c −c
kL = ln Ai Ao (2-22)
l c Ai − cAl
is obtained, where k L and k L are local and average mass transfer coefficients for
liquid phase. On the other hand for Re < 100, the first term of the equation (2-21) will
be sufficient. If this term is inserted into equation (2-22),
ux δ e5.1213 η u δ D
kL = ln = x (0.241 + 5.1213η) ≅ 3.41 AB (2-23)
l 0.7857 l δ
kL δ
or = Sh av. = 3.41 (2-24)
D AB
is finally obtained, where Shav. is average Sherwood number.

2o) Contact time is short or 100 < Re < 1 200: In this case, solute A can only
penetrate into the first layers of the liquid, hence ux can be replaced by ux,max. When
∂c A ∂ 2c A
this is done = D AB or by taking x/ux,max = θ, where θ is contact
∂ ( x / u x , max ) ∂z 2
time of gas-liquid,
∂c A ∂ 2cA
= D AB (2-25)
∂θ ∂z 2
is obtained. This equation is solved with the boundary conditions: at θ= 0 for 0 < z < ∞
cA= cAo , at θ > 0 for z =0 cA=cAi and at θ ≥ 0 for z = ∞ cA= c Ao . As it is seen,
because of very short contact time, the thickness of the liquid film is taken as ∞.
Laplace transformation technique can be used for the solution. Thus, by taking Laplace
transforms of both sides:
⎛ ∂c A (z, θ) ⎞ ⌠ ∂c A −sθ ∂ ∞
∞
₤⎜
⎝ ∂θ ⎠ ⌡ o ∂θ
⎟=⎮ e dθ =
∂θ ∫o
c A (z, θ) e −sθ dθ = s c A (z, s) − c Ao
∞
⎛ ∂ 2 c A (z, θ) ⎞ ⌠ ∂ c A (z, θ) e −sθ dθ = D ∂ c (z, θ)e −sθ dθ = D d c A (z, s)
2 2 ∞ 2
∂z 2 ∫o
₤ ⎜ D AB ⎟ = D AB ⎮
⎝ ∂z 2 ⎠ ⌡ ∂z 2
AB A AB
dz 2
o
are obtained, where s is Laplace parameter. By inserting these transformations into

equation (2-25), ordinary differential equation,
d 2 c A ( z, s ) s c Ao
− c A ( z, s ) = − (2-26)
dx 2 D AB D AB
is obtained, the solution of which is :
− z s / D AB s / DAB c Ao
c A ( z, s ) = K 1 e + K 2 ez + (2-27)
s
where, K1 and K2 are integration constants. In order to evaluate these constants the two
remaining boundary conditions, after the Laplace transformations, are used. The
transformations of these boundary conditions lead to:
₤[cA(0,θ)]=cA(0,s)=₤(cAi)=cAi/s and ₤[cA(z,θ)]= cA(z,s)= ₤ ( cAo ) = cAo / s .
z→∞
c Ao c
Since from second boundary condition, = K1 (0) + K 2 e ∞ + Ao is written, K2 = 0 is
s s
found. From the first boundary condition cAi/s = K1 (1) + cAo / s and K1 = (c Ai − c Ao ) / s
is written. By substituting all these into equation (2-27) finally,
− z s / D AB
e cAo
c A (z, s) = (c Ai − cAo ) + (2-28)
s s
is obtained. Taking the anti-Laplace of this equation with the help of Table.App.2.1,
the concentration profile of solute A is found as:
z
c A (z, θ) = cAo + (c Ai − cAo ) erfc (2-29)
4D ABθ
where, erfc (z / 4D AB θ ) = 1 − erf (z / 4D AB θ ) is error function complementary. As it
2 u −z2
is known, error function, which is defined by erf u = ∫ e dz , is an infinite series
π o
and its value for various u is given in Table.App.2.2.
Returning back to the equation (2-29) and substituting (x/ ux,max) for θ,
z
c A (z, x ) = c Ao + (c Ai − c Ao ) erfc (2-30)
4D AB x / u x , max
is obtained. Again, by inserting x = l in the equation (2-30), the concentration profile
of solute A in the outlet liquid, cAl is found, and this is:
z
c Al − c Ao = (c Ai − c Ao ) erfc (2-31)
4D AB l / u x ,max
Average concentration cAl is found as,
1 ∞ (c Ai − cAo ) ∞ z
c Al − c Ao = ∫
δb o
( c Al
− c Ao
) b dz =
δ ∫
o
erfc
4D AB l / u x ,max
dz
(c Ai − cAo ) 4D ABl/u x,max

cAl − cAo = (2-32)
δ π
In this case, by writing solute A balance for the differential volume, an equation
similar to equation (2-22) is obtained. When this is done,
u δ c −c
k L = x,max ln Ai Ao (2-33)
l c Ai − cAl
is found. In short contact time the change in the A content of the liquid will be very
small, as a result of this,
c −c c −c
ln Ai Ao ≅ Al Ao can be approximated. Hence, from the
c Ai − cAl c Ai − cAo
combination of equations (2-32) and (2-33) finally,
4D AB u x,max 6D AB Γ
kL = = (2-34)
πl πρδ l
is obtained, where Γ is the mass flow rate of liquid per unit width of the plate (kg/ms)
and is defined by
Γ =m & /b = ρ u x δ (2-35)
If it is remembered that u x = ρgδ 2 /3µ , from these two equations, the thickness of the
liquid film δ;
δ = (3µΓ / ρ 2 g )1 / 3 (2-36)
is found.
As it is seen, after very long mathematical manipulations, two theoretical equations for
the calculation of average liquid phase mass transfer coefficient, k L , when solute A
transfers from a gas into a liquid in laminar flow on a vertical plate, have been derived.
These average coefficients, as will be proved in section 2.7, are used in the equation
below, to compute the average mass transfer flux.
N A = k L (c Ai − cA ) ln (2-37)
As stated in the derivations, k L is computed from equation (2-23), when Reynolds
number is smaller than 100, and from equation (2-34), when Reynolds number is
between 100 and 1200.
In order to obtain reliable results, 8 assumptions made at the start of the derivations
must be met. From the comparison of the experimentally determined k L values with
the computed values, it has been found that experimentally measured values are
greater than computed values. The deviations are more pronounced at high Reynolds
numbers, as the ripples that form at gas-liquid interface are more stable at these
conditions.
Example-2.1 Calculation of Mass Transfer Coefficient
Cl2 gas is being absorbed into water film flowing down on a vertical plate which is 1.2 m high and
200 mm wide. Calculate the average liquid phase mass transfer coefficient for a water flow rate of
0.15 m3/h at 25 oC. Density and viscosity of water and molecular diffusivity of Cl2 in water at 25 oC
are 977 kg/m3, 0.894 cP and 1.44*10-9 m2/s.
Solution:
Mass flow rate of water, m & = (0.15 * 997) / 3600 = 0.0415 kg / s .

Mass flow rate of water per unit width of plate, from equation (2-35), Γ = 0.0415/0.20 = 0.208 kg/ms
Thickness of the liquid film from equation (2-36),
δ = [(3 * 0.894 *10−3 * 0.208) /(997) 2 (9.81)]1 / 3 = 3.85 *10−4 m.
Reynolds number, Re = 4Γ/µ = 4*0.208/(0.894*10-3) = 931. Hence, equation (2-34) is applicable.
6 * (1.44 *10 -9 ) * 0.208

kL = = 3.52 * 10 −5 m / s
π * 997 * (3.85 *10 -4 ) *1.2
is found.
2.5 Mass Transfer Correlations: As it has been shown above, even for a very simple
geometry for the solution of theoretically written mathematical expressions, many
simplifying assumptions are made and the solution still requires lengthy calculations.
In the end, because of the simplifying assumptions, the values computed from
theoretically derived equations might become quite different from experimentally
measured values. From this, it can easily be realized that why experimentally
measured mass transfer coefficients are preferred even in laminar flow.
In the turbulent mass transfer, even writing the mathematical equation describing the
process is almost impossible, let alone the solution of the equation. Hence,
experimentation is left as only alternative. To keep the number of the experimentations
at a reasonable level and also for the formulation of the results, a method which is
known as Dimensional Analysis is frequently used in the analysis of many
engineering problems, when the differential equation describing the process can not be
written and large number of variables are involved. As it can be realized, to find a
relationship between one dependent and large number of independent variables with
experimentation, one of the independent variables is changed, while the others are kept
constant and the effect of this changing independent variable on the dependent variable
is observed. This is repeated with all the independent variables systematically. It is
obvious then how lengthy will be the experimentation when large number of variables
are involved. But not only this, the organizing and expression of the results in the form
of a generalized equation become also very difficult. Instead of this, before
experimentation, the variables both dependent and independent are grouped such that
resultant group is dimensionless. Once grouped, the effect of group is important not
the individual variables contained in the group. It is obvious that number of the groups
is much smaller than the number of the variables. After grouping, experimentations are
conducted and a relationship among the groups is obtained. To some dimensionless
groups or numbers the names of the renowned scientists were assigned, such as
Reynolds Number, Schmidt Number, Sherwood Number etc. Before giving an
example to the analysis, which will be conducted in this way for mass transfer, let us
mention from a theorem, which is known as Buckingham Theorem and enables one
to compute the number of the dimensionless groups from number of the variables. The
statement of this theorem is as follows: The functional relationship among q
quantities, whose units may be given in terms of n fundamental units, may be written
as m = q-n dimensionless groups or numbers.
Now, as example let us consider mass transfer from a pipe wall to a fluid flowing
inside the pipe at steady-state, where A shows the transferring component and B the
fluid. Determination of the independent variables that affect the mass transfer
coefficient k ′c constitutes the first step of the analysis. Let us assume that these are:
inside diameter of the pipe D, molecular diffusivity of A in B DAB, density and the
viscosity of the fluid ρ , µ and finally the average velocity of the fluid u x . An error in
estimating the variables either in excess or less at this stage yields no result in
dimensional analysis. So,
k ′c = f ( D, D AB , ρ, µ, u x ) (2-38)
can be written, from which q = 6. If the dimension of each term is found from its
definition equation n =3, which are length l, mass M and time θ, is obtained. Thus,
from m = 6-3 = 3, the number of the dimensionless groups required to give the
relationship among the variables is found as 3. Now, let us find these dimensionless
groups. Let us assume that the variables in the dimensionless groups are with the
powers given in the equation below:
k ′c = f { [D] [D AB ] [ρ] [µ] d [u x ] }
a b c e
(2-39)
If the dimensions of all the variables are substituted,
lθ −1 = l a l 2 b θ − b M c l −3c M d l −d θ − d l e θ −e (2-40)
is obtained. As the equation to be found will be homogeneous in dimension, the sum
of the powers of each dimension on the left of the equation (2-40) must equal the sum
of the powers of the same dimension on the right of the equation. Hence,
For l : 1 = a+2b-3c-d+e
For M : 0 = c+d
For θ : -1 = -b-d-e are written. Since there are 3 equations but 5 unknowns,
then, if c and e are kept constant and a, b and d are expressed in terms of c and e ;
a = -1+e, b =1+c-e and d = -c are found.
From equation (2-39) k ′c = f (D D AB ρ µ u x )
−1+ e 1+ c − e c −c e
and from here,
e c
k ′c D ⎛ Dux ⎞ ⎛ D AB ρ ⎞
= f ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ can be written. By setting e and c arbitrarily equal to 1
D AB ⎝ D AB ⎠ ⎝ µ ⎠
⎛ Dux ⎞ ⎛ D AB ρ ⎞ ρ D u x
and multiplying the last two terms, ⎜⎜ ⎟⎟ * ⎜⎜ ⎟⎟ =
⎝ D AB ⎠ ⎝ µ ⎠ µ
finally,
β γ
k ′c D ⎛ ρ D ux ⎞ ⎛ µ ⎞
= α ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ (2-41)
D AB ⎝ µ ⎠ ⎝ ρ D AB ⎠
Table 2-2. Mass transfer correlations for widely used geometries
Type
Charact.
No. Geometry Equation Application range of
dimension
fluid
1 Sh= 0.023 Re0.83 Sc0.33 4 000< Re< 60 000
Inside pipe 0.6 <Sc <3 000 Pipe Fluid
flow diameter
Sh= 0.0149 Re0.88 Sc0.33 10 000< Re<4*105
Sc > 100
2 JD = 0.664 Re −x0.5 Re < 50 000
Flow parallel Length of
0.25
to a flat plate ⎛ Sc
⎞ 5*105<Rex <3*107 plate Fluid
Sh=0.037 Re 0x.8 Sc 0.43 ⎜⎜ ⎟
⎟ 0.7<Sc <380
⎝ Sc i
⎠
0.25
⎛ Sc ⎞ 2*104<Rex< 5*105
Sh= 0.027 Re x Sc 0.43 ⎜⎜ ⎟
⎟
⎝ Sc i ⎠ 0.7<Sc <380
3 Gas flow
Parallel to a flat JD = 0.11 Re-0.29 2 600<Re <22 000 Length of Gas
plate in plate
confined duct
4 Sh = 3.41 4Γ
Re= < 100
Wetted-wall µ Thickness Liquid
column of liquid
0.5 100<Re < 1200 film
⎛ 3δ ⎞
Sh= ⎜ Re Sc ⎟
⎝ 2πh ⎠
1 300< Re <8 300

Sh= 1.76*10-5 Re1.506 Sc0.5
5
Flow Sh = 0.281 Re 0.60 Sc 0.44 400 <Re< 25 000 Gas
Perpendicular 0.6<Sc<2.6 Diameter
To cylinder of cylinder
Sh= (0.35+0.34 Re0.5 + 0.15 Re0.58) Sc0.3 0.1<Re< 105 Fluid
0.7<Sc< 1 500
6
Flow past Sh = Sho + 0.347 (Re.Sc0.5)0.62 1.8<Re.Sc0.5<6*105 Diameter
single sphere of sphere
{2 + 0.569(Gr Sc) 0.25 Gr Sc < 10
8 Fluid
{
Sho= 0.6<Sc<3 200
0.333 0.244 8
2 + 0.0254 (Gr Sc) Sc Gr Sc > 10
7
Re − 5.75
Packed 2.06 90< Re< 4 000 Gas
JD=
column (*) ε Sc=0.6
5 000< Re < 10 300 Gas

Re − 0.815
20.4
JD= Sc=0.6 Diameter
ε
of packing
1.09 − 2 / 3 0.0016 < Re <55
JD= Re 168 < Sc < 70 600 Liquid
ε
Re − 0.31
0.250
JD = 5 < Re < 1 500
ε 168 < Sc < 70 600 Liquid
3 2
gl ∆ρ ⎛ ρ ⎞ Sh
Grashof number, Gr = ⎜ ⎟ ; JD- factor , J D = ; ε : Void fraction
ρ ⎝µ⎠ Re Sc 0.33
(*) In the Reynolds numbers superficial velocities (velocity based on empty column) are used.
is obtained. As the three dimensionless groups are named as Sherwood (Sh), Reynolds
(Re) and Schmidt (Sc) numbers respectively, equation (2-41) can also be written as;
Sh = α Re β Sc γ (2-42)
where the constants α, β and γ must be determined experimentally. This is
accomplished by making several experiments with different A and B under different
conditions in pipes. So obtained equation is now a general equation and it can be used
to compute the mass transfer coefficient of the fluid, when mass transfer takes place
from (to) the wall of a pipe to (from) a fluid flowing inside the pipe. For different
geometries, similar but not the same equations can be derived. Extensive lists of mass
transfer correlations thus obtained, are given in the Tables.5.21-5.28 (pages: 5-59 to
5-77) in Perry’s Handbook. Some of them are shown in Table 2.2 below. In using
these empirical correlations, one must be very careful with the four points given
below: 1o) Check whether the equation to be used is developed for the geometry you
are going to use. 2o) Find out what characteristic dimensions are used in Re and Sh
numbers of the equation you are going to use and use the same characteristic
dimensions in your calculations. 3o) Be careful with the application ranges of Re and
Sc numbers. And never use any equation outside the application ranges. 4o) Check for
what type of fluid the equation is valid, as some equations are valid for only liquids or
for only gases.
2.6 Mass Transfer Theories : In the design of process equipment generally mass
transfer coefficients obtained from empirical correlations are used. However some
theoretical methods have been developed to give an explanation of mass transfer
coefficients. These are known as mass transfer theories. Only two of them are briefly
presented below.
2.6.1 Film theory : The film theory which is the oldest of the mass transfer theories,
was first proposed by Whitman in 1923. According to this theory, “There is a thin
fictitious laminar film adjacent to the phase boundary in which all the resistance to
mass transfer is concentrated. Rest of the fluid is in turbulent motion and does not have
any resistance to the transfer. Mass transfer takes place across this film by molecular
diffusion under steady-state condition unidirectionally. As the capacity of the film is
very small, concentration profile in the film is established instantaneously. Due to low
solute concentration in the film, zero net-flux approximation can be made”. It is
obvious that thickness of the fictitious film should be greater than the thickness of the
laminar sub-layer.
With these assumptions, general equation for mass transfer (eqn.1-59) simplifies to the
equation below:
d 2cA
D AB =0 (2-43)
dz 2
The boundary conditions required for the solution are obtained from the statement of
the theory as :
B.C. 1) at z = 0 cA = cAi
2) at z = zL cA = cAL
where, zL is the thickness of the fictitious film, cAi and cAL are the interface and bulk
concentrations which are both constant.
Solution of equation (2-43) with the stated boundary conditions gives the
concentration profile as :
⎡ c − c AL ⎤
c A = c Ai − ⎢ Ai ⎥z (2-44)
⎣ z L ⎦
Since this is a straight line equation, change of concentration of solute in the film is
linear.
Then, total molar flux of solute A crossing the interface becomes;
⎛ dc ⎞ ⎡ c − c AL ⎤ D AB
N A = − D AB ⎜ A ⎟ = − D AB ⎢− Ai ⎥= (c Ai − c AL ) (2-45)
⎝ dz ⎠ z = 0 ⎣ z L ⎦ z L
As mass transfer coefficient is defined by
Total molar flux NA

kL = = (2-46)
Molar driving force (c Ai − c AL )
by substituting NA from equations (2-45) into equation (2-46),
D AB
kL = (2-47)
zL
is obtained.
So, according to the film theory, mass transfer coefficient is proportional to D 1AB.0 .But
most of the empirical mass transfer correlations shows that kL is proportional to D 2AB/ 3 .
Later on, some attempts have been made to modify the original film theory so that
k L α D 2AB/ 3 is obtained. It follows from this that original film theory oversimplifies the
mass transfer mechanism across a phase boundary. However because of its simplicity,
original form of the film theory is still used in complex cases such as mass transfer
accompanied by a chemical reaction.
2.6.2 Penetration theory : This theory was first proposed by Higbie and modified
later by Danckwerts. The statement of the model is as follows: “Hydrodynamic
conditions exist which allow for unidirectional mass transfer to take place by unsteady
molecular diffusion. A constant concentration is instantaneously established at the
interface and significant depth of penetration of solute is smaller than the depth of
undisturbed fluid. Solute concentration is low so that zero net flux conditions are
approximated.”
With these assumptions, general equation for mass transfer (eqn.1-59) simplifies to the
equation below:
∂c A ∂ 2cA
= D AB (2-48)
∂θ ∂z 2
The boundary conditions required for the solution are obtained from the statement of
the theory as follows:
B.C. 1) at θ = 0 for 0 < z < ∞ cA = cAo
2) at θ > 0 for z=0 cA = cAi
3) at θ ≥ 0 for z=∞ cA = cAo
where, cAi and cAo are the solute concentrations at the interface and at the undisturbed
fluid.
Solution of equation(2-48) can be done by using Laplace transformation technique.
The result is:
c A − c Ao z
= 1 − erf (2-49)
c Ai − c Ao 2 D AB θ
Then, instantaneous total molar flux of solute A crossing the interface becomes;
⎛ dc ⎞ D AB
N A (θ) = − D AB ⎜ A ⎟ = (c Ai − c Ao ) (2-50)
⎝ dz ⎠ z = 0 πθ
According to regular surface renewal model (Higbie model) average total molar flux;
D AB
NA = 2 (c Ai − c Ao ) (2-51)
πτ
and then average mass transfer coefficient,
D AB
kL = 2 (2-52)
πτ
are obtained.
According to random surface renewal model (Danckwerts model) average total molar
flux;
N A = D AB s (c Ai − c Ao ) (2-53)
and then average mass transfer coefficient,
k L = D AB s (2-54)
where τ is the time of penetration of the solute(s), s is the fractional surface renewal
rate(sec-1 ).
As it is seen, the penetration theory predicts that mass transfer coefficient is
proportional to D 0AB.5 . This is valid in some mass transfer systems, such as mass transfer
from gas to liquid in packed column where liquid flows over packing and contact
surface is renewed constantly in short periods.
Other mass transfer theories-some combining film and penetration theories- have been
developed which predict a gradual change of the exponent of DAB from 0 to 1.0
depending upon degree of turbulence.
2.7 Determination of Effective Concentration Difference for Calculation of

Average Flux: The flux equations given above are used to compute the local fluxes in
the equipment, as the mass transfer coefficients and the concentration differences are
local values. Since the mass transfer coefficients and the concentration differences
change along the equipment, what concentration difference should be taken to
compute the average flux for the equipment? To reply this, let us consider mass
transfer from a horizontal solid plate of length l, and width b, as shown in Fig.2.3 to a
z
ux cA Q
Liquid B A A
c A1 cA 2
cAi Sm dSm cAi b
x x+dx Dissolving solid

x= 0 x= l
Fig.2.3 Determination of effective concentration difference
liquid which flows over the plate with an average velocity of u x (m/s), and a
volumetric flow rate of Q (m3/s). Let us show with cA1 and cA2 (k-molA/m3) the
average concentrations of solute A in the inlet and outlet solutions. As it was stated
before, the concentration of solute A in the first liquid layer on the solid plate reaches
its solubility value, cAi at the prevailing temperature almost instantaneously and
remains at this value throughout the mass transfer.
The average concentration of solute A in the liquid c A , increases with increasing x.
The concentration difference, which causes mass transfer in z-direction also changes
with x, is being (c Ai − c A1 ) at the inlet, (c Ai − c A ) at any x and (c Ai − c A 2 ) at the outlet.
So, which one of these should be used to compute the average mass transfer flux?
Let us consider the liquid on the differential area of dS, and at steady-state write the
mass balance for solute A;
The molar rate of dissolution of A from the area dSm = Molar rate of transfer of solute A
in z-direction normal to the surface dSm.
Hence,
Q d cA = N A dSm = k L (c Ai − cA ) dSm (2-55)
is written, where kL is local mass transfer coefficient and d c A is the increase in the
concentration of liquid as liquid flows a distance of dx. Separating the variables and
integrating gives:
c A2
l
Q ⌠ dc Q c − cA2
Sm = ∫ dSm = ⎮ =− ln Ai (2-56)
o
k L ⌡ c Ai − cA kL c Ai − cA1
c A1
where k L is the average mass transfer coefficient for the liquid for the whole plate.
On the other hand, if the same is repeated for the whole plate,
The molar rate of dissolution of A from the area Sm = Molar rate of transfer of
solute A in z-direction normal to the surface Sm.
By defining an average concentration difference with ( c Ai − cA ) av. for the whole plate,
Q
NA = (cA2 − cA1 ) = k L (c Ai − cA ) av. (2-57)
Sm
is written. The value of so-defined ( c Ai − cA ) av. can easily be found by eliminating
k L between equations (2-56) and (2-57).
Q Q c − cA2
(cA2 − cA1 ) = − (c Ai − cA ) av. ln Ai
Sm Sm c Ai − cA1
From this,
(c − cA1 ) − (c Ai − cA2 )
(c Ai − cA ) av. = Ai (2-58)
(c Ai − cA1 )
ln
(c Ai − cA2 )
is finally obtained. As it is seen from the equation above, the average concentration
difference(driving force for mass transfer) to be used to compute the average molar
flux is the logarithmic mean of the concentration differences obtained at the inlet and
outlet of the equipment. Hence,
(c Ai − cA ) av. = (c Ai − cA ) ln . So, for the average flux, the following equation can be
written;
N A = k L (c Ai − cA ) ln (2-59)
The average mass transfer coefficient k L to be used in the equation is the arithmetic
mean of the mass transfer coefficients computed at the inlet and outlet conditions of
the equipment.
Example-2.2) Calculation of Gas Phase Mass Transfer Coefficient
As water flows down as a thin film on the inside surface of a vertical pipe of 100 mm diameter, dry air
flows upward at 30 oC and 1 bar pressure.
a) Calculate the mass transfer coefficient for the gas phase for an air flow rate of 30 m3/h.
b) For 60 % relative humidity of exit air, what must be the length of the pipe?
Density and viscosity of air at 30 oC and 1 bar are 0.019 cP and 1.14 kg/m3, and molecular diffusivity
of water vapor in air at 0 oC and 1 bar is 2.20*10-5 m2/s.Vapor pressure of water at 30 oC is 0.0424
bar.
Solution :
x water (A)
Water evaporates into air and transfers in z-direction.
Average air velocity in x-direction 2 A)
A pipe
QB (30 / 3600) z l
ux = = =1.06 m / s
A c ( π / 4)(100 *10 −3 ) 2
1
ρu D (1.14)(1.06)(100 *10 −3 )
Re = x = = 6 360 A)
µ (0.019)(1 *10−3 ) air(B)
1.75
⎛T ⎞
1.75
⎛ 273 + 30 ⎞
(D AB ) T = (D AB ) T ⎜⎜ 2 ⎟⎟ = (2.20 *10 −5 )⎜⎜ ⎟ = 2.64 *10 −5 m 2 / s
2 1
⎝ T1 ⎠ ⎝ 273 + 0) ⎟⎠
µ (0.019)(1*10 ) −3
Sc = = = 0.631 (Note that in the calculations of Re & Sc numbers

ρD AB (1.14)(2.64 *10 −5 )
density and viscosity of air are taken.)
From Table.2-2 Sh = 0.023 Re0.83 Sc0.33
k′c D k G RT (p B ) ln D
Sh= 0.023 (6 360)0.83 (0.631)0.33 = 28.31 Sh = = = 28.31
D AB D AB P
(p B ) ln (28.31)(D AB ) (28.31)(2.64 * 10 −5 )
kG = = −3
= 3.0 * 10 − 4 k − mol A / m 2 s bar
P D RT (100 * 10 )(0.083)(273 + 30)
(For dilute gas mixture (pB)ln / P≈1)
(b) Relative Humidty of air is defined as : (Partial pressure of water vapor in air/vapor pressure
of water at the prevailing temperature)
o
H A= pA2 / pA
The air leaving section-2 will be at 60 % realative humidity.

Then, pA2 = (60/100)(0.0424) = 0.02544 bar
Total molar flux of water vapor in z-direction for the whole pipe;
N A = k G (p Ai − p A )ln = k G (poA − p A )ln
Driving force for mass transfer at section-1 : (p oA − p A1 ) = p oA = 0.0424 bar
Driving force for mass transfer at section-2 : (p oA − p A 2 ) = 0.0424 − 0.02544 = 0.01696 bar
Average driving force for the pipe:
p oA − ( p oA − p A 2 ) 0.02544
(p oA − p A ) ln = o
= = 0.0278 bar
p 0.0424
ln o A ln
pA − pA2 0.01696
Assume that gas is dilute in water vapor (to be checked later). Then;
(p B ) ln
kG = k G = 3.0 * 10 −4 k − mol A / m 2 s bar
P
NA= (3.0*10-4)(0.0278) = 8.34*10-6 k-mol A /m2 s
Rate of evaporation of water into air = Rate of transfer of water vapor into air
QG (30 / 3600) = 8.43*10-6 k-mol A /s
N A = QG (c A 2 − c A1 ) = (p A2 − p A1 ) = (0.02544 − 0)
RT (0.083)(273 + 30)
(For dilute gas mixture: QG = QB ).
Mass transfer area and the length of the pipe needed under these conditions:
N A 8.43 *10 −6 l=
Sm
=
1.01
= 3.22 m.
Sm = = = 1.01 m 2
N A 8.34 *10 −6 πD (π)(100 *10 −3 )
Check whether dilute gas mixture assumption is correct or not !

At section-1: p Bi = P − p oA = 1 − 0.0424 = 0.9576 bar and p B = P − p A1 = 1 − 0 = 1 bar
p B − p Bi 1 − 0.9576
(p B )ln = = = 0.979 bar
ln(p B / p Bi ) ln(1 / 0.9576)
Then; (kG)1 = (3.0*10-4)(1/0.979) = 3.06*10-4 k-mol A /m2s bar

At section-2 : p Bi = P − p oA = 1 − 0.0424 = 0.9576 bar p B = P − p A 2 = 1 − 0.024544 = 0.974 bar
p B − p Bi 0.974 − 0.9576
(p B ) ln = = = 0.966 bar
ln(p B / p Bi ) ln(0.974 / 0.9576)
Then; (kG)2 = (3.0*10-4)(1/ 0.966) = 3.1*10-4 k-mol A /m2s bar

Average mass transfer coefficient for the pipe:
(3.06 + 3.10) *10 −4
kG = = 3.08 *10 − 4 k − mol / m 2 s bar
2
Average total molar flux for the pipe :
N A = k G (p oA − p A ) ln = (3.08 *10 −4 )(0.0278) = 8.56 *10 −6 k − molA / m 2 s

This gives l = 3.14 m. As it is seen, this is very close to 3.22 m (only 2.5 % excess), hence dilute gas
mixture assumption is valid.
Example-2.3) Calculation of Liquid Phase Mass Transfer Coefficient
100 mm diameter spherical solid was covered with benzoic acid. Water at 35 oC flows past this solid
with an average velocity of 0.12 m/s. Benzoic
Calculate: acid (A)
a) Liquid phase mass transfer coefficient, kc
b) Amount of benzoic asid dissolved in 1 hour as gr. Water(B)
Viscosity and density of water at 35 oC are 7.2*10-4 kg/ms
and 995 kg/m3. Solubility and molecular diffusivity of
benzoic acid in water at 35 oC are 0.31 gr B.Ac/100 ml
water and 1.25*10-9 m2 /s.
Solution:
Since the solubility of benzoic acid in water is very small, dilute solution assumption can easily be
done.
ρu d (995)(0.12)(100 *10 −3 )
Re = x p = =16 583
µ (7.2 *10− 4 )
µ (7.2 *10−4 )
Sc = = = 578.9 Then, from Table.2.2. Sh = Sho + 0.347 (Re.Sc0.5 )0.62
ρ D AB (995)(1.25 *10−9 )
For Sho Grashof number must be evaluated.
g d 3p ∆ρ ⎛ ρ ⎞
2
As ∆ρ = 0 then Gr =0 Hence from Table.2-2 Sho = 2
Gr = ⎜ ⎟
ρ ⎜⎝ µ ⎟⎠
Re Sc0.5 = (16 583)(578.9)0.5 = 398 990
Sh = 2 + 0.347 (398 990)0.62 = 1 032.2

k′ d k d
Sh = c p = c p =1 032.2
D AB D AB
D AB (1 032.2)(1.25 *10 −9 )
k c = (1 032.2 ) = = 1.29 *10 −5 m / s
dp (100 *10 −3 )
0.31 gr A 3.1 kg A (3.1 / 122) k − mol A

b) c Ai = . = = = 0.0254 k − mol A / m 3
100 ml B 1m 3 m3
N A = k c (c Ai − c A ) = (1.29 *10 −5 )(0.0254 − 0) = 3.28 *10 −7 k − molA / m 2 s
S m = πd 2p = (π)(100 * 10 −3 ) 2 = 0.0314 m 2
& A = N A S m M A (3600)(1000) = (3.28 * 10 −7 )(0.0314)(122)(3600)(1000) = 4.52 gr B.Ac / h

m
Problems
2.1 Gas phase mass transfer coefficient for the transfer of NH3(A) through non-transferring N2(B) at
760 mmHg and 20 oC has been given as kc=10.4 k-mol/m2h(k-mol/m3). The mixture is dilute for NH3.
Convert this coefficient to ky (k-mol/m2h), kG [k-mol/m2h(mmHg)], kY [k-mol/m2h(k-molA/k-molB)].
2.2 Ethanol flows through a pipe of 50 mm inside diameter, with a velocity of 1.0 m/s at 20 oC. The
inside surface of the pipe was covered with naphthalene, whose solubility in ethanol at 20 oC is 9.5 gr
naphthalene per 100 ml of solution.
a) Calculate the liquid phase mass transfer coefficient, kL.
b) What must be the length of the pipe, for an exit ethanol solution containing 1.2 gr naphthalene per
liter? Inlet ethanol does not contain naphthalene.
Density and viscosity of ethanol at 20 oC are 789 kg/m3 and 2*10-3 kg/ms, and molecular diffusivity of
naphthalene in ethanol at 20oC is 0.8*10-9 m2/s. [ Ans. b) ℓ = 7.03 m ]
2.3 In a channel which is 200 mm in diameter and 5 m in length, a gas flows at 2 bars and 20 oC with a
velocity of 2 m/s. To this gas solute A transfers from the wall of the channel. Calculate the mass
transfer coefficient k'G as k-mol/m2s bar. Viscosity and density of the gas and the molecular diffusivity
at the operating conditions are 0.68*10-3 Ns/m2, 1.51 kg/m3 and 1.25*10-4 m2/s .
In the literature, the following mass transfer correlations are given for the channel geometry:
i) Sh = 0.041 Re0.60 Sc1/3 Valid for 10 < Re < 25 000; for only liquids
(Characteristic dimension is length)
ii) JD= 0.068 Re-0.35 Valid for 10 < Re < 10 000; for fluids
(Characteristic dimension is diameter)
iii) Sh= 0.01 Re-0.44 Sc1/3 Valid for 1 000 < Re < 10 000; for only gases
(Characteristic dimension is diameter)
[Ans. k'G = 2.21*10-4 k-mol/m2 s bar ]
2.4 Pure water at 26°C is flowing at a rate of 2*10-3 m3/s through a packed bed of benzoic acid spheres
having a mass transfer area of 0.01 m2. The concentration of benzoic acid in the outlet liquid is
measured as 3*10-3 k-mol/m3. Calculate:
a) The molar rate of dissolution of benzoic acid,

b) The average mass transfer coefficient k L
The solubility of benzoic acid in water at 26 oC is 0.03 k-mol Ben.Ac./m3 of solution.
[Ans. b) k L = 0.021 m / s ]
2.5 Show that in a column filled (packed) with solid spheres of dp diameter, the area per unit volume
of packed bed, ap is given as;
6(1 − ε)
ap =
dp
where, ε is void fraction of the bed defined as volume of the voids divided by the total volume.
2.6 In order to find the liquid phase mass transfer coefficient, k L experimentally, water is made to flow
at an average velocity of 0.1 m/s through a pipe which is covered with benzoic acid. Diameter and
length of the pipe are 100 mm and 4 m. Concentration of benzoic acid in the outlet water is measured
as 0.0106 k-mol/m3. At the operating temperature, viscosity and density of water are 0.9*10-3 kg/ms
and 990 kg/m3. The solubility and the molecular diffusivity of benzoic acid in water at the given
temperature are 0.0205 k-mol/m3 and 7.2*10-7 m2/s.
a) Calculate k L at the experimental conditions,
b) Find the same k L from the appropriate correlation in Table.2.2 and compare the two values.
[Ans. a) 4.55*10-4 m/s ]
2.7 Pure gas B at 2 bars and 20oC is flowing over a solid surface wetted with water (A). The mass
transfer coefficient for the system is given as 0.006 k-mol/m2s. If the area of solid surface is 0.1 m2,
what is the rate of vaporisation of water as kg/h ?. Vapor pressure of water at 20 oC is 0.023 bar.
[Ans. 0.447 kg water / h]
2.8 From experiments conducted at atmospheric conditions in a wetted-wall column using an air
velocity of 2 m/s and a peripheral water rate of 1m3/h m, the following values were obtained for the
mass transfer coefficients:
kG = 2.5 k-mol/m2h bar for the absorption of ammonia in water
kL = 0.4 m/h for the absorption of CO2 in water
What value of the over-all mass transfer coefficient KG would you expect for the absorption of SO2 in
water at atmospheric pressure under the same flow conditions?
The equilibrium data for the absorption of SO2 in water, over the operating range employed, are
represented by the equation y = 10x, where y and x are weight fractions of SO2 in air and water
phases. At the experimental temperatures the molecular diffusivities of NH3 and SO2 in air are
2.32*10-5 and 1.16*10-5 m2/s and of CO2 and SO2 in water 1.5*10-9 and 1.25*10-9 m2/s.
2/3
Assume that transfer coefficients vary with D AB , and the solutions are dilute. Take the density of
water as 1000 kg/m3. [Ans.: KG = 0.70 k-mol/h m2 bar]
Chapter-3
MASS TRANSFER BETWEEN TWO PHASES
3.1 Introduction: So far we have seen the mass transfer within a single phase. In most
of the mass transfer applications such as in mass transfer operations, however, the two
insoluble phases are brought into contact in order to accomplish transfer of one or
more components between them. The two phases in contact may be gas-liquid, liquid-
liquid, gas-solid or liquid-solid. Important point here is the insolubility of the phases
within each other. If one of the phases contains a component, which can dissolve also
in the other phase, this component may transfer from the phase to the other. The
condition for the transfer is the non-equilibrium of the phases. If the two phases are in
equilibrium, transfer is not possible. Concentration gradients exist in the two phases in
contact is the indication of mass transfer taking place between the phases. When no
concentration gradients exist in the phases, the two phases are said to be in
equilibrium. It is obvious from these explanations that equilibrium is very important in
the understanding and analysis of mass transfer between two phases.
3.2 Equilibrium between Phases: Equilibrium characteristics of each system are
different and peculiar to the system. For example, equilibrium characteristics of a gas-
liquid system are quite different than that of a liquid-liquid system. Before
investigating the equilibrium concept, let us see the Phase Rule, which was first given
by Gibbs and is a very useful tool for finding the independent variables, which can be
changed without upsetting the equilibrium. According to this rule, P+F =C+2 is
always valid for a system at equilibrium, where P is the number of the phases in the
system, C is the total number of the components in the system and F is degree of
freedom that is to say, the number of independent variables. Typical independent
variables are: Pressure, temperature and concentrations of components in the phases.
For example number of independent variables for a system containing two phases and
three components, at most two being in each phase, is found as 3 from the equation
above. In this case, possible independent variables are: pressure, temperature and the
compositions of one component in each phase. If pressure and temperature are fixed,
the number of the variables that can be changed without upsetting the equilibrium is
left as one. Hence; if the concentration of the component in one phase is specified, the
concentration of the same component in the other phase is automatically set. Or, if the
temperature and the compositions of one component in two phases are fixed, we
cannot say anything about the pressure, as it has been set automatically.
Let us return to equilibrium concept and as an example take gas-liquid equilibria.
These equilibria are important in gas absorption operations. Suppose we have an
ammonia-nitrogen gaseous mixture and bring it in contact with a fixed amount of
liquid water in a closed container, which can be kept under constant temperature and
pressure. Since the ammonia but not nitrogen is soluble in water, some ammonia
molecules will transfer from gas to the liquid crossing the interface. This transfer
continues until no more ammonia can dissolve in the liquid. The concentrations within
each phase then become uniform by internal diffusion and do not change any more.
This condition is known as equilibrium condition. In reality the transfer of ammonia
molecules between the phases does not stop (dynamic equilibrium), but this transfer
does not result in net transfer of mass as the number of ammonia molecules going to
liquid at any time interval is exactly balanced by the number of the ammonia
molecules coming from the liquid phase at the same time interval. By analysing two
phases for ammonia, a set of equilibrium concentrations such as x and y (mole fraction
of ammonia in liquid and gas phases respectively) are obtained. These values do not
mole fraction of ammonia in gas, y P=cons

t=cons
o
o mole fraction of ammonia in liquid, x
Fig.3.1 An example for gas-liquid equilibrium
change any more with time. Suppose that we add some more ammonia to the gas
phase, as the equilibrium is upset some of the ammonia added to the gas phase
transfers to the liquid. This transfer continues until a new equilibrium is attained. Once
the equilibrium is reached, transfer of ammonia stops again. When the gas and liquid
samples are analysed again for ammonia, higher concentrations in each phase are
found. If these additions and analysis are repeated, a complete set of equilibrium
relationship is obtained. By plotting x values versus the y values, equilibrium
distribution curve for the ammonia as shown in Fig.3.1, is obtained. This curve results
irrespective of the amounts of water and gas that we start with and influenced only by
the temperature and pressure. It is important to note that at equilibrium the
concentrations of ammonia in the two phases are not equal. It may then be asked:
“what are equal at the equilibrium”? The answer to this question is: “the chemical
potentials of ammonia in each phase”. So, it is the equality of the chemical
potentials of the distributed component that stops the mass transfer. If the chemical
potentials of the ammonia in liquid and gas are shown with µ LA and µ GA , at
equilibrium µ LA = µ GA . Whenever a component distributes itself between insoluble
phases, a dynamic equilibrium is established. Each equilibria are peculiar to particular
system. For example replacement of water with toluene or replacement of ammonia
with SO2 will each result in new curves. The temperature and pressure each does affect
the equilibrium, resulting with another curves for the same system. Equilibrium
relationship for a liquid-liquid system will bear no relation to that for gas-liquid
system.
3.3 Mass Transfer between Two Phases: If the two phases in contact are not in
equilibrium, mass transfer will certainly take place between the phases. In many
engineering applications of mass transfer, the two phases flow at steady-state with
constant velocities in counter directions to each other. As an example, let us consider
again a gas-liquid system. Suppose that gaseous mixture consisting of A and C is
contacted with a solvent S, that can dissolve only solute A, in a simple equipment such
as wetted-wall column, which is shown in Fig.4.2. In this equipment, as liquid flows as
a thin film down the inside surface of the column, gaseous mixture flows upward. Gas
mixture changes its composition from high to a low solute concentration as it flows
upward, while liquid dissolves the solute A and leaves at bottom as solute-rich liquid.
interface
Gas phase Liquid phase
A+C A+S
Concentrations in liquid
Concentrations in gas
y A
xi
yi
z z
Distance from interface o Distance from interface
Fig.3.2 Concentration profiles in two phases
At every section of the column, solute A transfers from gas to liquid. Typical
concentration profiles of solute A in each phase at a particular level of the column are
shown schematically in Fig.3.2. As it is seen, concentration of solute A in the gas
phase drops from its bulk value y to its interface value yi, hence concentration
difference or driving force, which causes the transfer of solute A in the gas from bulk
to interface is y-yi. In the liquid phase, concentration of the same component decreases
from its interface value xi to its bulk value x, hence concentration difference or driving
force that causes the transfer of solute A from interface liquid to the bulk liquid is xi-x.
As there is mass transfer from gas to liquid, x and y cannot be equilibrium values. It is
assumed that there is no resistance to mass transfer (except at some special cases)
across the interface and as a result of this yi and xi are equilibrium values related by
the system’s equilibrium distribution curve. As they are equilibrium values, which one
will be greater, totally depends on the equilibrium relationship of the system. The
concentration rise at the interface from yi to xi as shown in Fig.3.2 is not a barrier to
mass transfer in the direction from gas to liquid. The determining factor for the
direction of mass transfer is neither the relationship between yi and xi nor the
difference between y and x, but is the difference between the bulk and interface
concentrations in a phase, hence, if y-yi or xi-x is positive, solute A transfers from gas
to liquid as shown in the Figure. On the other hand, if these differences are negative,
the transfer direction is from liquid to gas. There is no direct effect of y-x difference
on the transfer direction.
3.4 Mass Transfer Flux: The most important point in a mass transfer between the
phases is to compute the mass transfer fluxes of the transferring components. At
steady-state, since the mass transfer flux of solute A from bulk gas to the interface gas
equals the flux of the same component in the liquid from interface liquid to the bulk
liquid, the following equations can be written for solute A:
k ′y k ′x
NA = (y − yi ) = (x i − x) (3-1)
β iy β ix
where, k ′y and k ′x are the individual mass transfer coefficients for gas and liquid
phases and β iy and β ix are the bulk flow correction terms for the same phases, which
can be given by the following equations:
( N R − y) − ( N R − y i ) (N R − x) − (N R − x i )
β iy = and β ix = (3-2)
N R ln( N R − y) /( N R − y i ) N R ln( N R − x ) /( N R − x i )
Any one of the two equations in (3-1) can be used to compute the total molar flux of
solute A. Since y and x are the bulk concentrations, they can easily be determined with
sampling from the phases and analysing them. Individual mass transfer coefficients, on
the other hand, can be computed from the appropriate mass transfer correlations by
inserting the system’s properties and flow parameters. Bulk flow contribution terms
can be found from the equations given in (3-2). But, since it is almost impossible to
take samples right through the interface fluids, yi and xi can not be determined
experimentally, but they can be computed from simultaneous solution of system’s
equilibrium relationship and equations given in (3-1). Since, in the majority of the
cases, equilibrium relationship is given in graphical form, the solution is done on the
graph. If equation (3-1) is rearranged,
k ′x / β ix y − yi
− = (3-3)
k ′y / β iy x − xi
is obtained. As it is seen, this equation represents a straight line on xy-diagram,
k ′x / β ix
passing through points P(x;y) and M(xi;yi) with a slope of − . Since xi and yi
k ′y / β iy
Mole fraction of solute A in gas, y
k ′x / β ix
slope= −
k ′y / β iy
y P
E Equilibrium distribution curve
slope= m''
yi
M
y*
R slope= m'
o x xi x*
Mole fraction of solute A in liquid, x
Fig.3.3 Determination of interface concentrations
values are equilibrium values, point M must also lie on the equilibrium distribution
curve. As point P and slope are known, by drawing the line starting at P with known
slope, point M, hence xi and yi are found. Now, flux can be computed by using any
one of the equations in (3-1).
In reality, drawing of PM line is not so easy, as the slope contains the sought for xi
and yi. Nevertheless, if transfer of solute A in two phases takes place in dilute
solutions or under the condition of equimolar counter transfer , then β iy = β ix = 1 and
slope of PM line is simply: − k ′x / k ′y and hence drawing of PM line is straightforward.
But, if solute A transfers through non-transferring C in the gas and through non-
transferring S in the liquid as in the example above, and in addition if the solutions are
not dilute for solute A, the bulk flow correction terms and hence the slope of PM line
k ′x /(1 − x ) i ln
becomes, (1 − y)iln and (1 − x) iln and − , where (1-y)iln and (1-x)iln
k ′y /(1 − y) i ln
are given as:
(1 − y) − (1 − y i ) (1 − x) − (1 − x i )
(1 − y)iln = and (1 − x)iln = (3-4)
ln(1 − y)/(1 − y i ) ln(1 − x)/(1 − x i )
In this case, drawing of PM line can only be done by trial and error. In other cases,
first NR is calculated from the relationship between the fluxes, then with the help of
equations (3-2) and (3-3) and by trial and error xi and yi are found.
3.5 Overall Mass Transfer Coefficients and Overall Driving Forces: To compute
the molar flux of transferring solute A; yi or xi must be known, which are in many
cases found by trial and error. In addition to this, mass transfer coefficients are
obtained experimentally. At some experimental conditions, the measurements of
k ′y and k ′x , the individual mass transfer coefficients, are very difficult, as the
complete elimination of the resistance to mass transfer in one phase is almost
impossible and hence overall mass transfer coefficients based on gas or liquid phase
K′y and K′x are measured. Computing total molar flux by using these overall
coefficients requires the definitions of overall concentration differences or driving
forces for the system. It is obvious that (y-x) or (x-y) cannot be taken as overall
driving forces, as the real driving force for mass transfer is the difference between the
chemical potentials of the transferring component in two phases, not the difference
between its concentrations in two phases. It is very well known from thermodynamics
that, the relationship between the concentration of solute A in the gas y and its
chemical potential µ G is quite different from the relationship of x and its chemical
potential µ L . Hence, if concentration differences are to be used with overall mass
transfer coefficients, the measure of x in terms of gas phase unit must be subtracted
from y, not the x itself. If this is shown by y ∗ , the overall driving force in terms of gas
phase concentrations for the system then becomes ( y − y ∗ ), where y ∗ is the equilibrium
value of x and hence, point R(x, y ∗ ) is a point on the equilibrium distribution curve.
On the other hand, if the overall driving force is to be expressed in terms of liquid
phase concentrations, this should be written as ( x ∗ − x ), where x ∗ is the measure of y
in terms of liquid phase units and this is equilibrium value of y and hence, point
E( x ∗ ;y) lies on the equilibrium distribution curve of the system. In the light of these
explanations, for the total molar flux of solute A, which transfers from gas phase to the
liquid, in addition to the equations (3-1),
K ′y ∗ K ∗x
NA = (y − y ) = (x ∗ − x) (3-5)
β ∗y β∗x
can be written, where K′y and K′x are overall mass transfer coefficients based on
gas and liquid phase respectively, β∗y ve β∗x are bulk flow correction terms for gas
and liquid phases , which are defined by;
∗ ( N R − y) − ( N R − y ∗ ) ∗ (N R − x) − ( N R − x ∗ )
β = and β = (3-6)
N R ln( N R − y) /( N R − y ∗ ) N R ln( N R − x ) /( N R − x ∗ )
y x
For dilute solutions and for “equimolar counter transfer” conditions β∗y = β∗x = 1 and
hence equation (3-5) simplifies to:
N A = K ′y ( y − y ∗ ) = K ′x ( x ∗ − x ) (3-7)
If solute A transfers in both phases through non-transferring components as in the
example above: β∗y = (1 − y)∗ln and β∗x = (1 − x)∗ln and hence equation (3-5) is written
as:
N A = K y ( y − y∗ ) = K x (x ∗ − x) (3-8)
where, K y = K ′y /(1 − y)∗ln and K x = K ′x /(1 − x)∗ln . (1 − y) ∗ln and (1 − x ) ∗ln are defined
by:
(1 − y) − (1 − y∗ )
∗ ∗ (1 − x) − (1 − x ∗ )
(1 − y) = and (1 − x) ln = (3-9)
ln(1 − y)/(1 − y∗ )
ln
ln(1 − x)/(1 − x ∗ )
3.6 The Relationships between Individual and Overall Mass Transfer
Coefficients: If the individual mass transfer coefficients are computed from mass
transfer correlations, overall mass transfer coefficients can easily be synthesized from
them. To derive the relationship between them, first write (y-y*) = (y-yi) + (yi-y*) =
(y-yi) + m′ (xİ-x) from Fig.3.3, where m′ is the slope of RM line. Then, substitute the
driving forces from equations (3-1) and (3-5) and make the necessary simplifications.
The result is:
1 1 m′
= + (3-10)
K ′y / β ∗y k ′y / β iy k ′x / β ix
Similarly, from the same figure, (x*-x) =(x*-xi) + (xi-x) =m"(x*-x) + (xi-x) can be
written. Substituting the driving forces from equations (3-1) and (3-5) gives;
1 1 1
= + (3-11)
K ′x / β ∗x m ′′ k ′y / β iy k ′x / β ix
where, m ′′ is the slope of EM line. If the equilibrium distribution curve is a straight
line then, m′ = m′′ = m.
The term on the left hand side of equation (3-10) gives the total resistance to mass
transfer in the system. On the other hand, the first term on the right hand side is the
resistance to mass transfer in the gas phase only, and the second term is the resistance
to mass transfer in the liquid phase only. Hence, total resistance to mass transfer in the
system is the sum of the resistances lying in each phase. The same can be said by
looking at the equation (3-11). It follows from this that multiplication of the ratio of
the first terms on the right hand sides to the terms on the left hand sides of the
equations (3-10) and (3-11) with 100 gives the percent of resistance lying in the gas
phase and subtraction of this from 100 is the percent of resistance in the liquid. This,
which is known as resistance analysis, is very useful in deciding at what phase changes
must be made in order to increase the rate of mass transfer occurring between the
phases. It is obvious that, changes made in the right direction in the phase, which has
the greater resistance will increase the rate of mass transfer significantly. In many
cases, the magnitudes of individual mass transfer coefficients are almost the same. In
these cases then the value of the slope of equilibrium distribution curve determines the
values of resistances in each phase. If the slope m′ is very great (this is so when the
solubility of A in S is very small) the first term on the right hand side of equation (3-
10) can be neglected. Thus,
1 m′
≅ (3-12)
K ′y / β ∗y k ′x / β ix
can be written. It follows from this that total resistance to mass transfer in the system
is almost in the liquid phase. This special case is known as “mass transfer under the
control of liquid phase”. It is obvious then that in order to increase the rate of mass
transfer, measures must be taken in the liquid phase not in the gas phase. On the
contrary to this, if the slope m′ is very small (this is so when the solubility of A in S is
very great) the second term on the right hand side of equation (3-10) can be neglected.
Thus,
1 1
≅ (3-13)
K ′y / β∗y k ′y / β iy
can be written. It follows from this equation that total resistance to mass transfer lays
almost in the gas phase. This special case is known as “mass transfer under the
control of gas phase”. Then, in order to speed up the mass transfer, measures must be
taken in the gas phase, not in the liquid phase.
Example-3.1) Interphase Mass Transfer
In a distillation operation, one of the components transfers from a binary vapor mixture of A+B into
the liquid , during which other component transfers from liquid to vapor. The molar latent heats of
vaporization of components are such that λA = 3λB. At one section of the equipment, the mole fractions
of component A in liquid and vapor are measured as 0.25 and 0.32 respectively.
a) Find the transfer directions of the components,
b) Calculate total molar fluxes of components,
c) Calculate the percentage resistances in liquid and vapor phases,
d) Plot the concentration profiles of components A and B in both phases qualitatively.
The individual mass transfer coefficients for liquid and vapor phases were calculated at the operating
conditions from the appropriate correlations as;
k′x = 3 *10−4 k − mol / m 2s k′y =1.5 *10 −4 k − mol / m 2s.
The equilibrium relationship within the operating range is linear and expressed as y =1.8 x, where y
and x are the mole fractions of component A in vapor and liquid respectively.
Solution:
a) Nothing can be said for the transfer directions by looking at x and y values.
NA NA
From NB = - (λA /λB ) NA = - 3NA Then, NA = = = − 0.5
N A + N B N A − 3N A
Solution is by trial and error.
k ′x / βix k ′ βiy 3 *10 −4 βiy βiy

slope of PM line; m=− =− x . = . = −2 (1)
k ′y / βiy k ′y βix 1.5 *10 βix
−4
βix
As first trial, assume βix = βiy =1 then; m = - 2
From eqn.(3-3) and yi=1.8xi
0.32 – 1.8 xi = -2 (0.25 - xi)
xi = 0.216 and yi = 1.8 (0.216) = 0.389 Substitute these into eqn.(3-2)
( −0.5 − 0.32) − ( −0.5 − 0.389) (−0.5 − 0.25) − (−0.5 − 0.216)

βiy = =1.71 βix = = 1.466
(−0.5 − 0.32) (−0.5 − 0.25)
(−0.5) ln (−0.5) ln
( −0.5 − 0.389) (−0.5 − 0.216)
1.71
Then, new slope of PM line; m = ( −2) = −2.33
1.466
New values for xi and yi with this m;
0.32- 1.8 xi = - 2.33 (0.25 – xi)
xi = 0.219 and yi = 1.8 (0.219) = 0.394
These are sufficiently close to the previous ones and hence trial is stopped. Final values are
xi = 0.219 , yi = 0.394 , βix= 1.466 and βiy= 1.71
As (y-yi) = (0.32-0.394) < 0 then , component A transfers from liquid to vapor, and the other
component B transfers from vapor to liquid.
k ′y 1.5 * 10 −4
b) NA = (y − y i ) = (0.32 − 0.394 ) = − 6.49 * 10 − 6 k − mol A / m 2 s
β iy 1.71
or k′x 3 *10−4
NA = (x i − x) = (0.219 − 0.25) = − 6.35 *10 −6 k − mol A / m 2s
βix 1.466
(-) sign shows that component A transfers from liquid to vapor.
NB = - 3 NA = (-3)(-6.42*10-6) = 1.93*10-5 k-mol B/m2 s
c) m' = m" = 1.8 Hence, from eqn.(3-10)

b) 1 1 1.8
= + =11 400 + 8 797 = 20 196
K′y / β y
∗
(1.5 *10 ) / 1.71 (3 *10 − 4 ) / 1.466
−4
Percentage resistance in liquid : Percentage resistance in vapor:

1 / k′y / βiy 11 400
m′ / k′x / βix 8 796 .100 = .100 = 56.5 %
.100 = .100 = 43.5 % 1 / K′y / β y
∗
20 196
1 / K′y / β y
∗
20 196
For check, calculate NA by using over-all values;
y* = 1.8 x = (1.8)(0.25) = 0.45 x* = y/1.8 = (0.32)/(1.8) = 0.178
K′y 1 K′x 1
= = 4.95 *10 −5 k − mol / m 2s ∗
= = 8.91*10 −5 k − mol / m 2s
β∗y 20 196 β x 11 220
From eqn.(3-5)
K′y
NA = ( y − y∗ ) = (4.95 *10−5 )(0.32 − 0.45) = − 6.44 *10 −6 k − mol A / m 2s
βy
∗
K ∗x ∗
NA = ( x − x ) = (8.91*10 −5 )(0.178 − 0.25) = − 6.42 *10 −6 k − mol A / m 2 s
βx
∗
d) x = 0.25 y = 0.32
xi = 0.219 yi = 0.394
xB = 1- x = 1- 0.25 = 0.75 yB = 1- 0.32 = 0.68
xBi =1- xi =1- 0.219 = 0.781 yBi = 1- 0.394 = 0.606
interface
VAPOR (A + B) LIQUID (A + B)
B
0.8 A 0.8
yB =f(z)
xB
yB xBi xB =f(z)
0.6 yBi 0.6
y, yB x, xB
yi
0.4 x =f(z) 0.4
y
x
0.2 xi 0.2
y=f(z)
0.0 0.0
z 0.0 z
Problems
3.1 A saturated binary vapor mixture consisting of A and B, contains 16 mole percent component A.
This mixture is contacted with a saturated binary liquid solution consisting of the same components
and containing 11 mole percent component A, at the same pressure. Latent heats of vaporization of
both components are the same. Individual mass transfer coefficients at the operating conditions are
2*10-3 k-mol/m2s for liquid and 2.2*10-3 k-mol/m2s for the vapor phase.
At the operating pressure and concentration range involved equilibrium distribution curve may be
represented by y= 5.5 x, where y and x are mole fractions of component A in vapor and liquid phases
respectively.
a) Calculate the interface compositions,
b) Find the transfer directions of components A and B,
c) Calculate percentage resistance to mass transfer in the liquid phase.
3.2 Air containing 4 mole percent of acetylene is contacted with water containing 0.02 mole percent
acetylene in an equilibrium unit at 25 oC and 3.039 bar.
a) Determine the transfer direction of acetylene
b) Calculate the interface compositions of acetylene in both phases
c) Compute the ratio of the resistance in gas phase to the total resistance of both phases.
Equilibrium relationship can be given as pA = 1.01*106 x, where pA is the partial pressure (mm Hg) of
acetylene in air and x is the mole fraction of acetylene in water. Individual mass transfer coefficients
are given as kx = 6.0*10-3 kmol/m2s; ky = 3.0*10-4 kmol/m2s.
3.3 An air-SO2 gaseous mixture, containing 3 % SO2 (A) by volume is in contact with water (S)
containing 1 % SO2 by mole at 750 mmHg and 20 oC. At the operating conditions individual mass
transfer coefficients are calculated from the appropriate correlations as kx = 5*10-3 k-mol/m2s and
ky = 2.5*10-3 k-mol/m2s. The equilibrium relationship of the system is given as pA = 30x, where pA is
the partial pressure of SO2 in mmHg and x is the mole fraction of SO2 in the liquid.
a) Find the transfer direction of SO2.
b) Calculate total molar flux of SO2.
c) Calculate percentage resistances to mass transfer in liquid and gas phases, and comment on the
result.
3.4 In a wetted-wall column an air-H2S (A) gas mixture is flowing up by a water (S) film which is
flowing down on the inner surface at 1.50 atm and 30 oC. The gas phase mass transfer coefficient, kc
has been predicted as 9.57*10-4 m/s. At a certain plane, the mole fraction of H2S in the liquid at the
gas-liquid interface is 2*10-5 and partial pressure of H2S in the bulk gas is 0.05 atm.
Calculate the total molar flux of absorption of H2S.
Equilibrium relationship is given as pA= 609 x , where pA is the partial pressure of H2S in atm. and x is
the mole fraction of H2S in liquid. [ Ans. a) NA = 1.46*10-6 k-mol H2S/m2s ]
3.5 Benzene and toluene are being separated by distillation in a column at 760 mmHg. At a particular
point in the column vapor and liquid phases contain 63 and 50 mole percent benzene respectively and
local value of the total molar flux of benzene is 0.05 k-mol/h m2. If 85 percent of the total resistance to
mass transfer is in the vapor phase, calculate:
a) The interfacial compositions,
b) The values of local individual mass transfer coefficients.
3.6 In the distillation of a binary solution of A+B in a packed column, the mole fractions of A in liquid
and vapor are measured as 0.28 and 0.26 at one section. If the ratio of mass transfer resistance in the
liquid to that in the vapor is 1.5,
a) What are the values of interface compositions?
b) What are the transfer directions of the components?
Vapor liquid equilibrium at the operating conditions may be given as y = 3x, where y and x are the
mole fractions of component A in vapor and liquid. [Ans. a) xi = 0.164, yi = 0.492 ]
Chapter-4
GAS ABSORPTION
4.1 Introduction: Gas absorption is a mass transfer operation by which a gaseous

mixture is separated into its components by contacting it with a suitable liquid solvent,
such that one or more components of the gas phase transfer from gas to liquid phase.
In this operation, the original phase is a gas mixture and liquid solvent is brought from
the outside. This operation depends on the difference in the solubility of gases in
liquids. Operation is carried out at low temperatures so that liquid solvent itself does
not evaporate into gas phase. Hence, direction of mass transfer is from gas to liquid
only. This operation is not a final separation operation, as upon the absorption, a liquid
solution is produced, from which solute A can only be recovered by applying another
mass transfer operation, such as stripping or distillation. Gas absorption is used either
to recover the valuable components or to remove the noxious substances from the
gaseous mixtures. For the latter, it has also found wide applications in the
environmental engineering in the recent years. Removal of sulphur oxides from stack
gases of a power generator burning coal is a good example for this. Because of large
amounts of gas to be processed, absorption towers up to 20-meter diameters are in use
today. If solute A is transferred from liquid solution to a gas phase, by contacting the
solution with an inert gas C, operation is then called as stripping or desorption. As
the transfer direction of mass in this case is from liquid to gas, desorption operation is
the reverse of gas absorption operation. As it is seen, in the desorption operation, the
original phase is liquid and the second phase, which is brought from the outside, is a
gas. Desorption operation may be used alone or with the combination of gas
absorption. As an example for gas absorption in chemical industry and the combined
use of absorption-desorption, let us consider the separation and purification of coke-
oven gases. The gas phase leaving a coke-oven is a mixture of benzene, toluene and
xylenes vapors with nitrogen, hydrogen and carbon oxides gases. When this gas phase
is contacted with a high molecular weight liquid solution of paraffinic hydro-carbons
at low temperature, organic vapors benzene, toluene and xylenes are absorbed into the
liquid, leaving back the inert gas mixture of nitrogen, hydrogen and carbon oxides.
Thus, the separation of organic vapors from inert gases is accomplished. The liquid
solution is then heated up and sent to a desorption tower, where it is contacted with
superheated steam. The superheated steam there strips off the absorbed organics from
the liquid, leaving behind the solvent liquid, which is, upon cooling, re-circulated back
to the absorption column. The gas mixture consisting of steam and organics is then
passed to a cooler-condenser, where total condensation occurs, giving two liquid
phases in the decanter; water phase being at the bottom, because of insolubility of
organics in the water. Thus, recovery of organics from coke-oven gas has been
realized with the application of absorption and desorption operations. For the recovery
of benzene, toluene and xylenes in pure states from the liquid solution, another mass
transfer operation called rectification is used.
In the gas absorption and desorption operations, the two phases involved are the same:
gas and liquid. Mass transfer takes place between these two phases, only the directions
of transfer being different. Hence, for the understanding of these two operations, gas-
liquid equilibria must be known very well.
4.2 Gas-Liquid Equilibria: If a pure gas is brought to equilibrium with a liquid that
can dissolve this gas, at a constant pressure and temperature, the concentration of the
gas in the solution is known as equilibrium solubility or simply solubility of the gas
in this liquid. The solubility is generally obtained experimentally. If the pressure is
increased, keeping the temperature constant, the solubility of gas increases. By plotting
the solubilities against the pressures, the so-called solubility or equilibrium
(distribution) curve for this gas-liquid system is produced. This is shown in Fig.4.1 for
t2 t1 t: temperature
A1 A2
t2 > t1
Pressures of A1,A2,A3 gases
t1
A1
A3 t1
o
o x2 x1 x3
Mole fractions of A1,A2,A3 gases in liquid
Fig.4.1 The solubilities of gases in liquid
gases of A1, A2 and A3 in a certain liquid. The solubility of a gas in a liquid decreases
with increasing temperature. This is because of the fact that the dissolving of a gas in a
liquid results in the liberation of heat. This effect is shown in the figure for gas A1. The
solubilities of different gases in the same liquid at the same pressure and temperature
are different. It is obvious from Fig.4.1 that the solubility of gas A3 is greater than the
solubilities of gases A1 and A2. The solubilities of many industrially important gases in
water were measured experimentally and some are given in Table.App.4.1-4.4.
Let us now consider the solubilities of gas mixtures in the liquids. It has been found
that, at two special cases, the solubility of a component in the gas mixture is not
influenced by the existences of the other components in the gas, provided that partial
pressure of the component, instead of total pressure is taken. One of the special cases
occurs, when only one component of the gas mixture is soluble in the liquid
considered. For example if this special case is valid, then the solubility curve of gas,
say A3 in Fig.4.1 is also the solubility curve of this gas, when this gas is mixed with an
insoluble (inert) gas. This enormously reduces the number of the experimentation
needed for the determination of solubilities of gas mixtures. The second special case is
met, when the binary solutions obtained upon the dissolving of each component of a
gas mixture in the liquid considered are ideal. For example, if the solutions produced
by dissolving each of the A1, A2 and A3 gases in a certain liquid are ideal, the
solubility curve of say A1, when it is mixed with A2 and A3 is the same with the one
given in Fig.4.1. This applies of course to the other gases, A2 and A3. But, on the other
hand if the binary solutions produced are not ideal, the solubility curves obtained with
pure gases cannot be used for the gas mixtures. New experiments are needed for each
composition of the mixture.
4.2.1 Ideal Solutions: It was stated that gas-liquid equilibria are found experimentally.
There is an exception to this. This is the ideal solutions case. Because, as first stated by
Raoult, in an ideal solution, the partial pressure of solute A in the gas, pA is simply
equals the product of its vapor pressure, p oA at the prevailing temperature and its mole
fraction in the liquid solution, x. Thus Raoult’s law is written as:
p A = p oA x (4-1)
As it is seen, any term showing the effect of solvent S does not appear in the equation.
But it mustn’t be forgotten that S should be such a solvent that solution of A in S will
be ideal. So, it follows from equation (4-1) that solubility of a solute in ideal solution
in any solvent is always the same in terms of mole fractions. The vapor pressure of
each component is only the function of temperature and experimentally determined
relationship is given either in graphical form or by Antoine type equation. Since p oA is
only function of the temperature, the equation (4-1) is represented by a straight line
passing through the origin at a constant temperature. Hence, the solubility curve for an
ideal system is a straight line passing through the origin, which requires only one point
to draw. For a solution to be considered ideal, the following four points must be
fulfilled at the same time: 1o) Attraction and repulsion forces between S-S and A-S
molecules must be the same. 2o) The volume of the liquid solution must change
linearly with the composition of the solution. 3o) Dissolving of solute A in solvent S
must neither release nor absorb heat. Latent heat of condensation associated with the
condensing of vapor is excluded from this. 4o) The total pressure of gas must change
linearly with gas composition expressed as mole fraction.
In reality there is no solution fulfilling all these four conditions at the same time. The
closest approach is seen at the solutions of optic isomers, where the size, the structure
and the chemical nature of A and S molecules are the same. In practice, many
solutions can be considered ideal from engineering point of view, when the deviations
from ideality are not so significant. Especially, the solutions of adjacent or near
adjacent members of a homologous series of organic chemicals are considered so.
Example-4.1) Ideal Solution

Solutions of propane and butane in paraffin oil (M.W.=300) are both ideal. A gaseous mixture
consisting of propane-and butane is brought to equilibrium in paraffin oil at 2 bars and 10 oC, at which
volume percents of propane and butane in the gas are measured as 80 and 20 respectively.
Calculate the equilibrium solubilities of propane and butane at the given conditions as mole and mass
percent.
Antoine constants of propane and butane are as follows:
a b c
Propane 6.82973 813.200 248.000
Butane 6.83029 945.900 240.000
b
Antoine equation is , log p o = a − where po (mmHg) and t(oC)
c+t
Solution:
vapor pressures of propane and butane at 10oC

813.2 p oA1 = 4762.03 mmHg
Propane(1) : log p oA1 = 6.82973 − = 3.678
248 + 10
945.9 p oA 2 =1113.5 mmHg
Butane(2) : log p oA 2 = 6.83029 − = 3.047
240 + 10
In the gas mixtures : volume percent = mole percent, then y1=80/100=0.8 and y2=20/100=0.2
Raoult’s law : p A = p oA x ; Dalton’s law : p A = yP , combining these two : x = yP
p oA
Propane mole fraction in the liquid: y1 P (0.8)(2)
x1 = = = 0.252
p oA1 (4 762.03 / 760) *1.013
y2P (0.2)(2)
Butane mole fraction in the liquid: x2 =
o
= = 0.270
p A 2 (1 113.5 / 760) *1.013
Mole fraction of paraffin oil in the liquid: xB=1-(x1+x2) =1-(0.252+0.270)= 0.478
MA1 = 44, MA2 = 58, MS = 300
In 100 k-mol liquid solution:
25.2 k-mol Propane = (25.2)(44) = 1 108.8 kg Propane
27.0 k-mol Butane = (27.0)(58) = 1 566 kg Butane
47.8 k-mol Paraffin oil = (47.8)(300) = 14 340 kg Paraffin oil
Total mass of the liquid solution of 100 k-mol = 17 014.8 kg
mole/mole w/w
Propane : 25.2 (1 108.8/17 014.8)*100 = 6.52

Butane : 27.0 (1 566/17 014.8)*100 = 9.20
Paraffin oil : 47.8 (14 240/17 014.8)*100 = 84.28
100 100
4.2.2 Real Solutions: The solutions, which are far from fulfilling the conditions given
above, are called non-ideal or real solutions. The solubility diagrams of such solutions
cannot be represented by straight lines passing through the origin. They are mostly
curves. But, at most of them, solubility curve, which is determined experimentally, is
almost a straight line at very low solute concentration range and hence at this region,
p A = H A′ x (4-2)
can be written. This equation is known as Henry’s law equation, as it is first given by
Henry. H A′ (bar), which is known as Henry’s law constant, is only function of
temperature for a A-S system. Experimentally found Henry’s law constants for many
gases dissolved in water at various temperatures are given in Table.4.1. It follows from
equation (4-2) that the dimension of Henry’s law constant is pressure. Henry’s law is
also written as,
pA =ΉA cA (4-2b)
or as, y = mA x (4-2c)
Here, ΉA(bar m3/k-mol) and mA(-) are also known as Henry’s law constants.
Interrelationships between them are;
mA= Ή’A/P = ΉA c/P (4-3)
3
where, c (k-mol/m ) is the total molar concentration of liquid solution.
Table 4-1. Values of Henry’s law constants for some gases in water,
( H A′ * 10-4 bar)
t( oC) Air CO2 CO C2H6 H2 H2S CH4 NO N2 O2

0 4.38 0.0738 3.57 1.28 5.87 0.0272 2.27 1.71 5.36 2.58
10 5.56 0.105 4.48 1.92 6.44 0.0381 3.01 2.21 6.77 3.31
20 6.73 0.144 5.43 2.66 6.92 0.0489 3.81 2.67 8.15 4.06
30 7.81 0.188 6.28 3.47 7.39 0.0617 4.55 3.14 9.36 4.81
40 8.81 0.236 7.05 4.29 7.61 0.0755 5.27 3.57 10.54 5.42
50 9.58 0.287 7.71 5.07 7.75 0.0896 5.85 3.95 11.45 5.96
60 10.23 0.345 8.32 5.72 7.75 0.104 6.34 4.23 12.16 6.37
70 10.64 8.56 6.31 7.71 0.121 6.75 4.44 12.66 6.72
80 10.84 8.56 6.70 7.65 0.137 6.91 4.54 12.76 6.96
90 10.94 8.57 6.96 7.61 0.146 7.01 4.58 12.76 7.08
100 10.84 8.57 7.01 7.55 0.150 7.10 4.60 12.76 7.10
There is a relationship between Henry’s law constant, Ή’A and the heat of absorption,
∆Hs (kJ/k-mol), which is given as;
Ή’A = C e − ∆H / RT S
(4-4)
where, C is a constant that depends on A-S pair, R(=8.314 kJ/k-mol K) and T(K) are
general gas constant and absolute temperature. So, if the values of Henry’s law
constants at two different temperatures are known, heat of absorption of the system
can easily be computed from equation (4-4).
Example-4.2) Calculation of Heat of Absorption
For the system ammonia-water, which obeys Henry’s law for low concentration of ammonia, the
Henry’s law constant has the following values:
Temperature(oC) 20 25 30 35
Constant (bar) 0.73 0.96 1.23 1.55
What is the value of heat of absorption (solution) of ammonia in water over this temperature range ?
Solution :
∆H s
Take ln of both sides of the eqn.(4-4) lnΉ’A = ln C −
RT
or,
∆H s
logΉ’A = log C −
2.303 RT
So, slope of logΉ’A vs. 1 / T line = − ∆H s
2.303 R
t (oC) 20 25 30 35
1 −1 0.00341 0.00335 0.00330 0.003247

(K )
T
Ή’A (bar) 0.73 0.96 1.23 1.55
logΉ’A -0.137 -0.018 0.090 0.190
0.2 .
logΉ’A
H 0.1. y
∆y tg θ = -tgα
θ
0. α 1
( K −1 )
0. T
0.0033 0.0034
.0
-0.1 0.003243 ∆x x 0.003345
-0.2 .0
∆y 0 .2 − 0 . 0
slope = − tgα = − =− = − 1 906 .8
∆x (3.345 − 3.243) *10 −3
Then, ∆Hs = - (-1960.8)(2.303)(8.314) = 37 544 kJ / k-mol A absorbed
4.3 Selection of Solvent: As it was explained in the introduction section, in

absorption operations solvent S is selected and brought from outside. In many
absorption operations, there is large number of potential solvents, (excluding the cases
at which main purpose is to produce certain solution such as ammonia solution in
water, for which solvent is already fixed), among which, the most suitable one should
be selected by the designer. In selecting the most suitable solvent, the following points
should be considered: 1o) Solubility of the gas: select the solvent in which the
solubility of solute A is the highest, as this will require small quantity of solvent for
the operation. In looking at the solubilities, mass units should be used not the mole
units, as high molar solubility may mean low mass solubility due to the high molecular
weight of the solvent. 2o) Volatility of the solvent: the inert gas leaving the absorber is
almost saturated with the solvent vapor at the prevailing temperature. Hence, if the
vapor pressure of solvent is high at this temperature, considerable amount of solvent
loss will occur. This will not only result in loss of money but may also cause air
pollution, as the inert gas is normally let to the atmosphere. So, in order to prevent or
reduce these, the solvent, which has the lowest vapor pressure at the operating
temperature, should be selected. 3o) Corrosiveness of the solvent: the selected solvent
should not be corrosive to the ordinary construction materials, otherwise either the
equipment or part of it will be replaced frequently or expensive construction materials,
which are resistant to the attack of solvent should be selected. 4o) Viscosity of solvent:
viscosity of the liquid is not only important in heat and mass transfer taking place in it,
but also important in pumping it. It is seen from mass and heat transfer correlations
that high viscosity affects both heat and mass transfer coefficients adversely. Since
low transfer coefficients mean low rates of transfer, then the size of equipment should
be great. Hence, the viscosity of solvent should be as low as possible. This is also
important for the flooding, which will be dealt with later. 5o) Cost of solvent: although
the solvent is recovered and re-used in absorption operation, solvent losses are
inevitable. So, to keep the initial cost and the cost due to the solvent losses low, the
unit purchasing cost of solvent should be low. 6o) Other points: In addition to the
points cited above, some other properties of potential solvents should also be
considered. These are: toxicity, chemical stability, flammability and freezing point of
solvent.
Example-4.3) Selection of Absorption Temperature
In the production of maleic anhydride (MAN) from benzene with air oxidation, a new scheme is being
considered to recover the MAN from reactor exit gas mixture. For this purpose, the gas mixture
containing 3.5 mass percent MAN vapor (remaining may be assumed as air) will be washed with
dibutyl phthalate solvent (B.P.=340 oC, MS=278) in an absorber operating at 760 mmHg.
Find the solvent losses per ton of MAN recovered at the following 5 absorption temperatures,
assuming that all the MAN is recovered and the inert gas(air) leaving the absorber is saturated with
solvent vapor. Absorption temperatures are: 25, 50, 100, 150, 200 oC. The vapor pressures of dibutyl
phthalate at these temperatures are : 2.5*10-5; 4.8*10-4; 0.044; 1.07 and 11.52 mmHg.
Solution:
As the gas entering the absorber contains 3.5 mass percent MAN vapor, the amount of inert gas(air)
per ton of MAN is:
mc= (96.5)(1 000)/3.5 = 27 571.4 kg or nc= 27 571.4/29 = 950.7 k-mol
The amount of dibutyl phthalate vapor (mB) in the absorber exit gas is found as;
po p
yS = B yc = c p So + p c = P
P P
n S p oB n c pc
= = nS + n c = nT
nT P nT P
From these equations,
p So
nS = nc or,
P − p So
p So p So p So
mS = M Sn c = (278)(950.7) = 264 294.6
P − p So 760 − p So 760 − p So
is obtained. After calculating mS values at each temperature from the equation above and finding the
density of the absorber exit gas from ideal gas law, the following table has been constructed.
As it is seen from the table, at elevated absorption temperatures considerable loss of solvent occurs.
This results not only in loss of money but also in air pollution. As the maximum emission of dibutyl
phthalate to atmosphere is limited to 5 mg/m3 gas, absorption temperature must be kept below 50 oC.
t(oC) 25 50 100 150 200

-5 -4
p So (mmHg) 2.5*10 4.8*10 0.044 1.07 11.52
mS (kg dibp/ton MAN) 0.0087 0.167 15.30 372.62 4 067.7
3
ρG (kg/m ) 1.187 1.10 0.95 0.84 0.84
Dose (mg dibp/m3 gas) 0.375 6.7 527.2 11 252.4 123 928
4.4 Absorption Operations: The absorption operations carried out in chemical

industry can be divided in two main groups by looking at the contact type of gas and
liquid phases. In one group of operations, the gas and liquid phases are in close contact
with each other from the inlet points to the outlet points. Hence, the mass transfer from
gas to liquid takes place at every point of the equipment. These types of operations are
called as continuous-contact type of operations and the equipment in which these types
of operations are carried out are named as continuous-contact type of equipment.
Wetted-wall columns, spray columns and packed columns are typical continuous
contact type equipment. In other group of operations, gas and liquid phases come in
contact with each other at certain compartments of the equipment, which are called
stages, and where mass transfer from gas to liquid takes place. After certain time of
contact, the phases separate out and gas phase goes to the next stage up, and liquid
phase flows to the next stage down through different channels, during which they are
not in contact, hence there is no mass transfer between. As these types of operations
are called as stage-wise operations, the equipment in which these types of operations
are carried out, are named as stage-wise contact type of equipment. Plate (tray)
columns are typical stage-wise contact type of equipment.
In both type of operations, the two phases flow counter-currently in the equipment,
which is normally operated continuously at steady-state. Below, gas absorption
operations will be first dealt with in continuous contact type of equipment and later in
stage-wise contact type of equipment.
4.4.1 Gas Absorption in Continuous Contact Type of Equipment: As it was
explained above, gas absorption operations are carried out in wetted-wall columns,
spray columns and packed columns as continuous-contact type of operation.
4.4.1.1 Wetted-Wall Column: This is the simplest equipment used in gas absorption.
In a vertical pipe, while liquid solvent flows as a thin film down on inside surface of
the pipe, the gas phase is made to flow through the pipe upward, as shown in Fig.4.2.a.
Down flowing liquid absorbs solute A from gas at every section of the pipe. Since the
mass transfer area is limited with the diameter and the length of the pipe, this
equipment has very small mass transfer area per unit volume. For that reason, wetted-
wall columns are no longer used in modern plants except the case that when heat of
absorption is large and is the main problem in the design of absorber. In these cases
wetted-wall columns equipped with cooling jackets are quite useful. By circulating a
suitable cooling medium in the jacket, heat of absorption is removed from the system
and thus absorption medium is kept at constant temperature. If the heat of absorption is
very great, construction of the absorber in the form of shell and tube heat exchanger is
advised, as in this case more heat transfer area (of course also mass transfer area) per
unit volume can be stacked. In the design of such wetted-wall absorbers not only the
absorption duty but also the heat transfer duty is taken into consideration. If the
diameter and length of the tubes are specified, the number of the tubes required for
heat and mass transfer are computed independently and greater one is taken for the
Gas
A+C
Gas
A+C
Liquid solvent Liquid
solvent
S S
A Cooling liquid Cooling

Tubes liquid
Column
A Liquid film Liquid film
Column
A Cooling
liquid
Cooling Cooling liquid
jacket A
Gas
A+C
Gas Solution Solution

A+C
(b)
(a)
Fig.4.2 Wetted-wall columns : (a) Single pipe type, (b) Shell and tube type
construction. The required mass transfer area (Sm), hence the number of the tubes (n)
for a given absorption duty ( N A ) is computed from,
N
Sm = n π d i l = A (4-5)
NA
where, di(m) and l(m) are the inside diameter and the length of each tube, NA is the
total molar flux of solute A, which is computed from suitable equations given in
Chapter-3. The absorption duty, N A can easily be calculated from the given molar
flow rate of gas and from the mole fractions of solute A at inlet and outlet gas.
Example-4.4) Design of Wetted-Wall Absorber
A binary gas mixture containing 5 percent solute A by volume is to be scrubbed with a liquid in a
wetted- wall absorber operating counter-currently at 35 °C and 1 bar pressure. The wetted-wall
column, due to the large heat of absorption, is to be constructed in ‘shell & tube’ form, from 6 m long
∅25*2 mm stainless steel tubes. Calculate the number of the tubes required for the below given values:
Gas and liquid flow rates to the absorber are 25k-mol/h and 45 k-mol/h respectively. Exit gas will not
contain more than 0.5 percent solute A by volume. Equilibrium relationship for the system at the
operating conditions may be represented as y*= 0.52x, where y and x are mole fractions of solute A in
gas and liquid respectively. Over-all mass transfer coefficient based on gas phase is calculated as K'y
= 6.02 *10-4 k-mol/m2s. Heat of absorption of solute A in the solvent is 120.103 kJ/k-mol A absorbed.
Over-all heat transfer coefficient based on outside tube area is estimated as 140 W/m2 K. Inlet and
outlet temperatures of cooling water, which circulates in the shell are 25 °C and 30 oC respectively.
Solution:
First, find G2, L1 and x1

G2
Total material balance :
y2=0.005
G1+ L2 = G2 + L1
Solute A balance :
G1y1 + L2 x2 = G2 y2 + L1x1
Inert C balance :
Gs= G2 (1 - y2) = G1(1 - y1)
G1 (1 − y1 ) 25 (1 − 0.05)
G2 = = = 23.87 k − mol / h L2= 45 k-mol/h
1 − y2 1 − 0.005
x2=0.0
L1= G1+L2-G2=25+45-23.87= 46.13 k-mol / h 2
(25)(0.05)+(45)(0.0)=(23.87)(0.005) + (46.13) x1 tco=30 oC
x1 = 0.0245
Now, calculate the required number of the tubes l=6 m
for mass transfer duty;
NA
S mi = = n π di l Smi=n smi
NA tci=25 oC
1
do
y1=0.05
G1=25 k-mol/h
dii smi= π di l
L1,x1
l
N A = G1 y1 − G 2 y 2 = (25)(0.05) − (23.87)(0.005)
ao= π dol k − mol A k − mol A
=1.13 = 3.14 *10 −4
tube h s
K′y
Total molar flux of solute A : NA = ( y − y∗ ) ln
β∗y
t
Driving force for mass transfer at the bottom : ∆y1 = ( y1 − y1∗ )
y1∗ = 0.52 x1 = 0.52(0.0245) = 0.01274 ∆y1 = (0.05 − 0.01274) = 0.0373

Driving force for mass transfer at the top : ∆y 2 = ( y 2 − y∗2 )
y∗2 = 0.52 x 2 = 0.52(0.0) = 0.0 ∆y 2 = (0.005 − 0.0) = 0.005
∆y1 − ∆y 2 0.0373 − 0.005

( ∆y) ln = ( y − y∗ ) ln = = = 0.0161
ln(∆y1 / ∆y 2 ) ln(0.0373 / 0.005)
Average driving force for the absorber :
K′y 6.02 *10−4 k − mol A

Total molar flux of solute A : NA = ( y − y ∗
) = (0.0161) = 9.69 *10−6
βy
∗ ln
1 m2 s
−4
Then, required mass transfer area; N 3.14 * 10
S mi = A = = 32.42 m 2
N A 9.69 * 10 −6
Smi S mi 32.42
Then, required number of the tubes; n= = = = 81.9 = 82
s mi π d i l π (0.021)(6)
Required heat transfer area ; A = q where, Ao= n ao
U o (∆T ) ln
o
Heat load : q = N A
∆H s
= ( 3.14 * 10 −4
)(120 * 10 3
) = 37.68 kJ / s (= kW )
Driving force for heat transfer at the bottom and at the top: ∆T1= 35-25 = 10 oC , ∆T2=35-30 = 5 oC
∆T1 − ∆T2 10 − 5
Average driving force for heat transfer for the absorber: (∆T) ln = = = 7.2 o C = 7.2 K
ln(∆T1 / ∆T2 ) ln(10 / 5)
q 37.68 *103
Then, required heat transfer area ; Ao = = = 37.38 m 2
U o (∆T) ln (140)(7.2)
Ao A 37.38
Then, required number of the tubes; n= = o = = 79.4 = 80
a o π d o l π (0.025)(6)
Conclusion: An absorber with 82 tubes will be sufficient for the specified heat and mass transfer
duties.
4.4.1.2 Spray Column: This simple
equipment is essentially a vertical pipe
Gas equipped with a liquid-spraying nozzle-group
A+C
at the top. As the solvent droplets formed at
the nozzles rain down in the column, the gas
liquid mixture flows upward coming in contact with
distributor
Liquid the liquid droplets, during which solute A
solvent S transfers from gas to liquid. The surfaces of
liquid
liquid drops act as mass transfer area; hence
column drops creating large number of small diameter drops
at the spray nozzles is preferred from mass
transfer point of view. But, because of the
back-mixing, drops cannot be made very
Gas small. In addition to this, drops tend to
A+C
coalesce by touching with each other, after
they travelled certain distance. For that, the
height of column cannot be made very long.
solution This means spray columns can only be used
when the concentration change required in the
Fig.4.3 Spray column used in gas absorption gas phase is small.
4.4.1.3 Packed Column: The most commonly
used continuous-contact type of equipment is
the packed column. As the name implies, these columns are vertical pipes filled with
suitable packing materials. German chemist Dr.F.Raschig, in search for increasing the
efficiency of wetted-wall columns, filled the empty pipe with inert solid particles and
used for the first time the so-obtained columns in mass transfer operations. Later on,
use of packed columns has extended rapidly with the inventions of various new
packing materials. In packed columns, the liquid solvent, which is introduced to the
column at the top through a liquid distributor, flows down through the voids by
wetting the surfaces of all the packings as thin films. The gas phase, which enters the
column at the bottom, flows upward through the same voids by coming in contact with
the liquid films on the packing, during which solute A transfers from gas to liquid
films. It follows from this that the surfaces of all the packings act as mass transfer area.
For that reasons, the packed columns are the columns, which have the highest mass
transfer area per unit volume of the equipment and because of this, they are the most
widely used continuous-contact type mass transfer equipment.
Packing materials: There is large number of packing materials of different shape and
size and improvement of the existing ones and invention of new ones continue without
interruption. The common features of the packing materials that are to be looked at for
the selection of the best ones for a specific operation are: 1o) Specific surface, aP
(m2/m3): it is defined as the surface area per unit volume of packed bed and it must be
as great as possible, since these surfaces act as mass transfer area, if of course are
wetted properly with the liquid. 2o) Void fraction, ε (m3/m3): the void fraction is
defined as the volume of the empty spaces divided by total volume of the packing. As
the liquid and gas flow through these voids, whenever possible void fraction should be
very large. Small ε results in high pressure drop in the gas phase and also reduces the
flooding gas velocity; in turns the first one increases the operating cost, the latter one
the fixed capital cost. 3o) Inertness of the packing, which is known as insolubility of
the packing material in gas and liquid at the operating conditions, is important for
keeping the mass transfer area in the column as unchanged and insuring the solution
against contamination. 4o) Robustness: the packing should have sufficient strength
against breakages and distortions during filling, emptying and piling. 5o) Cost: as in
many cases the cost of packing material is the main factor determining the total cost of
column, its unit cost should be as low as possible.
As stated above, various types of packing were developed by various companies, and
some of them are shown in Fig.4.4. These may be divided in three groups. Ring types:
these are hollow cylinders whose diameters are equal to the lengths. Raschig Rings,
Lessing Rings and Pall Rings are the most commonly known types. Saddle types:
these are more complicated in structure and common types are: Berl, Intalox, Torus,
Novalox Saddles . Structured types: they are produced with weaving the thin wires
or stripes in different shapes and are used at special applications, as they are rather
expensive. Montz-Pak, Koch-Flexipac and Sulzer-Mellapak are the very well
known types. All these packings are produced from different materials. Ceramic,
carbon, various metals and various plastics are selected as construction material
depending upon the corrosiveness of gas and liquid to secure the inertness property of
the packing stated above. Ring and saddle types are mostly constructed from ceramic,
as this is resistant to the attack of many gases and liquids. Packings are produced in
different sizes, which are standardized. The important properties of some of the
packings in the first and second groups are given in Table.4.2. More detailed
information is obtained from the catalogues of the producers. The packings in the third
group whose aP and ε are much higher than others, are constructed specially in the
modules of 0.25 to 0.50 m heights for the specified column diameter. For large
Raschig Rings Lessing Rings Pall Rings diameter
Berl Saddles Novalox Saddles Torus Saddles Intalox Saddles
columns, the modules are produced in segments to facilitate easy
Montz-Pak type: BSH Koch-Flexipac Sulzer-Mellapak
Fig.4.4 Types of some packings
Table 4-2. Properties of some randomly filled packings
S i z e of p a c k i n g, mm
Packing
6 9.5 13 16 19 25 32 38 50 76
R a s c h i g R i n g s
Ceramic
Wall thickness,mm 0.8 1.6 2.4 2.4 2.4 3 4.8 4.8 6 9.5
Cf 1 600 1 000 580 380 255 155 125 95 65 37
ε 0.73 0.68 0.63 0.68 0.73 0.73 0.74 0.71 0.74 0.78
ap , m2/m3 787 508 364 328 262 190 148 125 92 62
Metal
0.8 mm thickness
Cf 700 390 300 170 155 115
ε 0.69 0.84 0.88 0.92
ap , m2/m3 774 420 274 206
1.6 mm thickness
Cf 410 29 220 137 110 83 57 32
ε 0.73 0.78 0.85 0.87 0.90 0.92 0.95
ap , m2/m3 387 236 186 162 135 103 68
P a l l R i n g s
Plastics
Cf 97 52 40 25
ε 0.87 0.90 0.91 0.92
ap , m2/m3 341 206 128 102
Metal
Cf 70 48 28 20
ε 0.93 0.94 0.95 0.96
ap , m2/m3 341 206 128 102
Flexiring
Cf 78 45 28 22
ε 0.92 0.94 0.96 0.96
ap , m2/m3 341 213 131 115
Hy-pak
Cf 45 18 15
ε 0.96 0.97 0.97
B e r l S a d d l e s
Ceramic
Cf 900 240 170 110 65 45
ε 0.60 0.63 0.66 0.69 0.75 0.72
ap , m2/m3 899 466 269 249 144 105
I n t a l o x S a d d l e s
Ceramic
Cf 725 330 200 145 98 52 40 22
ε 0.75 0.78 0.77 0.775 0.81 0.79
ap , m2/m3 984 623 335 256 195 118
Plastics
Cf 33 21 16
ε 0.91 0.93 0.94
ap , m2/m3 207 108 89
diameter columns, the modules are produced in segments to facilitate easy
installation. Ring type packings are filled into the column either in stacked or more
commonly randomly. It is obvious that the packings in the second group can only be
filled randomly. To minimize the breakages of packings in random filling, the
column is first filled with water and then the packings are poured in.
Column internals: In the construction of a packed column, apart from the packings
some ancillary equipment is also used. These are: 1o) Packing support: packing
supports are used at the bottoms of each packed section to carry the weight of packing
materials. Hence packing supports should be strong enough to carry the weight, which
is especially important for heavy material packings. In addition to this, packing
support should have a large void area to permit the passages of gas and liquid phases
without causing high pressure drops in them, and must not prevent the uniform
distribution of the phases across the whole cross-section of the column. Various types
of packing supports have been developed to accomplish these points. The bar grid is
obtained by welding metal strips at equal spaces in vertical positions to a metal
circular strip, which fits the column. In the more sophisticated ones, which are used in
large diameter columns, gas and liquid phases pass through separate slots and holes. In
Fig.4.5 some of the packing supports, used in industry are shown. 2o) Liquid
distributors and re-distributors: It is very important to wet all the surfaces of the
packings as otherwise these will not act as mass transfer area. Hence, requirement for a
uniform distribution of liquid throughout the whole cross-section of the column is
obvious. For that a liquid distributor at the top of the column should be installed to
distribute the liquid very well. Various liquid distributors were developed for this
purpose.
In randomly filled columns, the density of packing is smaller near the wall, and this
causes a tendency of liquid to separate and flow near the wall and gas to flow in the
centre. This is known as channelling and results in loss of efficiency of the column.
Although this can be reduced by making the ratio of packing diameter to the column
diameter smaller than 1/8, complete elimination of channelling is only possible by
installing liquid re-distributors at interval varying from 3 to 10 times the diameter of
column but at least every 6 to 7 meter. The liquid re-distributors collect the liquid near
the column wall and re-distribute it throughout the whole cross-section again. In
practice column is made in sections of 3 to 10 diameter heights and to the bottom of
each section a packing support and a liquid re-distributor are installed. In Fig.4.6 the
most commonly used liquid distributors and re-distributors are shown. 3o) Hold-down
plates: To prevent the carry over of packing materials of type-1 and type-2 by the gas,
a hold-down plate is placed at the top of a packed section (just below the liquid
distributor) of the column. This is especially important, when the gas velocity is high.
For packings made from heavy materials such as ceramic, hold-down plate may
restrain on the packed section freely, but for plastic packings hold -down plate must be
clamped to the wall of the column. As shown in Fig. 4.7, bar grid type hold-down
plates are generally used for this purpose. 4o) Entrainment eliminators: Especially at
high gas velocities, the gas leaving the top of the packing may carry off droplets of
liquid. This not only causes the loss of solvent but also may cause pollution of
atmosphere. To prevent this, above the liquid distributor a mist eliminator is installed.
Various types of mist eliminators are in use. A plate obtained by placing a layer of
about 100 mm thick wire mesh of 98-99 percent voids in a circular metal chamber can
collect almost all the droplets in the gas (Fig.4.7 d). Randomly filled about 1 meter
high packed bed will do the same duty.
Fig.4.5 Different types of packing supports
a b
c d
e f
g h
Fig.4.6 Liquid distributors (a,b,c,d,e,f) and re-distributors (g,h)
a b
c d
Fig.4.7 Hold-down plates (a,b) and Entrainment eliminators (c,d)
The view of vertical cut of a randomly packed column containing all these ancillaries
is shown in Fig.4.8
4.4.2 Gas Absorption in Packed Column: The calculation of height of packing of a

packed absorption column is the most important step of the design. We will derive an
equation now for the calculation of this. We assume that only one component
(component A) of the gas mixture is absorbed in isothermally operating column.
Consider the schematically drawn column in Fig.4.9, where G and L are the total
molar flow rates of gas and liquid as k-mol/s respectively. As the flow rates of gas and
liquid change along the column, with G1, L1 at the bottom, with G2, L2 at the top and
hence with G, L at any section of the column theirs values are shown. If x and y show
the mole fractions of solute A in liquid and gas, similarly with x1, y1 at the bottom,
with x2, y2 at the top and with x, y at any section of the column theirs values are
shown. Although G and L change along the column, Gs and Ls which show the molar
flow rates of inert gas component and liquid solvent respectively as k-mol/s remain
constant throughout the column.
Let us write total material balance for the whole column at steady-state: As the total
material entering the column is equal to the total material leaving the column,
G1 + L 2 = G 2 + L 1 (4-6)
is written.
gas
liquid
G2,y2
L2,x2
2 h=z
dh
L,x G,y
1 h=0
G1,y1
L1,x1
Fig.4.9 Schematic representation of a

packed column
Fig.4.8 View of vertical cut of a

packed absorption column
Similarly at steady-state, solute A balance for the whole column becomes,
G1 y1 + L2 x2 = G2 y2 + L1 x1 (4-7)
For the inert components of gas and liquid,

Gs = G1(1-y1) = G(1-y) = G2(1-y2)
Ls = L1(1-x1) = L(1-x) = L2(1-x2) (4-8)
are written.
Now, similar equations between any section and top of the column are written as,
G + L2 = G2 + L (4-9)
G y + L 2 x 2 = G2 y 2 + L x (4-10)
If the last equation is solved for y,
L G y − L2 x 2
y= x+ 2 2 (4-11)
G G
is obtained. This equation, which gives the relationship between gas and liquid
compositions at any section of the column, is known as operating line equation. So,
if this equation is known for the column, by knowing the composition of any phase at
any level of the column the composition of the other phase at the same level can easily
be computed from this equation. As shown in Fig.4.10 a, equation (4-11) represents a
curve on xy-diagram, limited by the points T(x2,y2) and D(x1,y1) and having a variable
slope of L/G .
If both gas and liquid phases are dilute for solute A, G1 ≅ G 2 ≅ G = cons. and
L1 ≅ L 2 ≅ L =cons. , and then equation (4-11) becomes,
L L
y= x + y2 − x 2 (4-12)
G G
This equation is represented with a straight line on xy-diagram, again limited by the
points T and D (Fig.4-10 b). As it is seen, operating line is a straight line for dilute
solutions. When the solutions are not dilute, operating line as was shown above, is a
curve. As the drawing of a curve is not easy, we prefer to write operating line equation
in a different way so that its representation on the diagram is still made by a straight
line. For this, if G, L, G2, L2 are taken from the material balance equations and
substituted into equation (4-11),
Ls /(1 − x ) G y /(1 − y 2 ) − Ls x 2 /(1 − x 2 )

y= x+ s 2 and from here,
G s /(1 − y) G s /(1 − y)
L L
Y = s X + Y2 − s X 2 (4-13)
Gs Gs
is obtained, where Y and X which are defined by Y= y/(1-y) and X = x /(1-x) are the
mole ratios in the gas and liquid phases respectively. Namely, Y is the moles of solute
A in the gas divided by the moles of inert gas component, and X is the moles of solute
A in the liquid divided by the moles of liquid solvent.
As it is seen from Fig.4-10 c, the equation (4-13) is represented by a straight line on
XY diagram, limited by the points T(X2,Y2) and D(X1,Y1) and with a constant slope
of Ls/Gs. So, working with mole ratios instead of mole fractions the operating line is
linearized. Summing up, if both solutions are dilute (x ≤ 0.05 and y ≤ 0.05 is sufficient
to consider the solutions dilute) equation (4-12), if the solutions are strong, equation
(4-13) is used as operating line equation.
y y Y
equation(4-11) equation(4-13)
equation(4-12) D
y1 D y1 D Y1
y2 slope=(L/G)≠cons. slope=(Ls/Gs) =cons.

T y2 slope=(L/G)=cons. Y2 T
T
x x X
x2 x1 x2 x1 X2 X1
(a) (b) (c)
Fig.4.10 Representation of Operating Lines on the graph
For the derivation of an equation from which height of packing can be computed, start
with considering a differential volume dv in the packing. Note that height of
differential volume, dh is related to this volume by dv = Ac dh, where Ac is the cross-
sectional area of the empty column.
At steady-state, along this differential volume solute A balance is written as:
The loss of solute A by the gas = The gain of solute A by the liquid
Hence, -d(G y) = d(L x) = NA dSm (4-14)
is obtained, where NA is the total molar flux of A transferring from gas to liquid, dSm
is the total mass transfer area available in the differential volume dv. If a mass transfer
area per unit volume of packing is defined by av(m2/m3) dSm becomes dSm = av Ac dh.
As it is seen, here av instead of ap is taken. This is because of the fact that
geometrically available area ap is mass transfer area only when it is wetted thoroughly.
Un-wetted part of ap does not act as mass transfer area. It is assumed that so-defined av
is constant throughout the column. This is so, when column is filled uniformly with the
packing and distribution of gas and liquid phases across the column cross-section is
the same at any height. By substituting dSm from equation above and solving for dh,
G2 y2 L1 x 1
Z
⌠ d (G y ) ⌠ d(L x )
Z= ∫ dh = − ⎮
⌡ NA Ac a v
= ⎮ N A a
⌡
(4-15)
o A c v
G 1 y1 L2 x2
is obtained. In reality, this equation is general equation for mass transfer between two
phases represented by G and L, in a packed column. Different solutions of equation
(4-15) is obtained for each mass transfer operation, as NA is differently expressed in
terms of mass transfer coefficients and driving forces for each operation. If it is
remembered from Chapter-3, for “A transferring through non-transferring
components” in both phases, as it is the case for gas absorption, NA is given as:
k ′y k ′x K ′y K ′x
NA = (y − yi ) = (x i − x) = ∗
(y − y∗ ) = ∗
( x ∗ − x ) (4-16)
(1 − y) i ln (1 − x ) i ln (1 − y) ln (1 − x ) ln
On the other hand,
⎛G y⎞ ⎛ y ⎞ G dy G dy
d(G y) = d⎜⎜ s ⎟⎟ = G s d ⎜⎜ ⎟⎟ = s
= and
⎝1 − y ⎠ ⎝ 1 − y ⎠ (1 − y) 1− y
2
⎛ Ls x ⎞ ⎛ x ⎞ L dx L dx
d(L x) = d⎜ ⎟ = L s d⎜ ⎟= s 2 = (4-17)
⎝1− x ⎠ ⎝ 1 − x ⎠ (1 − x ) 1− x
can be written. By substituting all these into equation (4-15) and taking constants Ac,
av outside the integral and furthermore assuming k ′y , K ′y ∝ G1.0 , k ′x , K ′x ∝ L1.0 and
hence G/k ′y ≅ cons., G/K ′y ≅ cons., L/k ′x ≅ cons. , L/K ′x ≅ cons. (If it is looked at mass
transfer correlations k ′y , K ′y ∝ G 0.8 and k ′x , K ′x ∝ L0.8 are seen. But here assuming the
powers as 1.0, instead of 0.8 the error involved is negligible from engineering point of
view) finally;
y1 x1
G ⌠ (1 − y) i ln dy L ⌠ (1 − x ) i ln dx
Z= ⎮ =
k ′y a v A c ⌡ (1 − y)( y − y i ) k ′x a v A c ⎮
⌡ (1 − x )( x i − x )
y2 x2
y1 x1
G ⌠ (1 − y) ∗ln
dy L ⌠ (1 − x ) ∗ln dx
= ⎮ = ⎮ (4-18)
K ′y a v A c ⌡ (1 − y)( y − y ∗ ) K ′x a v A c ⌡ (1 − x )( x ∗ − x )
y2 x2
are obtained. In the equations above, the terms outside the integrals are abbreviated
with HG, HL, HOG, HOL respectively and the terms under the integral signs with NG, NL,
NOG, NOL respectively, Hence;
G L G L
HG = , HL = , HOG = , HOL = (4-19)
k ′y a v A c k ′x a v A c K ′y a v A c K ′x a v A c
Height of one gas Height of one liquid Height of one overall Height of one overall
transfer unit transfer unit gas transfer unit liquid transfer unit
y1 x1 y1 x1
⌠ (1 − y) i ln dy ⌠ (1 − x ) i ln dx ⌠ (1 − y) ∗ln dy ⌠ (1 − x ) ∗ln dx
NG= ⎮ NL= ⎮ NOG= ⎮ NOL= ⎮
∗ ∗
⌡ (1 − y)( y − y i ) ⌡ (1 − x )( x i − x ) ⌡ (1 − y)( y − y ) ⌡ (1 − x )( x − x )
y2 x2 y2 x2
Number of gas Number of liquid Number of overall Number of overall
transfer units transfer units gas transfer units liquid transfer units
and in shorthand writing,
Z = HG NG = HL NL = HOG NOG = HOL NOL (4-20)
is obtained. Depending upon the information available any one of these four equations
can be used to compute the height of packing, z.
N values are named as number of transfer units and H values as height of one
transfer unit. Hence the height of packing required to make a change in the
composition of a phase (for gas this is from y1 to y2) is found by multiplying the
number of the transfer units needed to accomplish this change (this is NG or NOG for
gas) with the height of one transfer unit (this is HG for NG and HOG for NOG). Note that
N’s are dimensionless and H’s have the dimensions of length. Equation (4-20) can also
be used at the desorption operations, as in these operations solute A transfers through
non-transferring components in both phases as well. But, since transfer direction of
solute A is from liquid to gas, the driving forces in N’s should be taken as (yi-y),
(x-xi), (y*-y) and (x-x*) respectively.
4.4.2.1 Calculation of Number of Transfer Units: N values are obtained by

performing the integrals. These integrals however cannot be solved directly, when the
P=cons. D
y1
t=cons.
Mole fraction of solute A in gas, y
Operating line
Equilibrium
P distribution curve
y
E
yi k ′x /(1 − x ) i ln
M slope= -
y2 k ′y /(1 − y) i ln
T
y*
R
0
0 x2 x xi x* x1
Mole fraction of solute A in liquid, x
Fig.4.11 Graphical integration of N values
relationships between say y and yi or x and xi are not given functionally as is the case
at many applications. Then graphical integration is resorted to.
Graphical integration: First, operating line and equilibrium distribution curve are
both drawn on a millimetric paper as shown in Fig.4.11. Point P’s are then arbitrarily
chosen between T and D and from these points PM lines are drawn by trial and error
as explained in Chapter-3. For the calculation of NG, yi values and for the calculation
of NL , xi values are read from points M and the following table is constructed. In the
select read from graph c a l c u l a t e
y yi (1-y) (1-yi) (y-yi) (1-y)iln (1-y)iln/(1-y)(y-yi)
y1 - - - - - -
- - - - - - -
- - - - - - -
y2 - - - - - -
table, only the values required for the calculation of NG are shown. The values in the
last column of the table are taken against the corresponding values in the first column
on a millimetric paper. The area under the curve between limits of y1 and y2 gives the
value of NG. The accuracy of the calculation depends on the number of the P points
selected. The calculations of NOG and NOL are much easier, as in this case; drawing of
PM lines is not required. For the calculation of NOG ,the ordinates of points R and for
NOL , the abscissa values of points E are needed. Note that at desorption the operating
line lies below the equilibrium distribution curve.
Dilute solutions: If both solutions are dilute then 1 can be neglected next to x and y
and integral terms simplify so that analytical solutions can be derived. Take NOG as an
example, with this assumption it is written as,
y1
⌠ dy
N OG = ⎮ (4-21)
⌡ y − y∗
y2
if the equilibrium distribution curve is given by the following linear equation between
x1 and x2 (m and n being constants);
y* = mx + n (4-22)
and if it is remembered that equation (4-12) is the operating line equation for dilute
solutions,
L L
y= x + y2 − x 2 (4-12)
G G
Then by substituting the equation below, which is obtained by eliminating x between
equations (4-12) and (4-22), into equation (4-21)
mG
y∗ = ( y − y 2 ) + mx 2 + n (4-23)
L
y1 y1
⌠ dy ⌠ dy
N OG = ⎮ = ⎮
⎮ y−
mG
( y − y 2 ) − mx 2 − n ⎮ y(1 −
mG
)+
mG
y 2 − mx 2 − n
⌡ ⌡
y2 L y2 L L
mG mG
y1 (1 − )+ y 2 − mx 2 − n
1 L L
= mG
ln
mG mG
1− y 2 (1 − ) + y 2 − mx 2 − n
L L L
⎡ mG ⎤
y1 − ⎢ ( y 1 − y 2 ) + mx 2 + n ⎥
1 ⎣ L ⎦ 1 ( y − y∗ )1
= ln = ln (4-24)
1−
mG y 2 − (mx 2 + n ) 1−
mG ( y − y∗ ) 2
L L
is obtained. If equation (4-23) is first written at top conditions and then ( y1∗ − y ∗2 ) is
mG
solved, by noting that [(mx2 + n ) = y ∗2 ]; ( y1∗ − y ∗2 ) = ( y1 − y 2 ) is obtained. It
L
mG y ∗ − y ∗2 ( y − y ∗ )1 − ( y − y ∗ ) 2
follows from this that: 1− = 1− 1 =
L y1 − y 2 ( y1 − y 2 )
when this is substituted into equation (4-24) finally,
y1 − y 2
NOG = (4-25)
( y − y ∗ ) ln,1,2
is found. Note that (y-y*)ln,1,2 ,which is given by the equation below, is the logarithmic
mean of the overall driving forces for mass transfer calculated at the top and at bottom
of the column.
( y − y ∗ )1 − ( y − y ∗ ) 2
( y − y ∗ ) ln,1, 2 =
[
ln ( y − y ∗ )1 /( y − y ∗ ) 2 ]
Hence, the number of the overall gas transfer units, NOG required for the creation of a
concentration difference in the gas phase, which is (y1-y2), is simply obtained by
dividing this concentration difference with the logarithmic mean of the overall driving
forces calculated at the top and bottom of the column.
If the system obeys Henry’s law, the equilibrium distribution curve is given by y*= mx
and then NOG becomes:
1 ⎡ y − mx 2 1⎤
N OG = ln ⎢ 1 (1 − 1 / α) + ⎥ (4-26)
1 −1/ α ⎣ y 2 − mx 2 α⎦
L/G
where, α is known as absorption factor and given as α = .
m
Similarly, at the desorption operation for NOL;
⎡ x − y1 / m ⎤
ln ⎢ 2 (1 − α) + α ⎥
x − y1 / m
N OL = ⎣ 1 ⎦ (4-27)
1− α
can be derived.
Graphical Construction of Transfer Units (Baker’s Method): It follows from
equation (4-21) that one overall gas transfer unit results when the change in gas
composition equals the mean overall driving force for mass transfer, causing the
change. Baker, considering this fact, developed a graphical method for the calculation
of number of transfer units by drawing. According to this method, first, operating line
and equilibrium distribution curve are plotted on a millimetric paper as shown in
Fig.4.12. Then, if NOG is to be calculated a so-called bisect line, dividing the vertical
distances between operating line and equilibrium distribution curve in two equal parts
everywhere, is drawn. By starting at any end (in the Figure this is top end) of the
column number of the overall gas transfer units are drawn as follows: A horizontal line
TF is so drawn that TE=EF and then is continued vertically until cutting the operating
line (point R). Now, if it can be shown that HI = FR, then the right angle triangle TFR
represent one overall gas transfer unit, as FR is the concentration difference occurred
in the gas and HI is the mean overall driving force causing this change. THE and TFR
are similar triangles and hence, TE/TF = HE/FR can be written. On the other hand
TF=2TE from the drawing and 2HE = HI from the definition of bisect line and hence
finally, FR =2HE = HI is obtained. This proves that right angle triangle TFR is an
overall gas transfer unit. The drawing in this way is continued until reaching point D.
The number of the right angle triangles found gives the required number of the overall
gas transfer units. For Fig.4.11 this is slightly smaller than 4.
y
D
y1 K
P=cons.
t=cons.
Operating line
Equilibrium
disribution curve
yR R Bisect line
H
yH
y2 T
E F
yI
C I Draw TE=EF
0
0
x
x2 x1
Fig.4.12 Determination of NOG by Baker’s Method
By drawing the bisect line which divides the horizontal distances between operating
line and equilibrium distribution curve in two equal parts everywhere, and following
the same steps explained above starting at point D, the number of the overall liquid
transfer units, NOL can be calculated.
Example-4.5 Calculation of Number of Transfer Units
Air, containing 3 % acetone by volume is to be washed with water in a packed column operating
counter-currently at 1 bar and 25 oC, to reduce the acetone content to 0.5 % by volume. The flow rates
of the gas and acetone-free water to the column are 300 k-mol/h and 690 k-mol/h respectively.
a) Write the operating line equation,
b) Calculate the concentration of liquid solution leaving the column as mass percent,
c) Calculate the percentage recovery of acetone,
d) Calculate number of the over-all gas transfer units required.
At the operating pressure, temperature and the concentration range the equilibrium distribution of
acetone between air and water is given as y*=2.2x, where y and x are the mole fraction of acetone in
gas and liquid respectively.
Solution :
Assumption : Solutions are dilute (to be checked later !)

a) Equation (4-12) is the operating line equation for dilute solutions. y2=0.005
690 690
Then; y= x + 0.005 − (0.0) L=690 k-mol/h
300 300
y = 2.3 x + 0.005 2 x2=0
b) Operating line equation at the bottom of the column;
y1 = 2.3 x 1 + 0.005
Then, y − 0.05 0.03 − 0.005
x1 = 1 = = 0.0109
2.3 2.3
As it is seen, dilute solutions assumption is valid. 1 G=300 k-mol/h
Absorbed acetone : L(x1-x2)= 690(0.0109-0.0)= 7.51 k-mol/h
Amount of solution leaving the column, y1=0.03
L& = (690)(18) + (7.51)(58) = 12 855.6 kg / h

x1=?
Then, mass percent of acetone in the solution;
(7.51)(58)
x& 1 100 = .100 = 3.39 %
12 855.6
7.51
c) Percentage recovery of acetone = .100 = 83.4 %
(300)(0.03)
d) Since the solutions are dilute, equation (4-21) or (4-25) can be used. From equation (4-21)
0.03
y 0.03 ⌠ 0.03
⌠ dy ⌠ ⌠
1
dy dy dy
N OG =⎮ = ⎮ = ⎮ = ⎮
⌡y − ∗
⌡0.005 − ⎮ y − 2.2( − + 0.0048
2
y y y 2. 2 x
⌡0.005
y 0 .005
) ⌡0.005 0.0435 y
2.3
1 (0.0435)(0.03) + 0.0048
= ln = 4.51 is obtained.
0.0435 (0.0435)(0.005) + 0.0048
4.4.2.2 Calculation of Individual Heights of Transfer Units: For the calculation of

height of packing by using the number of gas or liquid transfer units, the relevant
height of one transfer unit is needed. These can only be found experimentally as they
contain mass transfer coefficients. Instead of determining individual mass transfer
coefficients and mass transfer area per unit volume of packing separately and then
substituting them into equations defining H’s, H values are directly measured. For the
experimental determination of HL, sparingly soluble gases in water such as O2, N2 are
used as test gas. Sherwood and Holloway have given the so-obtained results by
H L = a (L′ / µ L ) b Sc 0L.5 (4-28)
where, HL is the height of one liquid transfer unit in (m), L' is the mass flow flux of
liquid phase in (kg/m2s), µL is the viscosity of liquid in (kg/ms), and ScL is the
Schmidt number of the liquid phase. a and b are the constants that depend on the type
and the size of packing. Their values for Raschig rings and Berl saddles for the most
commonly used sizes are given in Table.4.3.
Table 4-3. The constants of Sherwood-Holloway equation
Packing mmxmm a b
Raschig ring
9.5x9.5 0.00032 0.46
12.7x12.7 0.00072 0.35
25x25 0.00235 0.22
38x38 0.00260 0.22
50x50 0.00293 0.22
Berl saddle
12.7x12.7 0.00146 0.28
25x25 0.00128 0.28
38x38 0.00137 0.28
For the determination of HG, the mixtures of very soluble gases with air, such as
ammonia are used as test gases. Fellinger has given the following dimensional
equation:
H G = a (G ′) b (L′) c Sc 0G.5 (4-29)
' '
where, HG is the height of one gas transfer unit in (m), G and L are the mass flow
fluxes of gas and liquid phases respectively in (kg/m2s), and ScG is the Schmidt
number of the gas phase. a, b and c are the constants that depend on the type and size
of packing. Their values for Raschig rings and Berl saddles for the most commonly
used sizes are given in Table.4.4
Table 4-4. The constants of Fellinger equation
Packing, mmxmm a b c
Raschig ring
9.5x9.5 0.62 0.45 -0.47
25x25 0.56 0.32 -0.51
38x38 0.69 0.38 -0.40
50x50 0.89 0.41 -.045
Berl saddle
12.7x12.7 0.54 0.30 -0.74
25x25 0.46 0.36 -0.24
38x38 0.65 0.32 -0.45
The equations given above should be used cautiously only when experimentally
measured value for the system with the specified packing is not available, as they have
wide scattering of data. In the literature, experimentally measured values for various
systems with different packings are available. Perry’s handbook contains a list of
references for various systems.
HOG and HOL can easily be synthesized from HG and HL. To show this, take the
following equation from Chapter-3:
1 1 m
= + (4-30)
K ′y k ′y k ′x
If both sides of this equation are multiplied with G/avAc and in addition, the last term
of the right hand side is multiplied also with L/L;
G G mG L
= + is obtained. By comparing this equation with
K ′y a v A c k ′y a v A c L k ′x a v A c
the equations (4-19),
mG
H OG = H G + HL (4-31)
L
is found. Similar analysis for HOL results in,
L
H OL = H L + HG (4-32)
mG
4.4.2.3 Determination of Diameter of a Packed Column: Determination of the

diameter of a packed column constitutes the second step in the design of a packed
column. As was explained before, gas and liquid phases flow counter currently
through the voids of the packing. The hydrodynamic interaction of gas and liquid in
these voids is the most important point influencing the diameter of the column.
Assume that a randomly packed column made of glass and equipped with a device to
measure the pressure drop of the gas along the packing, is used for experimentation.
The lines carrying the gas and liquid to the column contain rotameters to measure the
flow rates. In the first experiment let us assume that gas is made to flow through dry
packing. A table can be formed by writing the pressure drops in the gas (∆P) against
the increasing flow rates of gas. If the logarithms of pressure drops are plotted against
the logarithms of superficial gas velocities (uG), which are calculated by dividing the
volumetric flow rates of gas by the cross-sectional area of empty column, the line-1
shown in Fig.4.13 is obtained. Calculated slope of this line gives ∆P ∝ u1G.8 , which
indicates that gas flow through the voids is turbulent. If the experiment is repeated
with wet packing, this time the line-2 is obtained, indicating that higher pressure drops
at the same gas velocities, as expected, are recorded. In the third experiment, again the
pressure drops at various gas flow rates are monitored but unlike the first two, this
time liquid flows down at a constant flow rate of L1. In this case, the ∆P-uG
relationship has three distinct regions: Up to the point a the change of ∆P with uG is
the same, of course with higher ∆P values for the same uG, but after this point, the
change becomes steeper up until another point b, from where the change is even more
steeper than the previous one.
3 L3> L2 > L1
L3 L2 2
L1
1
Log(∆P)
b b b
a a a
L=0
0
0 uGF
Log uG
Fig.4.13 Loading and Flooding points
If we look at the inside of the column during this experiment, we notice that up to the
point a, gas and liquid phases flow through the column without affecting each other as
in the first two experiments. After point a, it is seen that interaction between liquid and
gas starts and so-called liquid hold-up (Ho), which is defined as the volume of the
liquid retained per unit volume of the packing, increases with increasing gas flow.
Point a is named as loading point. From point b on, liquid has no chance to flow
down the column as it is pushed up by the gas and forced out of the column through
the exit nozzle of gas. This condition, which is a hydrodynamic crisis, is known as
Flooding and the velocity of gas corresponding to point b, uGF is named as flooding
gas velocity. Repeating the experiments with higher constant liquid flows (L2 and L3)
produces the same phenomena, with loading and flooding points being at lower gas
velocities. It is obvious that in the design of packed columns, flooding should be
evaded. Hence, always a gas velocity below the flooding gas velocity must be selected.
It can easily be realized that flooding phenomena has nothing to do with mass transfer;
it is purely a hydrodynamic phenomena. By using various gases, liquids and packing
materials and by working under different flow rates and conditions, a generalized
equation in graphical form has been developed as shown in Fig.4.14, for calculating
flooding gas velocity for any gas-liquid pair in a randomly packed column at any
condition. The flooding curve is given as uppermost curve in the Figure. To the same
Figure, constant pressure drop curves of gas phase as Pascal per meter of packing are
also added, as the pressure drop in the gas phase along the packing is very important in
the design of packed columns. Here, L& ve G& are the mass flow rates of liquid and gas
as (kg/s) , ρ L ve ρ G are the densities of liquid and gas as (kg/m3), µL is the
viscosity of liquid as(kg/ms) and G' is the mass flow flux of the gas phase as (kg/m2s).
When reading the ordinate of the flooding curve, G ′ should be replaced by G ′F . The
effect of packing material on the flooding is given by Cf parameter, which is given for
various packings in Table.4.2. By dividing G ′F with the density of the gas, flooding
gas velocity uGF is first obtained, then by taking some percent (in practice usually 65-
75 %) of this velocity, operating gas velocity uG is found . Then from,
Dc = (4G& / πρ G u G ) 0.5 the diameter is calculated. In some cases, the diameter is
calculated according to a specified pressure drop in the gas per unit height of packing.
In this case, G' is computed from the ordinate of the point, which is obtained by
Flooding curve
G ′ 2 C f µ 0L.1
ρ G (ρ L − ρ G )
Pressure drop in
gas(Pa/m.packing)
0.5
L& ⎛ ρ G ⎞
⎜ ⎟⎟
& ⎜ρ −ρ
G ⎝ L G ⎠
Fig.4.14 Flooding and pressure drops in randomly packed columns
going vertically up from the calculated abscissa value until cutting the specified
pressure drop curve. Then, first cross-sectional area from A c = G& / G ′ and later the
diameter from Dc = (4Ac/π)0.5 is calculated.
The diameter of a column, which is packed with structured packing material given in
the third group (page:84), is normally calculated by using the information given in the
producer’s catalogues. For example for the calculation of the diameter of a column
which will be packed with type: BHS-400 packing material of Montz GmbH (shown
& )(ρ / ρ ) 0.5 then a x-
in Fig.4.4), first an s parameter is calculated from s = (L& / G G L
factor from x = - 1.443 s and finally a flooding factor from FFL = C ρ 0L.5 e x , where
C is given by the producer as 0.115 for type :BHS-400. Finally by taking some percent
of FFL (a figure between 70-75 % is recommended by the producer) the load factor Fv
and then by using equation uG =Fv / ρ G operating gas velocity is computed.
It has been stated many times that in order to obtain the highest efficiency, the packing
should be wetted properly at every point of the column. It has been shown
experimentally that the wetting rate, which is defined as L w = L& / ρ L A c a p and is
related to the liquid hold-up by the equation Ho = 0.0136 ap L0w.33 , should not be smaller
than 2.10-5 m3/ms for randomly packed columns. If this cannot be secured by changing
the size of packing, liquid circulation will be tried. The packing materials given in the
third group have the advantages of being wetted thoroughly at very low liquid rates.
Example-4.6) Calculation of Diameter and Height of Packing
The column in Example-4.4) will be packed with 32*1.6 mm metal Raschig rings.
Calculate:
a) The diameter of the column for a gas side pressure drop of 400 N/m2 per m of packing,
b) The height of packing required,
c) Check for minimum wetting rate and if it is not satisfied make necessary changes,
d) Find out with what percent of the flooding gas velocity the operation is carried out,
Heights of transfer units for acetone absorption into water in a column packed with 32*1.6 mm
Raschig rings were found experimentally and given as ;
G ′ 0 .395 and H L = 0.345 L′ 0.22 where, HG & HL are in m. G ′ & L′ are in kg/m s.
2
H = 1 . 397
L′
G 0 . 417
Solution:
a) Calculate the diameter at the bottom of the column, where liquid and gas flow rates are the highest.
Average molecular weight of the gas at the bottom; M G = (0.97)(29) + (0.03)(58) = 29.87
Density of the gas; (1)(29.87)
ρG = =1.21 kg / m 3
(0.083)(273 + 25)
As the density and viscosity of the 3.39 % acetone solution at 25 oC the density and viscosity of water
may be taken ,which are 997 kg/m3 and 0.894 cP .
Mass flow rate of liquid, , L& = 12 855 .6 kg / h = 3.57 kg / s
& = G * M = (300 )( 29.87 ) = 8 961 kg / h = 2.49 kg / s

G
Mass flow rate of gas, G
0 .5
L& ⎛ ρ G ⎞
0 .5
3.57 ⎛ 1.21 ⎞ Then from Fig.4.14, for ∆P/z = 400 N/m2 per m.
⎜ ⎟⎟ = ⎜ ⎟ = 0.05
& ⎜ρ −ρ 2.49 ⎝ 997 − 1.21 ⎠
G ⎝ L G ⎠
G ′ 2 C f µ 0L.1 is read. From Table.4.2 Cf =110 and ap = 162 m-1. Then,
= 0.08
ρ G (ρ L − ρ G )
0.5
⎛ (0.08)(1.21)(997 − 1.21) ⎞
G′ = ⎜⎜ − 3 0.1
⎟⎟ = 1.33 kg / m 2s
⎝ (110)(0.894 *10 ) ⎠
&
Cross-sectional area required, A c = G = 2.49 = 1.872 m 2
G ′ 1.33
0.5
⎛ 4 * 1.872 ⎞
Diameter of the column, Dc = ⎜ ⎟ = 1.55 m
⎝ π ⎠
&
L 3. 57
b) L′ = = = 1.91 kg / m 2 s HL = (0.345)(1.91)0.22 = 0.398 m
A c 1.872
(1.33) 0.395
H G = (1.397) = 1.194 m
(1.91) 0.417
From equation (4-31), H OG = 1.194 + (2.2)(1 / 2.3)(0.398) = 1.575 m
Finally, from equation(4-20), the required height of packing, z = (1.575)(4.51) = 7.10 m
L& 3.57
c) Wetting rate, L W = = = 1.18 * 10 − 5 m 3 / ms
ρ L A c a p (997)(1.872)(162)
As this figure is less than the recommended value of 2*10-5 m3/ms, either re-circulation of the liquid
must be considered or the size of the packing must be increased. When possible the latter choice is
preferred to the first one otherwise reduction in the driving force and hence increase in the number
of the transfer units is inevitable. If 50*1.6 mm Raschig rings are taken , instead of 32*1.6 mm,
Cf =57 and ap =103 m-1 (from Table.4.2). Then,
0.5
⎛ 110 ⎞
G ′ = (1.33)⎜⎜ ⎟⎟ = 1.85 kg / m 2 s
⎝ 57 ⎠
New cros-section, AC = 2.49/1.85 = 1.346 m2 ; new diameter, Dc = [(4*1.346)/π]0.5 = 1.31 m.
L′ = 3.57 / 1.346 = 2.65 kg / m 2s , HL = 0.345 (2.65)0.22 = 0.428 m, (1.85) 0.395
H G = (1.397 ) = 1.186 m
( 2.65) 0.417
HOG= 1.186 + (2.2)(1/ 2.3) (0.428) = 1.595 m. and z = (1.595)(4.51) = 7.19 m. In reality height of
packing will increase more than this , as the constants and exponents of HG & HL correlations will be
higher for this size of the packing .
3.57
LW = = 2.58 * 10 − 5 m 3 / ms . The wetting rate is now satisfactory.
(997)(1.346)(103)
0 .5
L& ⎛ ρ G ⎞
d) From flooding curve of Fig.4.14, for ⎜ ⎟⎟ = 0.05
& ⎜ρ −ρ
G ⎝ L G ⎠
G ′F 2 C f µ 0L.1 G′F = (0.28 / 0.08) 0.5 (1.85) = 3.46 kg / m2s
= 0.28 is found. Then,
ρ G (ρ L − ρ G )
G′ 1.85
Hence, percent of flooding = .100 = .100 = 53.5 % , which allows for safe operation.
G′F 3.46
4.4.3 Stage-Wise Contact Type of Absorption: As was stated before, gas absorption
operations are also carried out in stage-wise contact type of equipment. The most
commonly used stage-wise contact type of equipment is plate (tray) column.
4.4.3.1 Gas Absorption in Plate Columns: The plate column is a vertical pipe
containing horizontal plates at certain distances, which are known as plate spacing.
Various types of plates have been developed and are in use in industry, the common
properties of all are: They are circular metal plates of the diameter which are slightly
smaller than the inside diameter of the column. At large diameter columns, they are
divided into segments to facilitate easy installation. A segmental part of the plate is cut
off and a vertical metal sheet, which is known as down comer apron, at a length
which is 40-50 mm shorter than the plate spacing is attached to the plate to create a
channel between column shell and the apron, which is known as down-comer and
through which liquid phase flows. By leaving a segmental area equals the area of
down comer cross-section at the other side of the plate untouched, holes or channels
are opened in the area between, to facilitate gas flow through the plate. When the holes
are opened in the size range of 3-15 mm diameters, no additional parts are added to the
holes and so-obtained plate is known as sieve or perforated plate. In the other types
of plates, the hole diameters are lager (50-150 mm) and some special parts are attached
into or onto them to distribute the gas as tiny bubbles in the liquid on the plate, thus
valve plate, bubble-cap plate, tunnel-plate etc. are formed. The down comer apron is
extended about 25-150 mm above the plate to form a weir, by which a liquid pool on
the plate is always secured during the operation. Gas and liquid phases come in contact
only in the liquid pools formed on the plates and hence mass transfer between the
phases can only take place here. Between the plates; gas and liquid phases flow
through separate channels without seeing each other. In Fig. 4.16 (a) the view of
vertical cut of a sieve plate absorption column is shown. The column is schematically
shown as in Fig.4.16 (b). The plates are numbered from top of the column, and with n
and N any plate and the last plate of the column are shown respectively. As the total
Gas
G1,y1
Liquid Lo,xo
Downcomer
1
Weir G2,y2 L1,x1

2
Plate Down-comer
G3,y3 L2,x2
apron
Gn+1,yn+1 Ln,xn
Shell
Gas
GN+1,yN+1
∇
LN,xN
Solution
(a) (b)
Fig.4.16 (a) View of vertical cut of a sieve-plate absorption column, (b) Schematicall showing
of a plate column
flow rates of gas and liquid (G and L) and the concentrations of these phases change
from plate to plate, in order to refer to a particular phase and composition, the number
of the plate from which this stream comes is given as subscript to this property. Thus,
L3 , G3 , x3 , y3 show the flow rates of liquid and gas leaving the third plate and the
mole fractions of solute A in these streams respectively. The streams and compositions
in the schematically shown column were numbered according to this principle. It is
easy to understand why the liquid and gas phases entering the column are shown by Lo
and GN+1. The compositions of gas and liquid phases entering any plate n, which are
xn-1 and yn+1 are not equilibrium values. During the contact, they approach the
equilibrium values, as solute A transfers from gas to liquid, and if sufficient contact
time is provided they finally reach in equilibrium. Then the compositions of the two
phases (Ln and Gn phases) leaving the plate, which are xn and yn become coordinates
of a point lying on the equilibrium distribution curve of the system. So-operating plate
is named as equilibrium plate, ideal plate or theoretical plate. On the other hand, if
the two phases do not remain sufficiently long time in contact, then the two phases
leaving the plate will not be in equilibrium and so-operating plate is named as real or
actual plate. In practice, the plates operate as real plate, since it is not economical to
keep the two phases in contact very long time. From these definitions, it is understood
that equilibrium plate accomplishes maximum possible change in the compositions of
the phases, whereas real plate does only part of this maximum change. Nevertheless, in
the analysis of plate columns; all the plates are first assumed as operating as
equilibrium plates and then the number of the equilibrium plates needed for the given
separation is computed. Then, by determining the approaches of the plates to the
equilibrium plates, this equilibrium plate number is converted to the actual plate
number, which really interests us. A concept, which is known as plate efficiency is
frequently used to determine the performances of real plates. Plate efficiency can be
defined in terms of gas and liquid phases. To the memory of Murphree, who first
used these efficiencies, Murphree gas and Murphree liquid efficiencies are defined as:
y n +1 − y n x n − x n −1
E MG = E ML = (4-33)
y n +1 − y ∗n x ∗n − x n −1
It follows from the equations above that the plate efficiency is defined as the ratio of
the actual change in the composition of a phase on a plate to the change that would
have been obtained, if the two phases leaving the plate were in equilibrium. The
changes in the compositions of gas and liquid on an equilibrium and on a real plate are
shown in Fig.4.17.
The value of the plate efficiencies defined by equation (4-33) may change from plate
y y
Real Plate
Equilibrium Plate
Slope=-L/G yn+1 Slope=-L/G

yn+1
yn
Equilibrium Equilibrium
yn distribution curve y ∗n distribution curve
x x
xn-1 xn xn-1 xn x ∗n
Fig.4.17 Changes in the compositions of gas and liquid on an Equilibrium and

on a Real Plate
to plate. Hence, it is more convenient to use over-all column efficiency, Eo in
converting the number of the equilibrium plates to the number of the real plates, as this
efficiency is defined as the ratio of the number of the equilibrium plates needed to
accomplish the desired change in the compositions, to the number of the real plates
needed to accomplish the same change.
Eo = Nideal/Nreal (4-34)
The efficiencies of both plate and column are determined in pilot size columns
experimentally. Some experimental results obtained in bubble-cap absorption columns
are listed in Table 14-56 of Perry’s Chemical Engineers’ Handbook (4th ed.
Page:14-38). The correlation given by O’Connell in graphical form and shown in
Fig.4.18 may be used to estimate the over all column efficiency, when experimentally
measured values are not available. Although this correlation was obtained with bubble-
cap absorber, it can be used for other types of plates for approximate calculations. In
the figure below; m(=y/x) is the slope of equilibrium distribution curve, ML,
µL(kg/m.s) and ρL(kg/m3) are the molecular weight, viscosity and the density of the
liquid phase.
By dividing the number of the ideal plates obtained for a given absorption by using
Over all column
efficiency, Eo
mM L µ L
ρL
Fig.4.18 Over all column efficiency for bubble-cap absorber
any one of the methods given below, by the over all column efficiency, the number of
the real plates is found. Although the number of the ideal plates may be a fractional
number, the number of the real plates must always be an integral number.
Calculation of the Number of the Ideal Plates: In the design of a plate type absorber,
calculation of the number of the ideal plates constitutes the first step. Below, necessary
equations are to be derived. Let us assume again that only one component of the gas
mixture is absorbed in an isothermally operating column.
By writing total material and solute A balances for the whole column shown in
Fig.4.16b,
Lo + GN+1 = LN + G1 (4-35)
Lo xo + GN+1 yN+1 = LN xN + G1 y1 (4-36)
are obtained. As the flow rates of the inert components of the gas and liquid phases are
constant then,
Gs = G1(1-y1) = G n+1(1-yn+1) = GN+1(1-yN+1) and
Ls = Lo(1-xo) = Ln(1-xn) = LN(1-xN) (4-37)

can be written. By writing the same balances between top of the column and any plate
(plate n),
Lo + Gn+1 = Ln + G1 (4-38)
Lo xo + Gn+1 yn+1 = Ln xn + G1y1 (4-39)

and by solving yn+1 from the last equation,
Ln G y − Lo x o
yn+1 = xn + 1 1 (4-40)
G n +1 G n +1
is obtained. This equation is the operating line equation, as it gives the relationship
between the composition of liquid leaving plate n and the composition of the gas
entering the same plate. Operating line in this form is represented by a curve on xy-
diagram between the points T(xo,y1) and D(xN,yN+1). When both solutions are dilute,
Lo=Ln=LN= L= cons. and GN+1=Gn+1 =G1= G= cons., and hence equation (4-40)
becomes:
L L xo
yn+1 = x n + y1 − (4-41)
G G
Operating line, written in this form is represented by a straight line on xy-diagram,
bounded by the same points. When the solutions are not dilute, equation (4-40), by
substituting the values of G1, Gn+1 , Lo and Ln from equation (4-37), can be written as,
Ls L
Yn +1 = X n + Y1 − s X o (4-42)
Gs Gs
As it is seen, operating line equation written in terms of mole ratios rather than mole
fractions is represented by a straight line on XY-diagram. Summing up, in dilute
solutions equation (4-41) and in strong solutions equation (4-42) is preferred.
After writing operating line equation, the calculation of the number of the ideal plates
is started. But before this, let us see what are known at the start of the design. These
are: molar flow rate of gas to the column GN+1, its composition yN+1, the permissible
concentration of the outlet gas y1, or percentage recovery of solute A from the inlet gas
and the operating pressure and temperature. The quantity and the composition of liquid
solvent (Lo,xo)must also be selected and set at the start of calculations by the designer.
Plate to Plate Calculation Method or Lewis Method: First, equilibrium data of the
system at operating conditions are obtained. If the solutions are dilute, these are
plotted on xy-, if not on XY- coordinates and thus equilibrium distribution curve is
obtained. Then, operating line is written either as equation (4-42) or (4-43). The
calculation is now started at the top of the column. Since y1 is known, by entering this
on the equilibrium distribution diagram, x1 is read. Later, this x1 is inserted into
operating line equation and y2 is calculated. Now the calculated y2 value is entered on
the equilibrium distribution diagram and x2 is read. Calculation is continued in this
way by using equilibrium distribution curve and operating line equation alternately
Y(y)
P=cons.
t=cons. D
YN+1=Y4
(yN+1= y4)
Y3 3
(y3)
Operating line
2
Y2
(y2) Equilibrium
distribution curve
T 1
Y1
(y1)
0 X(x)
0 Xo(xo) X1(x1) X2(x2) X3(x3)
Fig.4.19 Calculation of number of ideal plates by Mc Cabe-Thiele method
until yN+1 value is reached. The number, that is found by subtracting 1 from the
subscript of the last calculated y value, is the number of the ideal plates required to
accomplish the given absorption.
Graphical Calculation Method or Mc Cabe-Thiele Method: By drawing the
operating line on the same diagram with equilibrium distribution curve, the calculation
can be realized on the graph. As it is shown in Fig.4.19, the calculation is started again
at the top of the column. By drawing a horizontal line from point T until cutting the
equilibrium distribution curve and then a vertical line until cutting the operating line, a
right angle triangle is formed. If we look at the values around the triangle, we see that
these are the compositions of the streams around the first ideal plate of the column.
Hence, this triangle represents the first ideal plate in the column. By continuing the
construction of right angle triangles in this way until reaching the point D, and
counting the number of the triangles, the number of the ideal plates is found.
Example-4.7) Gas Absorption in Plate Column
A 150 k-mol/h gas consisting of ammonia (A) and air (C) will be washed with water (S) in a plate
column operating at 20 oC and 800 mmHg. Gas contains 20 percent ammonia by volume and this will
be reduced to 1.96 percent. The water, which is ammonia-free, will be supplied at a flow rate of 2 581
kg/h.
Calculate:
a) The concentration of liquid solution leaving the column,
b) The percentage recovery of ammonia,
c) The number of the equilibrium plates needed,
d) The quantity of ammonia transferred from gas to liquid on each equilibrium plate.
Solution:
Gas is not dilute, Hence work with mole ratios.
First, obtain equilibrium data at 20 oC and P = 800 y
y1=0.0196
mmHg, then convert these to X-Y and plot on a mm
paper.
From App.Table.4.1 Solubility of NH3 in water at 20 oC
y
1 L& o = 2 581 kg / h
xo =0.0
G2,y2 L1,x1
Mass of NH3 per
100 mass of H2O 20 15 10 7.5 5 4 3 2 2
Partial press. of G3,y3 L2,x2
NH3 (mmHg) 166 114 69.6 50.0 31.7 24.9 18.2 12.0
≈ ≈
n
Conversion of the data to X and Y
Gn+1,yn+1 Ln,xn
mA / MA x ≈ ≈
x= X =
(m A / M A ) + (m B / M B ) 1 − x N
LN,xN
p
y= A
y
Y =
P 1− y GN+1= 150 k-mol/h
The first values; LN,xN yN+1 = 0.20
20 / 17 0 .175
x= = 0 . 175 X= = 0 .212
( 20 / 17 ) + (100 / 18 ) 1 − 0 .175 Fig.Example-4.7a
0.208
y=
166
= 0 . 208 Y= = 0.262
800 1 − 0.208
With the conversion of other values, Equilibrium Data are obtained as follows :
X 0.212 0.159 0.106 0.079 0.053 0.042 0.032 0.021

Y 0.262 0.167 0.095 0.067 0.042 0.032 0.024 0.015
These are plotted on a millimetric paper as shown in Fig.Example-4.7b

y N +1 0.20 y1 0 . 0196 x o
YN +1 = = = 0.25 Y1 = = = 0 . 02 X = = 0 .0
1 − y N +1 1 − 0.20 1 − y 1 1 − 0 . 0196 1 − x
o
o
G s
=G N +1
(1 − y N + 1 ) = 150 (1 − 0 . 20 ) = 120 k − mol C / h L s = L o (1 − x o ) = L o (1 − 0 ) = L o
L s = L o = 2 581 / 18 = 143 . 4 k − mol B / h
143.4 143.4
Operating line equation; Yn +1 = X n + 0.02 − (0.0)
120 120
Yn +1 = 1.195 X n + 0.020
If we write this equation at the bottom of the column; YN +1 = 1.195 X N + 0.020
Then, 0.25 = 1.195 X N + 0.020 from here XN = 0.192 and xN = XN = 0.192 = 0.161 is found.
1+XN 1+0.192
( x N )( M A ) (0.161)(17 )
a) or as mass fraction : x& N = = = 0.153 is obtained.
( x N )( M A ) + (1 − x N )( M B ) (0.161)(17 ) + (1 − 0.161)(18)
b) Ammonia entering the column : GN+1 yN+1 = Gs YN+1 = (150)(0.20) = 30 k-mol/h
Ammonia recovered (absorbed): Gs (YN+1 - Y1) = 120 (0.25 – 0.02) = 27.6 k-mol/h
27.6
Then, percentage recovery of ammonia = .100 = 92 %
30.0
c) Locate points T (0.0; 0.02) and D (0.192; 0.25) on the XY-diagram and by joining them draw the
operating line. Then, using McCabe-Thiele method find the number of the ideal plates, which is found
as 6.
Y
P = 800 mm Hg, t = 20 oC
0.26 D
Y7
YN+1= 0.25
Y6 6
0.22
Y5 5
0.18
4
Y4
Equilibrium
Operating Line
0.14 distribution curve
0.1 Y3
2
0.06
Y2
1 0.192=XN
Y1= 0.02
T
X1 X2 X3 X4 X6
0 X5
X
Xo= 0 0.02 0.06 0.10 0.14 0.18 0.22
Fig.Example-4.7b
d) Read the X and Y values around each ideal plate from the Fig.Example-4.7b as:
Xo X1 X2 X3 X4 X5 X6
0.0 0.025 0.063 0.115 0.150 0.175 0.192
Y1 Y2 Y3 Y4 Y5 Y6 Y7
0.02 0.050 0.095 0.158 0.20 0.23 0.25
Loss of ammonia by the gas on plate n = GS(Yn+1-Yn)
On the first plate : GS(Y2-Y1) = 120 (0.050-0.02) = 3.6 k-mol /h
On the second plate : GS(Y3-Y2) = 120 (0.095-0.05) = 5.4 k-mol /h
On the third plate : GS(Y4-Y3) = 120 (0.158-0.095) = 7.56 k-mol /h
On the fourth plate : GS(Y5-Y4) = 120 (0.20-0.158) = 5.04 k-mol /h
On the fifth plate : GS(Y6-Y5) = 120 (0.23-0.20) = 3.6 k-mol /h
On the sixth plate : GS(Y7-Y6) = 120 (0.25-0.23) = 2.40 k-mol /h
+
Total = 27.6 k-mol NH3/h
Or, gain of ammonia by the liquid on each plate = LS(Xn-Xn-1)

On the first plate : LS(X1-Xo) = 143.4 (0.025-0.0) = 3.59 k-mol /h
On the second plate : LS(X2-X1) = 143.4 (0.063-0.025) = 5.45 k-mol /h
On the third plate : LS(X3-X2) = 143.4 (0.115-0.063) = 7.46 k-mol /h
On the fourth plate : LS(X4-X3) = 143.4 (0.15-0.115) = 5.02 k-mol /h
On the fifth plate : LS(X5-X4) = 143.4 (0.175-0.15) = 3.59 k-mol /h
On the sixth plate : LS(X6-X5) = 143.4 (0.192-0.175) = 2.44 k-mol /h
+
Total = 27.55 k-mol NH3/h
In section (b) ammonia recovery was calculated as 27.6 k-mol/h. These are in perfect agreement
considering graphical reading accuracy.
Absorption Factor Method: It is known that when the solutions are dilute; operating
line and the equilibrium relationship both written in terms of mole fractions are
represented by straight lines. If in this case, solute A balance and the equilibrium
relationship for the first plate are written:
L (xo-x1) = G (y1-y2) (4-43)
y1 = m x1 (4-44)
and, if x1 is eliminated between these two equations,
y 2 + (L / G ) x o
y1 = (4-45)
(L / mG) + 1
is obtained. When the absorption factor, which is defined as L/mG = α is substituted
into the equation above,
y + mα x o
y1 = 2 (4-46)
α +1
is found. If the similar steps are repeated for the second plate,
y + mα x1 y + α y1
y2 = 3 = 3 (4-47)
α +1 α +1
is obtained. Upon substituting y1 from equation (4-46),
(α + 1) y 3 + mα 2 x o
y2 = (4-48)
α2 + α +1
is found. Multiplying the nominator and denominator of the above equation by (α-1)
(α 2 − 1) y 3 + α 2 (α − 1) mx o
y2 = (4-49)
α3 − 1
is obtained. If similar steps are repeated for 3rd , 4th and finally for the last plate (plate
N ) of the column:
(α N − 1) y N +1 + α N (α − 1) mx o
yN = (4-50)
α N +1 − 1
is found.
On the other hand, the solute A balance for the whole column is written as:
L (xo-xN) = G (y1-yN+1) (4-51)
Since the equilibrium relationship for the last plate is yN/m = xN , substituting this into
equation above and solving for yN gives;
y − y1 + mα x o
y N = N +1 (4-52)
α
As the left hand sides of equation (4-50) and (4-52) are the same, then the right hand
sides must also be the same. Hence, by equating and rearranging these equations;
y N +1 − y1 α N +1 − α
= N +1 (4-53)
y N +1 − mx o α −1
s obtained. This equation can be used to compute the change in the composition of a
gas at a certain absorption factor in an existing column whose ideal plate number is
already known. Cross multiplication and then solution for αN+1 gives;
⎡y
α N +1 = (α − 1) ⎢ N +1
− mx o ⎤
⎥ +1
If both sides are divided by α, α N = ⎛⎜ α − 1 ⎞⎟⎛⎜ y N +1 − mx o ⎞⎟ + 1
⎣ y1 − mx o ⎦ ⎝ α ⎠⎜⎝ y1 − mx o ⎟⎠ α
is found. Finally by taking the logarithm of both sides,
⎡⎛ α − 1 ⎞⎛ y N +1 − mx o ⎞ 1 ⎤
log ⎢⎜ ⎟⎜⎜ ⎟⎟ + ⎥
⎣⎝ α ⎠ ⎝ 1y − mx o ⎠ α⎦
N= (4-54)
log α
is obtained.
This analytical equation can be used for the calculation of the number of the ideal
plates, when the solutions are dilute.
In desorption operation, following the same steps;
⎡ x − y N +1 / m ⎤
log ⎢ o (1 − α ) + α ⎥
N= ⎣ x N − y N +1 / m ⎦ (4-55)
log (1 / α)
is found.
Determination of Quantity of Liquid Solvent: The selection criteria of the most
suitable solvent among the potential solvents have been given in Section.4.3. Once the
type of solvent is selected, next the amount of solvent must be decided. The effect of
solvent quantity on the absorption will be seen now, by considering a plate type
absorber; the analysis applies to the packed columns as well. Let us try to draw the
operating line on the graph on which equilibrium distribution curve has already been
plotted on XY-coordinates as shown in Fig.4.20a. Since the values at the top of the
column are known, point T can easily be located on the graph. Only the ordinate value
of point D is known, if this YN+1 is entered on the graph it is then obvious that point D
will be on the horizontal line drawn from YN+1 . Gs is calculated from GN+1 and yN+1,
but as Lo is not known, Ls can not be calculated. Now let us assume that we select a
certain quantity of solvent Lo. Ls and the slope Ls/Gs can now be calculated. If we draw
the line from point T with the slope of Ls/Gs ,this will be the operating line for this
selected liquid quantity and the abscissa of point D, which is XN, gives the
composition of liquid solution leaving the column. The required number of the ideal
plates is then found by drawing the right angle triangles between equilibrium
distribution curve and operating line as explained above. Now, if we reduce the
quantity of solvent to be used, the slope of the operating line decreases and hence
operating line approaches the equilibrium distribution curve, and the bottom condition
of the column is shown now with point D1. As it is seen from the figure, the
concentration of solution leaving the column is greater now and the number of the
equilibrium plates needed for the same absorption is also greater, as the space between
the operating line and equilibrium curve became narrower. It follows from here that
when the quantity of solvent is decreased keeping everything else constant, the number
of the equilibrium plates (in the case of packed column, the height of packing)
increases. By decreasing the solvent rate further, a condition is reached at which
operating line touches the equilibrium distribution curve. This is shown with point D'
on Fig.4.20 (a) and with point K on Fig.4.20(b). An attempt to draw the right angle
triangles between operating line and equilibrium distribution curve results in a pinch
around point D' or K, indicating that the number of the equilibrium plates (or height of
packing) needed to accomplish the specified absorption with this solvent rate is
infinite. This solvent rate is then known as minimum solvent rate. In this case, the
Y Y
D D'
D D1 ' YN+1
YN+1 D
slope=Ls/Gs Equilibrium
slope=Ls/Gs
distribution curve
Equilibrium
distribution curve slope=(Ls/Gs)min
K
slope=(Ls/Gs)min
T T
Y1
Y1
X X
Xo XN (XN)max= X∗N Xo XN (XN)max
(a) (b)
Fig.4.20 Determination of Minimum Solvent Rate in gas absorption
concentration of liquid solution leaving the column-as expected- becomes maximum.

This maximum value of XN as shown in Fig.4.20(a), is the equilibrium value of YN+1 ,
when equilibrium distribution curve is concave upward. Desired absorption cannot be
accomplished even in an infinitely long column, at solvent rates smaller than minimum
solvent rate. It is obvious then that the solvent rate to be selected for an absorption
operation should be higher than the minimum solvent rate. The selected solvent rate is
generally expressed in terms of minimum solvent rate in the form of Ls = β (Ls)min. β ,
which is always greater than 1, is determined by considering the economy of the
separation. The β value, which makes the total separation cost minimum, is known as
optimum β value and the solvent rate corresponding to this β is also known as
optimum solvent rate. The total cost is the sum of the fixed capital cost of the system,
which includes either a stripping or a distillation column next to the absorption
column, and the operating cost.
For the determination of minimum solvent rate, the slope of operating line at minimum
solvent rate conditions is written as;
⎛ Ls ⎞ YN +1 − Y1
⎜⎜ ⎟⎟ = (4-56)
⎝ G s ⎠ min (X N )max . − X o
As Gs, Xo, Y1 and YN+1 are all known, reading the (XN)max. value from the graph,
(Ls)min is computed from equation (4-56). When the solutions are dilute, equation
(4-56) is written as;
⎛L⎞ y N +1 − y1
⎜ ⎟ = (4-57)
⎝ G ⎠ min (x N )max . − x o
In the stripping operation, the flow rate and the inlet and outlet concentrations of the
liquid phase are known and the designer selects the flow rate of the inert gas. So, in
this operation, we face with the problem of finding minimum and optimum gas flow
rates. First, point D is located with the known values on the diagram on which
equilibrium distribution curve has already been plotted. Notice that in the stripping,
operating line is below the equilibrium distribution curve and positions of points D and
T are switched. Only the abscissa value of point T, which is Xo is known and its
ordinate value Y1 is fixed by the quantity of gas selected. If the equilibrium
relationship is linear or concave downward, the intersection point of the vertical from
Xo with equilibrium distribution curve gives point T', by which the operating line at
minimum gas condition is obtained as shown in Fig.4.21 (a). If the equilibrium
distribution curve is concave upward as shown in Fig.4.21(b), the intersection point of
the line drawn vertically up from Xo with the line drawn tangent to the curve from
point D gives the point T'. The tangent is the operating line at minimum gas rate
conditions. Note that only the first of so-determined (Y1)max. is the equilibrium value of
Y Y
Equilibrium
(Y1)max distribution curve Equilibrium
'
T distribution curve
slope=(Ls/Gs)max '
(Y1)max T
Y1 T
slope=(Ls/Gs)max
Y1 T
slope=(Ls/Gs) K
slope=(Ls/Gs)
YN+1 D
YN+1
D X
X XN Xo
XN Xo
a) b)
Fig.4.21 Determination of minimum gas flow rate in desorption operation
Xo and the slope of operating line at minimum gas rate is a maximum. The minimum
gas flow rate is then calculated from the slope of so-obtained operating line, which is
given in equation (4-58), by inserting the known values of Ls, Xo, XN ,YN+1 and
(Y1)max.
⎛ Ls ⎞ (Y ) − YN +1
⎜⎜ ⎟⎟ = 1 max (4-58)
⎝ G s ⎠ max . Xo − X N
Example-4.8 Determination of Minimum Solvent Rate (Strong Solution)
Calculate the minimum water rate and hence the β value selected for the absorption operation given
in the Example-4.7.
Solution:
After plotting the equilibrium curve

Y
on XY-diagram, a horizontal line from P = 800 mm Hg, t = 20 oC
0.26
YN+1=0.25 is drawn until cutting the
YN+1= 0.25 D'
equilibrium distribution curve (point D'),
absis of which gives (XN)max = 0.206. L
Then, from equation (4-56), 0.22 Equilibrium
distribution curve
0.25 − 0.02
(L S ) min = 120
0.206 − 0.0 0.18
= 134.0 k-mol water/h

is found.
0.14
As the selected water rate was
2 581 kg/h, the value of β is;
2581 / 18
β= =1.07 0.1
134.0
It follows from this that at the absorption
operation in the Example-4.7 , only 7 % 0.06
excess water from the minimum was
used.
Y1= 0.02 T
(X N ) max = 0.206
0
X
Xo= 0 0.02 0.06 0.10 0.14 0.18 0.22
Example-4.9) Determination of Minimum Solvent Rate (Dilute Solution)
Find the minimum solvent rate and the β value for the Example-4.5.
Solution:
In this case solutions are dilute and equilibrium relationship is given as y*=2.2x. Hence, equation
(4-57) after writing for packed column, can be used for the calculation of minimum solvent rate.
y
First, x 1 is calculated from x 1∗ = 1 = 0.03 = 0.0136
∗
2 .2 2 .2
Then, from equation (4-57), L min = G y1 − y 2 = 300 0.03 − 0.005 = 551.5 k − mol / h is obtained.
x1∗ − x 2 0.0136 − 0.0
As in the Example-4.5 690 k-mol/h solvent was used,
690
β= = 1.25 is found.
551.5
This shows that 25 % excess of the solvent from the minimum was used in the Example-4.5.
Example-4.10) Estimation of Number of Real Plates
Estimate the number of the real plates from O’Connell correlation for the absorption operation given
in Example-4.7.
Solution:
As the slope of equilibrium curve changes, the geometric mean of the slopes calculated at the top and
bottom conditions of the colum is taken.
Equilibrium value of Y1= 0.02 is read from Fig.Example-4.7b as X1= 0.025
Y1 0.02 X1 0.025
Then, y1 = = = 0.0196 and x1 = = = 0.0244
1 + Y1 1 + 0.02 1 + X1 1 + 0.025
Hence, the slope at the top condition: mT = y1 / x1= (0.0196) / (0.0244) = 0.803
Equilibrium value of X6 = 0.192 is read from the Fig.Example-4.7b as Y6 =0.23
Y6 0.23 X6 0.192
Then, y6 = = = 0.187 and x6 = = = 0.161
1 + Y6 1 + 0.23 1 + X 6 1 + 0.192
Hence, the slope at the bottom condition: mD= y6/x6 = 0.187 / 0.161 =1.16
Average slope:; m = (m T )(m D ) = (0.803)(1.16) = 0.965
Liquid is water at the top and 15.3 % ammonia solution at the bottom. As average it can be considered
as 7.7 % ammonia solution. So, ML, ρL, µL will be taken for 7.7% ammonia solution at 20 oC.
From Perry’s Handbook , ρL = 965 kg/m3, but no value for µL is available. Hence take µL= µwater = 1
cP, and ML = Mwater = 18.
mM L µ L (0.965)(18)(1 * 10 −3 )
Then, = = 1.8 * 10 − 5 is obtained.
ρL 965
= y6 / x6
With this value as absis from Fig.4.18 4 E = 0.48 is read.
o
N Ideal 6
Hence; N Re al = = =12.5 NReal= 13 is found.
E o 0.48
m Example-4-11 Stripping in Plate Column
Propane will be stripped from a non-volatile oil by steam in a plate column operating at 138 oC and 2.5
bars absolute pressure. The flow rate of liquid to the column is 120 k-mol /h and it contains 18.1 mole
percent propane. The stripped oil should not contain more than 1.96 mole percent propane. Steam flow
rate to the column will be 1.25 times the minimum steam rate.
a) Calculate the steam rate as kg/h,
b) Find the composition of the gas phase leaving the column,
c) Find the percentage recovery of the propane,
d) Calculate the number of ideal plates needed,
e) Estimate the number of real plates from O’Connell correlation,
Equilibrium relationship at 138 oC and 2.5 bars is given as : Y= 34 X, where Y and X are mole ratios
in gas and liquid phases. The molecular weights of oil and propane are 300 and 44, and density and
viscosity of oil at 138 o C are 900 kg/m3 and 0.5 cP .
Solution:
A : propane, S : oil, C : steam G1y,y11

As the liquid solution is not dilute ,work with mole ratios.
y1 Lo=120 k-mol/h
xo 0.181 xN 0.0196 1
Xo = = = 0.22 XN = = = 0.02 xo= 0.181
1 − x o 1 − 0.181 1 − x N 1 − 0.0196
G2,y2 L1,x1
YN +1 = 0.0 2
LS=Lo(1-xo)=120(1-0.181)= 98.28 k-mol B/h G3,y3 L2,x2
≈ ≈
Y1 = 34 X o = (34)(0.22) = 7.48
∗ n
Gn+1,yn+1 Ln,xn
First, plot Equilibrium Line ( Y=34X) on X-Y coordinates ≈ ≈
with these in mind.
Operating line equation, N
LS L LN,xN GS
Yn +1 = X n + Y1 − S X o
GS GS GN+1
D= y6 / x6
At (G )
⎛L ⎞
⎜ ⎟ S
and Y1∗ = Y( X o )
LN
xN= 0.0196
yN+1
S min ⎜G ⎟
⎝ S ⎠ max
⎛ LS ⎞ Y ∗ − YN +1 7.48 − 0.0 (G S ) min =

L S 98.28
= = 2.63 k − mol steam / h
Then, ⎜⎜ ⎟⎟ = 1 = = 37.4 37.4 37.4
⎝ G S ⎠ max X o − X N 0.22 − 0.02
a) G S =β (G S ) min = (1.25)(2.63) = 3.29 k − mol steam / h
& =G
G & = (3.29 )M B = (3.29)(18) = 59.2 kg steam / h is obtained.
S N +1
98.28 98.28
b) Operating line equation, Yn +1 = X n + Y1 − (0.22)
3.29 3.29
Yn +1 = 29.87 X n + Y1 − 6.57
Operating line equation written at the bottom of the column: YN +1 = 29.87 X N + Y1 − 6.57
Then; 0 = (29.87)(0.02)+Y1-6.57 from which Y1= 5.97 and

Y1 5.97
y1 = = = 0.857 or,
1 + Y1 1 + 5.97
y1M A (0.857)(44)
as mass fraction; y& 1 = = = 0.94 is obtained.
y 1 M A + (1 − y 1 )M C (0.857)(44) + (1 − 0.857)(18)
c) Propane entered : Loxo = (120)(0.181) = 21.72 k-mol/h
Propane recovered(stripped) : GS(Y1-YN+1) = 3.29(5.97- 0) =19.64 k-mol/h
Then, percentage recovery of propane : (19.64 / 21.72)*100 = 90.4 %
d) As point T( 0.22 ; 5..97) and D ( 0.02 ; 0.0 ) are known, the operating line is plotted by joinning T
with D. Then, the number of the ideal plates is found by McCabe-Thiele method as shown in
Fig.Example-4.11 as;
ab 9 mm
N ideal = 6 + = 6+ = 6.3
ac 30 mm
Y
o
8.0 P = 2.5 bars t =138 C
T'
Y1 = 7 .48
∗
7.0 Y=34X Y
6.0 T
Y1=5.97
1 1.0
5.0 Operating Y6
Line at ⎛ L ⎞ 2 0.8
slope = ⎜⎜ ⎟⎟
s
4.0 6
⎝ s
G ⎠ max
3 0.6
3.0
Operating
2.0 4 0.4
Line
5 c b
1.0 0.2 a
6 7
D X3 X2 X1 Xo X6
X 0
YN+1 0.02 0.06 0.10 0.14 0.18 0.22 X
XN 0 X 0.01 D 0.03 0.05
7
Fig.Example-4.11
Or, since both equilibrium and operating lines are straight, equation (4-55) can be used for the
calculation of required number of the ideal plates after replacing y and x with Y and X.
⎡ X − YN +1 / m ⎤
log ⎢ o (1 − α ) + α ⎥
N= ⎣ X N − YN +1 / m ⎦ (4-55)
log (1 / α)
L /G 29.87
Here; m = Y*/ X =34 and α= S S= = 0.879
m 34
⎡ 0.22 − 0.0 / 34
log ⎢ (1 − 0.879) + 0.879⎤⎥
⎣ 0.02 − 0.0 / 34 ⎦ = 6.13
N= is obtained.
log (1 / 0.879)
Very close agreement between two methods is obvious.
e) At the top of the column : Y1=5.97 or y1 = 0.857

X1 0.176
X1=Y1/m= 5.97/ 34 = 0.176 and x 1 = = = 0.15 mT = y1 /x1 = 0.857 / 0.15 = 5.71
1 + X 1 1 + 0.176
At the bottom of the column : xN = 0.0196 or XN = 0.02
YN 0.68
YN =34 XN = (34)(0.02) =0.68 and yN = = = 0.405 mD =yN /xN=0.405/ 0.0196 =20.66
1 + YN 1 + 0.68
Average slope : m = ( m T )(m D ) = (5.71)(20.66) =10.86
Then, mM L µ L (10.86)(300)(0.5 *10 −3 ) From Fig. 4.18 Eo = 0.13 is read.

= =1.81*10 −3
ρL 900
N 6.3
Finally, N Re al = Ideal = = 48.5 NReal = 49 is obtained.
Eo 0.13
4.5. Non-isothermal Absorption: In all the analysis above, existence of isothermal

conditions are assumed. But, on the other hand it is very well known that absorption of
gases into liquids releases heat. So, in order to have constant temperature in an
absorption column, either the heat released must be removed or the heat of absorption
and/or rate of absorption must be very low. Cooling in plate type columns is easier
than in packed columns, as cooling coils can readily be attached to the plates as shown
in Fig.4.22, and through which cooling liquid is circulated. In some other applications,
the liquid solution is taken to the outside of the column from time to time and cooled
in an external heat exchanger and returned back to the column. When the cooling is
not applied and the heat of absorption is great, the rise of temperature in the column is
inevitable. This causes reduction in the capacity of the column. In order to prevent
capacity loss, higher liquid flow rates are used, which in turn, results in excessive
dilution of the solution leaving the column.
In the design of an adiabatically operating absorption column, not only mass balance
but also enthalpy balance equation is needed and the solution can only be made by trial
and error. It follows from the thermodynamics that molar specific enthalpy of a liquid
solution at temperature tL (oC) is written as;
Fig.4.22 A bubble-cap plate containing cooling pipes
h = c L ( t L − t R ) + ∆H s (4-59)
o
where tR is the reference temperature in ( C), c L ; is the specific heat of the liquid
solution in (kJ/k-moloC), and calculated at the arithmetic mean of tL and tR
temperatures and ∆H s is the heat of mixing or integral heat of solution at given
temperature and liquid composition in (kJ/k-molA). The specific heat of liquid
solution is computed from the pure component’s specific heats, cLA , cLS by using the
following equation,
cL = x cLA + (1 − x ) cLS (4-60)
When this equation is substituted into equation (4-59),
h = [x cLA + (1 − x ) cLS ]( t L − t R ) + ∆H s (4-61)
is obtained.
Similarly, the molar specific enthalpy of a binary gas mixture of A+C at temperature tG
is given by
H = y[c GA ( t G − t R ) + λ A ] + (1 − y) [c GC ( t G − t R ) ] + ∆H s (4-62)
where, λ A is the latent heat of vaporization of
component A at reference temperature in (kJ/k-mol G1,H1,y1,tG1
A), which is taken into consideration when
component A is liquid at reference temperature,
otherwise λ A = 0 . If total material, solute A and Lo,hO
t1 xo,tLo
enthalpy balances are written for a plate type 1
absorption column shown in Fig.4.23;
Lo + GN+1 = LN + G1 (4-63) 2
Lo xo + GN+1 yN+1 = LN xN + G1y1 (4-64)
L o h o + G N + 1 H N + 1 = L N h N + G 1 H1 (4-65) n
If the same balances are written between Gn+1,yn+1 Ln,hn,xn

column bottom and any plate n in the column. G N, H ,
N N y
Ln + GN+1 = LN + Gn+1 (4-66) GN+1 N tN
Ln xn + GN+1 yN+1 = LN xN + Gn+1yn+1 (4-67) HN+1
L n h n + G N +1H N +1 = L N h N + G n +1H n +1 (4-68) yN+1
tG,N+1
are obtained.
The knowns at the start of calculations are: GN+1,
yN+1 , tG,N+1 , y1 , Lo , xo , tLo . In addition to these LN,hN,xN,tLN
λ A , ∆H s , cLA=f(t), cLS =f(t), cGA = f(t), cGC =f(t)
and y*= m x, m= f(t) must be found from the Fig.4.23
relevant literature. Then, the calculations are
started at the bottom of the column. First, from
equation (4-61) ho and from equation (4-62) H N +1 are calculated. Then, from
Gs = G1(1-y1) = GN+1(1-yN+1) G1, Gs and from equations (4-63) and (4-64) LN and xN
are calculated. Now an assumption for the temperature of the first plate of the
column t1 is made (it is obvious that tL1=tG1=t1). As t1 is now known, H1 from
equation (4-62) and later hN from equation (4-65) are computed. Hence, all the streams
around the column and their compositions and specific enthalpies have been
determined. From equation (4-61) tLN and at this tLN mN are found. Then, from
yN=mN xN and GN =Gs/(1-yN) yN, GN and from equation (4-62) HN are computed.
Hence the gas phase leaving plate N, has been specified. By taking n=N-1 we come to
the plate above. First, from equation (4-66) LN-1 , from equation (4-67) xN-1 , from
equation (4-68) hN-1 and from equation (4-61) tN-1 are computed. Then, at this tN-1 mN-1
is read. From yN-1=mN-1 xN-1 and GN-1=Gs/(1-yN-1) yN-1 and GN-1 , and then from
equation (4-62) HN-1 are calculated. By taking n=N-2 from equation (4-66) LN-2 , from
equation (4-67) xN-2 , and from equation (4-68) hN-2 are computed. Calculation is
continued in this way until y1 value is reached. So-obtained t1 is then compared with
the assumed t1. If the difference between assumed and calculated values is acceptable,
the calculations and hence the solution are y
correct. If the difference is great, the calculations P=cons.
are repeated with a new t1 value. Repeating is
continued until the difference is reasonable. Adiabatic equilibrium tL1
As it is seen, calculations require trial and error curve
tL5
and in many cases this is very lengthy.
A short method giving reasonably accurate tL4
result has been developed by assuming that the t L3
heat liberated in the liquid phase upon the tL2
absorption, remains in the liquid. Although with

this assumption, the temperature of the liquid
x
hence, the number of the ideal plates (or height x2 x3 x4 x5 x1
of packing) required is found higher than the
actual values, this over-design in the number of
ideal plates (or in the height of packing) can be Fig.4.24 Equilibrium distribution
taken as design security. If an enthalpy balance is curve
written for a dZ height in the column, assuming
L and G are constant;
G dHG + ∆Hs L dx = L dhL (4-69)
or
G cG dtG + ∆Hs L dx = L cL dtL (4-70)
is obtained.
with the assumption of ∆Hs L dx > G cG dtG ,
∆H s ∫ dx = c L ∫
x tL
dt L and from here,
x2 tL 2
∆Hs (x-x2) = c L ( t L − t L 2 ) (4-71)

is found, where point 2 represents top of the column. If absorbed solute A is a liquid at
reference temperature, ∆Hs then includes the latent heat of vaporization. With the help
of this equation, the equilibrium distribution diagram of the adiabatic absorption
column is plotted as follows: equilibrium distribution lines at various tL temperatures
which are greater than tL2, are drawn on a millimetric paper. At the same time x values
corresponding to these temperatures are calculated from equation (4-71). The
calculated x values are then marked on the corresponding equilibrium distribution
lines and by joining these points, the equilibrium distribution curve at adiabatic
condition is obtained as shown in Fig.4.24. This equilibrium curve can now be used at
the absorption of solute A in an adiabatically operating packed or plate column.
)Example-4.12 Non-Isothermal Gas Absorption
The concentration of ammonia in a gas stream, consisting of ammonia and air is to be reduced from 5
to 0.5 % by volume, by contacting it with water, which is ammonia-free and at 20 oC, in an
absorption column at 1 bar pressure.. The molar heat of absoption is 37 544 kJ/k-mole of ammonia
absorbed and molar specific heat of liquid is 75.3 kJ/k-mole oC . Over the range of operation, the
equilibrium relationships at various temperatures are linear and given as y*= m x, where y and x are
the mole fractions of ammonia in gas and liquid respectively. The slope m changes with temperature
as follows:
Temperature(oC) 20 25 30 35
m 0.73 0.96 1.23 1.55
a) Draw the equilibrium curve for non-isothermal (adiabatic) absorption
b) Calculate the minimum solvent rate for a gas rate of 50 k-mol/h,
c) Draw the operating line for a solvent rate which is 1.15 times the minimum rate,
d) Explain, what would be, if isothermal absorption at 20 oC were assumed ?
Solution:
a) The short method can be used. Hence, from equation (4-71),
cL 73.5
x = x2 + (t L − t L2 ) = 0.0 + (t L − 20) = 0.002(t L − 20) is written.
∆Hs 37 544
If the x values are calculated at the given temperatures:
tL 20 25 30 35
x 0.0 0.01 0.02 0.03
is obtained.
After drawing y*= m x lines at the given temperatures, corresponding x values are marked on these
lines and by joining them, the equilibrium distribution curve at adyabatic condition is obtained as
shown in Fig.Example-4.12.
b) For dilute solutions operating line is given by the equation (4-12). At minimum liquid flow rate
this is written as,
L L
y1 = ( ) min x 1∗ + y 2 − ( ) min x 2
G G
⎛L⎞ y − y2
From which, ⎜ ⎟ = 1∗ is obtained. x 1 = 0.032 is read from
∗
⎝ G ⎠ min x1 − x 2
the diagram by drawing a horizontal line from y1 = 0.05 until cutting the adiabatic equilibrium curve.
0.05 − 0.005
Then, L min = 50 = 70.31 k − mol / h is found.
0.032 − 0.0
c) L = 1.15 (70.31) = 80.86 k-mol/h
80.86 80.86
Then, operating line, y= x + 0.005 − (0.0)
50 50
y = 1.62 x + 0.005
By writing operating line at the bottom of the column,
y 1 − 0 .005 0 .05 − 0 .005
x1 = = = 0 .028 is found.
1 .62 1 .62
With the help of this, point D is located and by joining D with T operating line is drawn.
d) Extend the horizontal line from y1= 0.05 until cutting the equilibrium line drawn at 20 oC and read
x 1∗ = 0.069
0.05 − 0.005
Then, minimum solvent rate L min = 50 = 32.61 k − mol / h and operating solvent
0.069 − 0.0
rate, L = 1.15 (32.61) = 37.5 k-mol/h are obtained. Hence, operating line is: y = 0.75 x + 0.005 and
x1= 0.06. With the help of this value, point D is located and the operating line for isothermal
absorption at 20 oC condition is drawn by joining D with T. As it is seen from the figure, this line cuts
the adiabatic equilibrium curve at point K, whose temperature is about 28 oC and x value is 0.014. This
means that if -with isotermal absorption at 20 oC assumption- a solvent rate of 37.5 k-mol/h is
selected, absorption stopes when the temperature of the liquid reaches 28 oC at which time mol
fraction of ammonia in the liquid is 0.014, much below the 0.028 value.
Adiabatic equilibrium curve

Mole fraction of ammonia in gas,y
35 oC
P=1 bar
0.06 30 oC
D 25 oC 20 oC
D D' D
y1= 0.05
D'
0.04 Operating
Line
Operating Line for Isothermal
K
0.02 Absorption at 20 oC
T
x1=0.028= x ∗ = 0.032 x1=0.06= x 1∗ = 0.069
y2 =0.005 x =0.014= 1
0
x2 = 0 0.01 0.02 0.03 0.04 0.05 0.06= 0.07=
Mole fraction of ammonia in liquid,x
Fig.Example-4.12
4.6 Gas Absorption with Chemical Reaction : In absorption operations as the

concentration of solute A in the liquid phase increases, rate of absorption of A slows
down due to the equilibrium back pressure of solute. This results in an increase in the
size of absorber or else excessive amount of solvent must be used. In order to reduce
this equilibrium back pressure and hence to keep the rate of absorption at a reasonable
level, the absorbed solute A may be reacted with a reactant B added into the solvent S,
according to the stoichiometry given below, to form a product P.
aA + bB pP (in solvent S)
Reaction of absorbed solute A with reactant B may enhance the rate of absorption
considerably. But, if solute A is to be recovered, the above given reaction must be
reversible.
For example reaction between ammonia and aqueous sulphuric acid proceeds toward
the right at low temperature, so that back pressure of ammonia is almost zero.
2 NH3 + H2SO4 (NH4)2SO4
But at elevated temperature, reaction drives to the left giving ammonia and sulphuric
acid back (regeneration).
In some other cases, the production of component P may be the main objective of the
process such as the absorption of NO2 in water for the production of HNO3 or
absorption of SO3 in H2SO4 for the manufacture of Oleum.
In some cases, absorbed solute A may react directly with solvent S. An example from
chemical industry to this is the absorption of maleic anhydride vapor from air into
water. Maleic anhydride upon absorption reacts with part of the water to form maleic
acid which can dissolve in water.
Overall rate of absorption of solute A is then influenced by both the mass transfer
resistance and the rate of chemical reaction, both in the liquid phase. From the values
of these two, overall rate is determined. In some cases, chemical reaction may be very
rapid (fast reaction) so that rate of mass transfer controls the overall rate of absorption.
In some other cases, rate of reaction is very small (slow reaction) and hence it controls
the overall absorption rate. Between these two extremes, rate of mass transfer is
comparable with the rate of chemical reaction and both must be considered in
computing the overall rate of absorption, which is the most difficult case to analyze.
In the analysis of gas absorption with chemical reaction, film or penetration theory
may be taken as model. In many analysis results obtained from these two theories are
very close to each other. Hence, in the analysis below the validity of film theory due to
its simplicity is to be assumed.
Typical concentration profiles of solute A in gas and liquid phases when the chemical
reaction taking place is slow are shown in Fig.4.25., along with the profiles at pure
physical absorption. As it is seen -due to the slow reaction-the absorbed solute A can
not be depleted completly in the liquid film with the reaction and concentration profile
of it in the liquid phase is no longer linear.
I
G a s p h a s e L i q u i d p h a s e
Molar concentration of solute A

Partial pressure of solute A
A+C Gas film Liquid film

pA
A
A+B+P+S
o
p Ai
pAi c oAi
cAi
c oA
cA
zG 0 zL
: Physical absorption : Absorption+chemical reaction
Fig.4.25 Concentration profiles in two phase at physical absorption and at absorption

with chemical reaction
But when the reaction is fast enough, absorbed solute A is completly consumed in the
liquid film with the reaction and the concentration profile of it along with that of the
rectant B in the liquid may be depicted as in Fig.4.26.
In the part of the liquid film to the left of reaction zone only solute A diffuses from
interface toward reaction zone, and in the part of the liquid film right to the reaction
zone only reactant B diffuses from bulk liquid toward reaction zone. In the reaction
zone itself diffusions of both components and chemical reaction take place
simultaneously.
I
G a s p h a s e L i q u i d p h a s e

pA A Reaction
Molar concentrations
zone
pAi B
cAi
cB
zG 0 zL
Fig.4.26 Concentration profiles in two phase at absorption+fast chemical reaction in

liquid phase
One extreme case of fast reaction is the instantaneous reaction. In this case reaction
zone reduces to a reaction plane as shown in Fig.4.27.
As there is no simultaneity between reaction and diffusion, this case is the most easy to
analyze
I L i q u i d p h a s e
G a s p h a s e

pA A
Reaction
plane
pAi B
cAi
cB
zG 0 zR zL
Fig.4.27 Concentration profiles in two phase at absorption with instantaneous chemical

reaction in liquid phase
4.6.1 Gas Absorption with Instantaneous Chemical Reaction: From film theory
representation; for the diffusion of solute A in the part of the liquid film shown in
Fig.4.27:
D
N A = AS (c Ai − 0) (4-72)
zR
can be written. By multiplying right hand side with zL/zL and remembering kL=DAS/zL
from film theory, this equation becomes;
D z z
N A = AS . L c Ai = k L L c Ai (4-73)
zL zR zR
Similarly, for the diffusion of reactant B in the other part of the liquid film:
D BS D D cB D cB
NB = − (c B − 0) = − BS . AS . = −k L BS . (4-74)
zL − zR D AS z L 1 − (z R / z L ) D AS 1 − (z R / z L )
On the other hand, from the stoichiometry of the reaction,
bNA +aNB = 0 (4-75)

can be written.
If, first zL/zR is solved from equation(4-73) and substituted in equation(4-74) and then
so-obtained NB is substituted into equation (4-75) finally,
a D
N A = k L (c Ai + . BS c B ) (4-76)
b D AS
is found. [At physical absorption this was : NA=kL(cAi-cA)]
With the elimination of cAi, equation(4-76) can be written in more appropriate form as
follows:
At steady-state, in the gas phase;
NA=kG(pA-pAi) (4-77)
can be written. Assuming that Henry’s law equation is valid for the gas-liquid
equilibrium,
pAi= ΉA cAi (4-78)
If pAi is eliminated between last two equations;

1 N
c Ai = (p A − A ) (4-79)
ΗA kG
By substituting this into equation (4-76);
⎡1 N a D ⎤
N A = k L ⎢ (p A − A ) + . BS c B ⎥ (4-80)
⎣ΗA kG b D AS ⎦
a D
p A + ΗA BS c B
b D AS
=
ΗA k G + k L
kGkL
On the other hand,
1 1 ΗA ΗA k G + k L
= + =
KG kG kL kGkL
If this is substituted into equation above finally,

N A = K G (p A + ΗA a . BS c B )
D
(4-81)
b D AS
is obtained.
Position of reaction plane in the liquid film is dependant on (DAS/DBS), (a/b), pA and
cB.
I L i q u i d p h a s e
G a s p h a s e

pA
A
Reaction
plane
(cB)crit.
zG 0 zL
zR
Fig.4.28 Concentration profiles in two phase at absorption with instantaneous chemical

reaction when cB ≥ (cB)crit.
If the first three terms are kept constant, zR changes only with cB. There is a value of cB
[which is known as critical value and shown with (cB)crit.] that at or above which zR =0,
which means that interface becomes reaction plane. Concentration profiles in this case
are to be as shown in Fig.4.28.
As it is seen from the Figure, at cB ≥ (cB)crit. equation(4-77) becomes,
NA=kG pA (4-82)
So, it follows from these that, for the calculation of total flux,
when, cB < (cB)crit equation(4-81),
when, cB ≥ (cB)crit equation(4-82) is used .
(cB)crit value for any given pA is found as follows;
From Fig.4.26, at or above (cB)crit ,
D D D D
N B = − BS (c B ) crit . = − AS . BS (c B ) crit . = − k L BS (c B ) crit (4-83)
zL z L D AS D AS
is obtained. If this and NA from equation(4-82) are substituted into equation(4-75)
b kG pA - a kL(DBS / DAS)(cB)crit. = 0 from which,
b D k
(c B ) crit . = . AS . G p A (4-84)
a D BS k L
is found. Or for a given value of cB; (pA)crit. is:
a D k
(p A ) crit . = . BS . L c B (4-84b)
b D AS k G
4.6.2 Calculation of Height of Packing when Chemical Reaction is Instantaneous::
With the assumption of dilute solutions, solute
A balance along dh differential height in the packed section; G pA2
Lv
-G(dpA/P) = NA dSm (4-85) cB2
= (a/b)LvdcB (4-85b) 2 h=z
where, G is total molar flow rate(k-mol/s) of gas and Lv
is volumetric flow rate(m3/s) of liquid, both are constant.
By defining a mass transfer area per unit volume
NA dh
of packing with av(m2/m3), total mass transfer area in
the differential volume becomes,
dSm= avAcdh pA cB
2
where Ac(m ) is the cross-sectional area of the empty
colum. Upon substitution of this into equation(4-85) 1 h=0
and integrating from bottom to the top of the packing; G
pA1
p A1
G ⌠ dp A
Z = ∫ dh =
z
Lv cB1
a v PA c ⎮
(4-86)
o
⌡p A 2 N A
Fig.4.29
is obtained.
pA
1
(pA)crit.= f(cB)
Case-3
1
Case-2
pAx
2
2
1
pA1
Case-1
pA2 2
cB
(cB2)crit. (cB1)crit. cB1 cBx cB2
Fig.4.30 Stoichiometric operating lines for

three different cases
Depending upon the values of cB1 and cB2 , three different cases are encountered at
which NAs to be substituted into equation(4-86) are different. These cases are shown
schematically in Fig.4.230.
Case-1) cB1 ≥ (cB1)crit and cB2 > (cB2)crit In this case NA=kGpA and then,
p
⌠ dp A
A1
G p
Z= ⎮ = H G ln A1 (4-87)
a v PA c k G ⌡p A 2 p A p A2
G
is obtained. Where H G = (m) is height of one gas transfer unit.
k G a v PA c
Case-2) ) cB1 < (cB1)crit and cB2 ≤ (cB2)crit In this case NA value must be substituted
from equation(4-81).
p A1 p A1
⌠ ⌠
G ⎮ dp dp A
Z= A
= H OG ⎮ (4-88)
a v PA c K G ⎮ a D BS ⎮ a D BS
⌡p A 2 p A + ΗA . cB ⌡p A 2 p A +ΗA . cB
b D AS b D AS
G
is found. Where, H OG = (m) is the height of one overall gas transfer unit.
K G a v PA c
By integrating equation(4-85b) between bottom and any section of the column,
-G(pA1-pA)/P = (a/b)Lv(cB1-cB) from which,

cB = cB1+(b/a)(G/LvP)(pA1-pA) (4-89)
is obtained. This equation is known as “stoichiometric operating line equation” If this
cB is substituted into equation (4-88) and integrated;
a D
(pA + ΗA . BS c B ) 1
H OG b D AS
Z= ln (4-90)
1 D a D
1 − . BS (pA + ΗA . BS c B ) 2
α D AS b D AS
(L v / G )
is found. Where α = is absorption factor.
ΗA / P
Case-3) cB1 < (cB1)crit and cB2 > (cB2)crit In this case between top and any
level(level-x) the solution of case-1 and between this level and bottom of the
column solution of case-2 apply.
Hence;
a D
(pA + ΗA . BS c B ) 1
p H OG b D AS
Z = H G ln Ax + ln (4-91)
p A2 1 D BS a D
1− . (pA + ΗA . BS
cB )x
α D AS b D AS
pAx and cBx are found by first writing equations (4-84) and(4-89) at level-x and then
solving;
a L P
p A1 + . v c B1
p Ax = b G (4-92)
L P D k
1 + v . AS . G
G D BS k L
a L P
p A1 + . v c B1
b b G
c Bx = . (4-93)
a D BS k L L v P
. +
D AS k G G
Example-4.13) Calculation of Height of Packing when Reaction is Instantaneous
An ammonia-air gaseous mixture is to be washed with aqueous sulfuric acid solution containing 0.25
k-mol acid per m3 of solution, in a packed column operating counter-currently at 1 bar and 20 oC, to
reduce the partial pressure of ammonia from 0.05 bar to 0.001 bar. The flow rates of gas and liquid to
the column are 150 k-mol/h and 25 m3/h respectively and cross-sectional area of the column is 1 m2.
An instantaneous reaction between ammonia and sulfuric acid in the liquid phase takes place
according to the stoichiometry below:
2 NH3 + H2SO4 (NH4)2SO4
At the operating conditions, volumetric mass transfer coefficients are given as:
kGav=50 k-mol/m3h bar and kLav = 2.0 h-1 , and the value of Henry’s law constant is 0.73 bar.
Calculate the required height of packing.
Solution: pA2=0.001 bar

First find cB1 from equations(4-85) and (4-85b); G
Lv=25 m3/h
-(150)(0.05-0.001)/1= (2/1)(25)(cB1-0.25)
cB1= 0.103 k-mol/m3 cB2=0.25 k-mol/m3
Molecular diffusivity of ammonia in water from Table.1.4, 2 z
-9 2
DAS=2.3*10 m /s. The molecular diffusivity of sulphuric acid
in water is taken from Example-1.8)
DBS= 2.55*10-9 m2/s.
Now, we can find which case is applicable for the solution.

From equation(4-84),
(cB)crit. =(1/2)(2.3 /2.55)(50/2) pA =11.3 pA
Then, at column bottom; (cB1)crit. = (11.3)(0.05)= 0.565 k-mol/m3
Hence, (cB1)crit. > cB1 1
3
At column top ; (cB2)crit. = (11.3)(0.001) = 0.0113 k-mol/m G=150 k-
Hence, (cB2)crit. < cB2
pA1=0.05 bar
It follows from here that case-3 is applicable.
Then, from equation (4-92); Lv cB1
0.05 + (2 / 1)[(25 * 1) / 150](0.103)
p Ax = = 0.0177 bar
1 + [(25 * 1) / 150](2.3 / 2.55)(50 / 2)
From equation (4-93);
0.05 + (2 / 1)[(25 * 1) / 150](0.103)
c Bx = (1 / 2) = 0.20 k − mol / m 3
( 2.55 / 2.3)(2 / 50) + [(25 * 1) / 150]
As the solution is dilute in ammonia and density of water at 20 oC is 998 kg/ m3 c=998/18=55.44 k-
mol/m3 and from equation(4-3)ΉA = Ή’A /c=(0.73)/(55.44) = 0.0132 bar m3/k-mol.
1 1 0.0132
HG =
150
=3 m = + = 0.0266 bar h m 3 / k − mol
(50)(1)(1) K G a v 50 2
G (150)(0.0266)
H OG = = = 3.99 m
K G a v PA c (1)(1)
hence; α = 25 / 150 = 12.63
0.0132 / 1
Substituting all these into equation (4-91);

0.05 + (0.0132)(2 / 1)(2.55 / 2.3)(1 / 1)(0.103)
ln[ ]
0.0177 3.99
Z = (3) ln +
0.001 1 0.0177 + (0.0132)(2 / 1).(2.55 / 2.3)(0.20)
1− .(2.55 / 2.3)
12.63
Z = 8.62 + 3.55 = 12.17 m is found.
4.6.3 Calculation of Height of Packing when Chemical Reaction is Slow:

When the chemical reaction is slow, only part of the
absorbed solute A reacts with reactant B and G pA2
unreacted part of it remains in the leaving solution. Lv
Again, with dilute solutions assumption; along dh cB2
differential height in the packed section: 2 cA2=0
-G(dpA/P) = NA dSm = NA av Ac dh (4-94) h=Z
= consumption of A by chemical reaction
+ increase in content of A in bulk liquid ZP
= -RAHoAc dh - Lv dcA (4-94b) NA dh
= (a/b) Lv dcB - Lv dcA (4-94c)
can be written.Where Ho (m3 liquid /m3 packing) is pA cB
the specific hold-up. ZR cA
Considering gas phase; h=0
NA =KG (pA- p ∗A )= KG (pA - ΗA cA) (4-95) 1 G
can be written.After substituting this into equation pA1
(4-94) and integrating from bottom to the top of
the column; Lv cB1 cA1
p p
⌠ ⌠
A1 A1
G dp A dp A
Z = ∫ dh =
z
⎮ = H OG ⎮ (4-96)
0
K G a v PA C ⌡p A 2 p A −ΗA c A ⌡p A 2 p A −ΗA c A
is obtained.
Note that in this case; cA = f (pA,cB) [ Remember: in physical absorption, cA = f(pA)]
In order to perform the integral, the following model may be assumed. Since incoming
liquid does not contain any solute A and the chemical reaction in the liquid phase is
directly proportional to the concentration of solute A, a zone at the top part of the
column may be assumed in which only physical absorption of solute A occurs,
followed by another zone in which-due to the sufficient concentration build-up of
solute A-chemical reaction is more significant than the absorption.
Hence, in the physical absorption zone from equation(4-94) and (4-94b) with the
assumption of Lv dcA ≫ RAHoAc dh ;
-G(dpA/P) = Lv dcA and from the integration of this between the top and any level
within the physical absorption zone with cA2 = 0.
G
cA = (p A − p A 2 ) (4-97)
LvP
is found. Substituting this into equation (4-96) and taking pA1= pAx (partial pressure of
solute A at the end of physical absorption zone), height of physical absorption zone;
p
⌠
Ax
dp A
Z P = H OG ⎮
⌡p A 2 p A (1 − 1 / α) + p A 2 / α
H OG ⎡ p 1⎤
ZP = ln ⎢(1 − 1 / α) Ax + ⎥ (4-98)
1 − 1/ α ⎣ p A2 α⎦
is obtained.
In the chemical reaction zone, from equations(4-94) and (4-94b) with the assumption
of RAHoAc dh ≫ Lv dcA ;
NA av Ac dh = - RAHoAc dh and from which, NA =-RAHo / av is found.

Substituting this into equation (4-95);
(pA - ΗA cA)= -RAHo/KG av (4-99)
and this into equation (4-96) and taking pA2 = pAx ; the height of chemical reaction
zone;
p
K G a v ⌠ A1 dp A
Z R = − H OG
Ho ⎮
(4-100)
⌡p Ax R A
is obtained.
Then, total height of the packing becomes;
Z = Z P + ZR (4-101)
For each specific reaction rate equation, there are special solutions of equations(4-98)
and (4-100).
Special case-1) Reaction between A and B is 0th order with respect to A; RA= - ko
Then from equation(4-100);
p
K G a v ⌠ A1 dp A H
Z R = H OG ⎮ = OG (p A1 − p Ax ) (4-102)
H o ⌡p Ax k o βo
is found. Where, β o = k o H o / K G a v
At h=ZR equations(4-97) and(4-99) become;
G
c Ax = (p Ax − p A 2 )
LvP
(pAx - ΗA cAx)= koHo/KG av =βo
β o − p A2 / α
From these two; p Ax = is obtained. Substituting this into
1 − 1/ α
equations(4-98) and (4-102);
H OG
Zp = ln(β o / p A 2 ) (4-103)
1 − 1/ α
ZR =
H OG
[(1 − 1 / α) p A1 + (p A 2 / α) − β o ] (4-104)
(1 − 1 / α) β o
are found.
Special case-2) Reaction between A and B is first order with respect to A; RA= - k1cA .
Then from equation(4-100)
p p
K G a v ⌠ A1 dp A H OG ⌠ A1 dp A
Z R = H OG = (4-105)
H ok1 ⎮ ⌡p Ax c A β1 ⎮
⌡p AxΗA c A
k 1H o kH
Where, β1 = = 1 o
ΗA K G a v K L a v
From equation(4-99) by noting the value of β1 ;

pA
ΗA c A = is found. After substitution into equation(4-105) and integration;
1 + β1
1 + β1 p
Z R = H OG ln A1 (4-106)
β1 p Ax
is obtained.
At h = ZR equations(4-97) and(4-99) become;
G
c Ax = (p Ax − p A 2 )
LvP
(pAx - ΗA cAx)= k1 cA Ho/KG av = ΗAcAx β1
p A2
From these two; p Ax = is obtained.. Substituting this into
1 − α /(1 + β 1 )
equations(4-98) and (4-106);
H OG β1
Zp = ln (4-107)
1 − 1/ α 1 + β1 − α
1 + β1 ⎡ α p A1 ⎤
ZR = H OG ln ⎢(1 − ) ⎥ (4-108)
β1 ⎣ 1 + β1 p A2 ⎦
are found.
Special case-3) Reaction between A and B is first order with respect to A and B ,
RA= - k2cAcB.
In this case solution is done by stepwise integration. Hence equations (4- 94) must be
written as finite difference:.
-G(dpA/P) = KG(pA- ΗA cA)av. avAc∆h (4-109) G pA2
= -RAHoAc ∆h - Lv ∆cA (4-109b) Lv
= (a/b) Lv ∆cB - Lv ∆cA (4-109c) cB2
These equations can be written for ∆hj height which cA2=0
is bounded with the planes j and j-1, as: cAj-1
pAj-1
cBj-1
G(pAj-pAj-1)/P = KG(pA- ΗA cA)av. avAc∆hj (4-110)
∆hj
= k2 (cAcB)av.HoAc∆hj+Lv(cAj-cAj-1) (4-110b)
=(a/b)Lv(cBj-1-cBj) + Lv(cAj-cAj-1) (4-110c) pAj cAj
cBj
Calculations may be started at the top of the column, where G
pAj-1, cAj-1 and cBj-1 are all known. By selecting a pAj value,
as a first approximation, pA1
(pA-ΗA cA)av. = (pA-ΗA cA)j-1
and (cAcB)av. = (cAcB)j-1 Lv cB1 cA1
can be written.
Then, from equation (4-110); ∆hj = HOG(pAj-pAj-1)/(pA- ΗA cA)j-1 (4-111)
From equation(4-110b), cAj = cAj-1 + (G/LvP)(pAj-pAj-1)-k2(cAcB)j-1 HoAc∆hj/Lv (4-111b)
From equation(4-110c), cBj = cBj-1 –(b/a)(G/LvP)(pAj-pAj-1)+(b/a)(cAj-cAj-1) (4-111c)
As a second approximation;
(pA- ΗA cA)av. = (1/2)[(pA- ΗA cA)j + (pA- ΗA cA)j-1] (4-112)
(cAcB)av. =(1/2)[(cAcB)j + (cAcB)j-1] (4-112b)

with these values ∆hj, cAj and cBj are re-calculated from equations (4-111). These are
repeated until practically no difference between the last and previous calculations is
observed. After then, to the second step of the calculations is leaped. The steps are
continued until reaching the bottom of the column. Summation of calculated ∆hj s
gives the required height of packing.
4.6.4 Calculation of Height of Packing when Rates of Diffusion and Chemical

Reaction are comparable:
In this case, basic equation with Film theory representation becomes,

d 2cA
D AS + RA = 0 (4-113)
dz 2
This equation must be solved with the following boundary conditions:
1o) at z = 0 cA =cAi = constant
o
2 ) at z = zL cA = cAL
where cAL is the concentration of solute A in the bulk liquid.
Special case-1) Reaction is 0th order with respect to solute A, RA=-ko
d 2cA k
Then, 2
− o =0 (4-114)
dz D AS
Double integration of this equation results in
k
c A = o z 2 + I1 z + I 2 (4-115)
2D AS
Integration constants I1 and I2 are evaluated from the boundary conditions as;
c AL − (k o / 2D AS )z 2L − c Ai
I1 = and I2 = cAi Substituting these into equation(4-115)
zL
and noting that, kL =DAS/zL
⎡k k ⎤ ko 2
c A = c Ai − ⎢ L (c Ai − c AL ) + o ⎥ z + z (4-116)
⎣ D AS 2k L ⎦ 2D AS
is obtained.
Total molar flux of solute A crossing the interface becomes;
⎛ dc ⎞ D k
N Ai = −D AS ⎜ A ⎟ = k L (c Ai − c AL ) + AS o (4-117)
⎝ dz ⎠ z = 0 2k L
Or, if cAi is solved from NAi=kG(pA-ΗA cAi) and substituted into equation above;
⎡ D k ⎤
N Ai = K G ⎢p A − ΗA (c AL − AS 2 o )⎥ (4-118)
⎣ 2k L ⎦
is found.
Calculation of the height of packing in this case is accomplished by substituting the
above given value for NA in equation (4-110) and then conducting stepwise integration
as explained in the previous section.
Special case-2) Reaction is 1st order with respect to solute A, RA=-k1cA
Then, from equation(4-113);
d 2cA k
2
− 1 cA = 0 (4-119)
dz D AS
This equation must be solved with the boundary conditions given above.
By taking q2=k1/DAS this equation can readily be integrated. Result is:
c A = I 1 e qz + I 2 e − qz (4-120)
Integration constants can be evaluated by applying the boundary conditions. These are:
2 c Ai sinh(qz L ) − c Ai e qz L + c AL c Ai e qz L − c AL
I1 = I2 =
2 sinh(qz L ) 2 sinh(qz L )
By substituting these into equation (4-120),
c AL sinh(qz) + c Ai sinh[q ( z L − z)]
cA = (4-121)
sinh(qz L )
is obtained.
Total molar flux crossing the interface;
dc c c
N Ai = −D AS ( A ) z = 0 = k L Ha (c Ai − AL ) = (k L ) R (c Ai − AL ) (4-122)
dz cosh β cosh β
is found. Where β=qzL , Ha is Hatta number defined by Ha=β/tghβ and (kL)R is liquid
phase mass transfer coefficient when chemical reaction exist and defined by
(kL)R=kLHa .
Eliminating cAi with the help of NAi=kG(pA- ΗA cAi), equation (4-122) can also be
written as;
⎛ ΗA ⎞
N Ai = (K G ) R ⎜⎜ p A − c AL ⎟⎟ (4-123)
⎝ cosh β ⎠
where,
1 1 ΗA 1 ΗA
= + = + (4-124)
(K G ) R k G (k L ) R k G k L Ha
Criteria for fast and slow reaction;
e β + e − β (1 + β + β 2 / 2) − (1 − β + β 2 / 2) β2
cosh β = = = 1+
2 2 2
e β − e − β (1 + β + β 2 / 2) − (1 − β + β 2 / 2) β
tghβ = = =
e +e
β −β
(1 + β + β / 2) + (1 − β + β / 2) 1 + β 2 / 2
2 2
β β2
Then, Ha = = 1+ is found.
tghβ 2
The reaction is slow if β2/2≪1 (or β ≤ 0.2). Then, as Ha =1 and. cosh β=1,
equation (4-122) becomes;
NAi = kL (cAi-cAL)
This is the flux equation for physical absorption. As expected, in this case contribution
of chemical reaction on the absorption is negligible.Height of packing is calculated by
using equations given in section 4.6.3.
The reaction is fast if β is great (β≫3). So, in this case;
1
e +e
β −β
e +e β
eβ
β
1 2
cosh β = = = and = β ≈0
2 2 2 cosh β e
e −e
β −β
tghβ = β =1 and Ha = β
e + e −β
And flux equation in this case from equations(4-122) and(4-123);
NAi= kL βcAi = (KG)R pA (4-125)
Where,
1 1 ΗA
= + (4-126)
(K G ) R k G k 1 D AS
For the calculation of height of packing;
-G dpA/P = (KG)R avAcpAdh

p
can be written. From this Z = (H OG ) R ln A1 (4-127)
p A2
is obtained. Where;
ΗA G
(H OG ) R = H G + (H L ) R (4-128)
Lv
Lv Lv
and (H L ) R = = (4-129)
(k L ) R a v A c a v A c k 1 D AS
In Fig.4.31 conditions for slow and fast reaction are summarized.
1.0
Slow
1 1 /(k L ) R
= reaction
Ha 1/ k L
0.5
Diffusion and reaction
are comparable
Fast reaction
0 logβ
0 0.2 3 10
Fig.4.31 Values of Ha number and β at slow and fast reaction
Problems
4.1 Plot equilibrium curves of ammonia(A)-air(C)-water (S) system at 20 oC and 800 mmHg in the
concentration units shown in the table below:
Concentration unit in the gas Concentration unit in the liquid
Partial pressure of A (mm Hg) Molar concentration (k-mol A/ m3solution)
Partial pressure of A (mm Hg) Mole fraction of A
Partial pressure of A (mm Hg) Mass fraction of A
Mole fraction of A Mole fraction of A
Mass fraction of A Mass fraction of A
Mole ratio of A Mole ratio of A
Mass ratio of A Mass ratio of A
Solubilities of ammonia in water are given in the Table. App. 4.1. Densities of aqueous ammonia
solutions are listed in Perry’s Handbook.
4.2 With the help of Table.4.1, compare the solubilities of CO2 and H2S in water at 1 bar and 20 oC.
4.3 A 20 k-mol/h binary gas mixture containing 4 percent solute A by volume is to be scrubbed with a
40 k-mol/h liquid in a wetted- wall absorber operating counter-currently at 38 °C and 1 bar pressure, to
reduce the solute A content of the gas to 0.3 percent by volume. The wetted-wall column, due to the
large heat of absorption, is to be constructed in ‘shell & tube’ form, from 3 m long Ø30×2 mm
stainless steel tubes. Heat transfer calculations have shown that 170 tubes will be sufficient. Check
whether this tube number is sufficient for mass transfer. Give your conclusion.
Equilibrium relationship for the system at the operating conditions may be represented as y*= 0.5 x,
where y and x are mole fractions of solute A in gas and liquid respectively. Over-all mass transfer
coefficient based on gas phase is calculated as K'y = 4.3*10-4 k-mol/m2s.
4.4.Show that solution of the equation below after replacing logarithmic mean with arithmetic mean
y1
⌠ (1 − y) i ln dy
NG = ⎮
⌡ (1 − y)( y − y i )
y2
1 − y2
y
⌠ dy
1
1
gives NG = ⎮ + ln
⌡y 2 y − y i 2 1 − y1
4.5 99 percent of the ammonia is to be recovered from 10 mole percent ammonia-air mixture by
scrubbing with water in a packed column operating counter-currently at 20 oC and 800 mmHg. The
mass flow rates of the gas and liquid to the column are 0.95 kg/s and 0.65 kg/s respectively and the
cross-sectional area of the empty column is 1 m2. If the over-all volumetric mass transfer coefficient
KGav = 0.1 k-mol/m3s bar, find the necessary height of packing.
4.6 Air, containing 3% acetone vapor by volume is to be washed with water in a packed column,
operating counter-currently at 1 bar and 25 oC. Permissible acetone in the exit gas is 0.5% by volume,
and the flow rate of the gas to the column is 300 k-mol /h. Water, which is acetone-free, will be
supplied at a rate of 1.25 times the minimum water flow rate. The column is to be packed with 32*1.6
mm metal Raschig rings:
a) Calculate the flow rate of water as kg/h,
b) Write the operating line equation,
c) Calculate the concentration of liquid solution leaving the column as mass percent,
d) Calculate the percentage recovery of acetone,
e) Calculate the diameter of the column, for a gas side pressure drop of 400 N/m2 per meter height of
packing,
f) Find out with what per cent of the flooding gas velocity the operation is carried out,
g) Calculate the height of packing required.
At the operating pressure and temperature and within the concentration range involved, equilibrium
distribution of acetone between air-water is given as y*=2.2x, where y and x are mole fractions of
acetone in gas and liquid respectively.
Height of transfer units for acetone absorption into water in a column packed with 32*1.6 mm
Raschig rings were found experimentally and given as:
HG =1.397[G' 0.395/L' 0.417]; HL = 0.395L' 0.22, where HG and HL are in m., G' and L' are in kg/m2 s
4.7. A packed absorption column is to be designed to reduce the solute A content of a gas mixture
from 1.5 mole percent to 0.01 mole percent by contacting it with a liquid solvent, which is solute-
free. Molar ratio of liquid to gas is constant at 9 throughout the column. The equilibrium relationship
at the operating conditions and the concentration range involved may be expressed as y*= 6x, where y
and x are the mole fractions of solute A in gas and liquid respectively. Calculate the number of the
overall gas transfer units needed, starting from the definition equation of it. [Ans. : 11.77]
4.8 An absorption column, packed with 38 mm ceramic Berl saddles, is to be designed to contact a gas
phase of 1.0 kg/s with a liquid phase of 7.23 kg/s , counter-currently.
a) Calculate the diameter of the column for a gas side pressure drop of 200 N/m2 per meter of packing.
b) If this diameter is selected, determine with what percent of the flooding gas velocity the column
operates.
At the operating conditions, the viscosity of liquid and the densities of gas and liquid are: 1.5 cP, 2.9
kg/m3, 950 kg/m3. [Ans. : a) 0.966 m, b) % 53.6 ]
4.9 Carbon disulfide CS2 and nitrogen N2 gas mixture, containing 4.5 % CS2 by volume is to be
scrubbed with a hydrocarbon oil in a plate column, operating counter-currently at 760 mmHg and 24
o
C, to reduce CS2 content to 0.5 % by volume. The entering oil is CS2-free. Using Mc Cabe-Thiele
method:
a) Calculate the minimum liquid/gas ratio.
b) For a liquid/gas ratio of 1.33 times the minimum, determine the number of the ideal plates needed.
This system obeys Raoult’s law and the vapor pressure of CS2 at 24 oC is 342 mmHg.
4.10 An absorption column packed with 25 mm plastic Pall rings is to be designed to recover solute A
at 1 bar and 27 oC. The flow rates of the gas and liquid phases are 14.4 k-mol/h and 32.8 k-mol/h
respectively.
a) Calculate the diameter of the column for a gas velocity of 60 % of the flooding gas velocity.
b) What will be the pressure drop per meter of packing ?
Density and viscosity of the liquid at 27 oC are 910 kg/m3 and 1.2 cP. The molecular weights of liquid
and gas phases are 55 and 31 kg/k-mol. [Ans. : a) 0.312 m, b) 400 N/m2]
4.11 A column of 350 mm inside diameter, packed with 25 mm plastic Pall rings to a depth of 4.0 m,
is already available. This column is now being considered for a new absorption operation. The flow
rate of the gas to be processed is 7.2 k-mol/h and the solute content of this gas should be reduced from
2% to 0.1% by volume. The operation will be carried out counter-currently at 27 oC and 1 bar. The
liquid solvent, which is solute-free, will be introduced at a flow rate which is 1.5 times the minimum
solvent rate. At these conditions: height of one over-all gas transfer unit, HOG is calculated as 0.56 m.
Gas fan connected to the column can develop a pressure difference of 400 N/m2 along 4.0 m packed
height.
Equilibrium relationship of the system may be represented by y*=1.6x, where y and x are the mole
fractions of solute in gas and liquid phases respectively.
Find out whether this column can be used for the new operation or not under the given conditions. If
your answer is not, what alterations would you recommend?
Density and viscosity of the liquid at 27 oC are 910 kg/m3 and 1.2 cP. The molecular weights of liquid
and gas are 55 and 31 kg/k-mol.
4.12 A packed column is to be designed to absorb benzene vapor from air by contacting it with a
hydrocarbon oil at 25 oC and 760 mmHg. The partial pressure of benzene will be reduced from 6
mmHg to 0.5 mmHg. The entering hydrocarbon oil is benzene-free. Calculate:
a) The minimum value of L/G ratio,
b) The number of the over-all gas transfer units needed, for an operating L/G ratio which is 1.25 times
the minimum L/G ratio.
* *
Equilibrium relationship at 25 0C and 760 mmHg is y = 0.12 x, where y and x are the mole fractions
of benzene in gas and liquid respectively. [ Ans. b) NOG = 6.86 ]
4.13 Solute A will be absorbed from an inert gas containing 3 mole percent solute A into a solvent S in
a packed column operating counter-currently at 20 oC and 2.26 bar. The gas leaving the column will
not contain more than 0.05 mole percent solute A. The flow rates of solvent and gas to the column are
110 k-mol/h and 100 k-mol/h respectively. The column will be packed with 50 mm ceramic Berl
saddles.
a) Calculate the required number of the overall gas transfer units NOG by using any suitable method.
b) For a gas side pressure drop of 200 N/m2 per meter height of packing, calculate the diameter of the
column.
At the operating conditions equilibrium relationship of the system is given as y =0.5x, where x and y
are the mole fractions of solute A in liquid and gas. At 20 oC density and viscosity of liquid are 860
kg/m3 and 0.5 cP ; molecular weights of gas and liquid are 28 and 47 kg/k-mol.
[Ans.: a) 6.42, b) 0.70 m ]
4.14 Two gas streams will be scrubbed with water at 20 oC and 800 mmHg in a packed column. The
first stream which contains 4.8 mole percent ammonia and 95.2 mole percent air will be introduced at
the bottom of the column at a rate of 126 k-mol/h. The second stream containing 2.5 mole percent
ammonia and 97.5 mole percent air will be fed at the proper point at a flow rate of 133 k-mol/h. The
mole fraction of ammonia in the leaving gas should not be more than 0.005. The water, which is
ammonia free will be supplied at a rate of 3 600 kg/h.
Calculate the total packed height required and the introduction point of the second stream.
The maximum gas flow flux at any level in the column is to be 120 k-mol/h m2 based on empty
column cross-section. For the packing used, over-all volumetric mass transfer coefficient
K y a v = 6.5 (G ′) ,where Kyav is in k-mol/m3h and G' is in k-mol/m2h.
0.57
Assume dilute solutions and hence take the flow rates of the streams entering the column constant
throughout the column.
4.15 In a certain absorption process conducted at 20 oC and atmospheric pressure, 1360 kg/h of gas of
molecular weight 30 is to be contacted with water in a packed column of 3.65 m packing height.
Ceramic Raschig rings are selected as the packing material. Liquid/gas mass ratio of 2 is to be
employed. For a gas operating velocity of 60 % of the flooding gas velocity:
a) Determine the column diameter for the best packing size among 25, 50 and 76 mm sizes,
b) Calculate the pressure drop along the packing in mbar.
Density and viscosity of liquid phase may be taken as 1000 kg/m3 and 1 cP.
4.16 An existing packed column, 3.3 m high, is to be employed for countercurrent absorption of a
solute from a carrier gas into a liquid solvent. The inlet gas contains 3.8 % by volume of the solute and
solvent enters the column solute-free.
What will be the solute content of the outlet gas if the liquid/gas molar ratio employed is 1.2 ?
Under the selected operating conditions the individual heights of the transfer units are known to be
0.23 m for the gas phase and 0.40 for the liquid phase. The equilibrium relation is y* = 0.96 x, where y
and x are the mole fractions of solute in gas and liquid.
4.17 A solute will be recovered from a binary gas mixture in a plate column by contacting it with a
solvent at 25 oC and 1 atm. The gas contains 4 mole percent solute and percentage recovery will be at
least 90. The maximum molar ratio for L/G is to be 1.7 during the operation. There are two alternative
solvents which can be used. The equilibrium relationships with these solvents at the operating
conditions are y* = 120 x2 (for solvent I) and y* = 1.36 x (for solvent II) , where y and x are the mole
fractions of solute in gas and liquid phases respectively.
a) Which solvent is suitable for the operation?
b) What is the number of the ideal plates needed with this solvent?
4.18 A 20 k-mol/h air-SO2 gaseous mixture containing 3 % SO2 by volume is contacted with a 30 k-
mol/h water containing 0.1 % SO2 by mole in a stage (on a plate). The leaving gas contains 2 % SO2
by volume.
a) Calculate the composition of the leaving liquid,
b) Find the Murphere gas and Murphere liquid phase efficiencies.
*
At the operating conditions, gas-liquid equilibrium is given as y =1.2x, where y and x are the mole
fractions of SO2 in gas and liquid.
[Ans. : a) x=0.0077, b) EMG = 0.48, EML = 0.43 ]
4.19 A packed laboratory column, 2 m long, is used to remove a solute from air by countercurrent
absorption in water. The mole fraction of solute in the inlet gas is 0.08 and this is reduced to 0.05 at
outlet. The equilibrium relation is given by y* = 0.75 x, where y and x are the mole fractions of solute
in the gas and liquid.
The column is provided with a number of liquid sampling points and the following results were
obtained in a trial run:
z(m) 0 0.2 0.5 0.8 1.2 1.6 1.8 2.0
x 0.075 0.066 0.054 0.043 0.027 0.011 0.05 0
where z is the distance up the column measured from the bottom of the packing and x is the mole
fraction of solute in the liquid.
From the above results, plot a curve of 1/HOL versus z, where HOL is the local height of one overall
liquid transfer unit. Use vertical axis for z.
4.20 A liquid solvent containing 5.3 mass percent solute A is contacted with a solute-free gas in a
counter-current stripping tower isothermally to reduce its solute content to 0.5 mass percent. The flow
rate of solute-free gas is selected as 1.4 times its minimum value.
Calculate the concentration of outlet gas and percentage recovery of solute.
The equilibrium data at the operating conditions are given as;
x 0.005 0.01 0.02 0.03 0.04 0.05 0.055

y 0.0006 0.00125 0.0027 0.0044 0.0065 0.009 0.0113
where x and y are the mass fractions of the solute A in liquid and gas. [Ans. : 0.0060 (mass fraction]
4.21 A thirty-plate column is to be used to recover n-pentane from solvent oil by steam stripping. The
liquid contains 6 k-mol of n-pentane per 100 k-mol of oil and it is desired to reduce the solute content
to 0.1 k-mol per 100 k-mol of oil. Assuming isothermal operation and an over-all column efficiency of
30 percent;
a) Find the required steam rate per 1 k-mol of liquid rate,
b) Calculate the ratio of steam rate to the minimum steam rate,
c) Find the number of the plates needed if this ratio were selected as 2.
The equilibrium relationship for the system at the operating conditions may be given as Y=3 X, where
Y and X are the mol ratios in the gas and liquid phases respectively. [Ans.: a) 0.414, b) 1.34]
4.22 An existing packed column, 3.9 m high, is to be employed for countercurrent desorption by live
steam (steam stripping) of a solute from a liquid solvent. The mole fraction of solute in the inlet liquid
is 0.045 and the steam enters solute-free. The process can be regarded as isothermal and the column is
well insulated so that no condensation occurs inside the column. If the recommended gas/liquid molar
ratio is 0.6, calculate the mole fraction of solute in the outlet solvent. The equilibrium relation for the
system is y* = 2 x, where y and x are the mole fractions of solute in the gas and liquid. Under the
operating conditions the heights of individual transfer units are 0.3 m for the gas phase and 0.4 m for
the liquid phase.
4.23 The concentration of solute A in a gas stream is to be reduced from 5 to 0.5 % by volume, by
contacting it with a solvent in an absorption column at 1 bar. Solvent is available as solute-free at 20
o
C. The molar heat of absoption is 42 000 kJ/k-mole of A absorbed and molar spesific heat of liquid
is 84 kJ/k-mole oC . Over the range of operation, the equilibrium relationships at various
temperatures are linear and given as y*= m x. The slope m changes with temperature as follows:
t(oC) 20 30 40 50
m 0.52 0.68 0.84 1.0
a) Draw the equilibrium curve for non-isothermal absorption,
b) Calculate the minimum solvent rate , for a gas rate of 50 k-mol/h,
c) Draw the operating line for a solvent rate which is 1.15 times the minimum rate,
d) Explain, what would be, if isothermal absorption at 20 oC were assumed ?
In the solution use “the short method”.
4.24 Neutralization reaction between ammonia and phosphoric acid shown below is instantaneous.
3NH3 + H3PO4 (NH4)3PO4
An air-ammonia gaseous mixture containing 10 percent ammonia by volume is to be washed with

aqueous phosphoric acid solution, contaning 0.37 k-mol acid per m3 of solution at 1 bar and 20 oC in a
packed column, to reduce the ammonia content of the air to 0.1 mole percent. The cross-sectional area
of the empty column is 1.6 m2. Flow rates of the gas and liquid to the column are 150 k-mol/h and
22.5 m3/h respectively. Volumetric mass transfer coefficients at the operating conditions were
estimated as kGav = 40 k-mol/m3h bar and kLav = 4.8 1/h. Henry’s law constant for ammonia water
system at 20oC is 0.0132 bar m3/k-mol. Molecular diffusivity of phosphoric acid in water at 20oC may
be taken as 2.85*10-9 m2/s.
Calculate the height of packing needed. [ Ans. Z = 3.78 m ]
4.25 Reaction between chlorine gas and aqueous sodium hydroxide is slow and first order,
Cl2 + NaOH NaOCl + HCl
Air containing 6 percent Cl2 gas by volume is to be scrubbed with aqueous NaOH solution in a
packed column operating counter-currently at 1 bar and 20 oC, to reduce the volume percent of Cl2 to
0.1. Calculate the height of packing required for the following case: [Ans. Z = 3.36 m ]
3
Volumetric flow rate of liquid : 10 m /h
Molar flow rate of gas : 150 k-mol/h
Cross-sectional area of the column : 1 m2
Rate constant of the reaction : 0.15 1/s
Volumetric mass transfer coefficient for the gas phase : 0.125 k-mol/m3sbar
Volumetric mass transfer coefficient for the liquid phase : 0.006 1/s
Liquid hold-up : 0.04 m3liquid/m3 of packing
Henry’s law constant : 0.04 bar m3/k-mol
4.26 Solute A is absorbed at atmospheric pressure by countercurrent contact with a liquid solvent
containing reactant B. The rection between A and B is instantaneous and proceeds according to the
stoichiometry below;
A+B P (in solvent S)
The partial pressure of A in the inlet gas is 50 mbar and the concentration of B in the inlet liquid is
0.15 k-mol/m3. If the height of packing is 0.9 m, calculate the partial pressure of A in the outlet gas.
The height of overall gas transfer unit for physical absorption is 1.0 m, the absorption factor is 1.3, the
Henry’s law constant is 0.25 bar m3/k-mol, the gas and liquid phase mass transfer coefficients are 3.0
k-mol/m2h bar and 0.1 m/h respectively. The liquid phase diffusivities of A and B may be taken as
equal.
Chapter-5
DISTILLATION
5.1 Introduction: Distillation operation is a mass transfer operation aimed at

separating a liquid solution into its components. The second phase, which is vapor, is
not brought from the outside as in other mass transfer operations, but is created from
the original liquid phase by partial vaporization. Then, in distillation operation, the two
phases involved are vapor and liquid and mass transfer taking place between these two
phases enriches the phases in the components. The principle, on which separation with
distillation is based, is the difference in the volatilities of the components of the
solution, which are all volatile but at different levels. Distillation differs hence from
Evaporation, which is an important unit operation, in that in evaporation only the
solvent of the liquid solution is volatile at the operating temperature and the solute,
which is practically non-volatile, does not transfer to the vapor phase. For example, the
separation of K2SO4 from its aqueous solution is an evaporation operation as K2SO4
solid is not volatile at the evaporation temperature of the solution. But, on the other
hand, separation of a methanol/ethanol solution is a distillation operation, as the vapor
obtained by partial vaporization contains both of the components. But, since the vapor
thus formed is richer in the more volatile methanol than the remaining liquid, a certain
degree of separation is thus achieved. Now, if so-obtained vapor mixture is partially
condensed, the remaining vapor is further enriched in methanol as more ethanol than
the methanol condenses. So, “partial vaporization of a liquid solution and partial
condensation of a vapor mixture always enrich the vapor in the more volatile
component, and the liquid in the less volatile component”. With the repeating of
partial vaporizations and partial condensations many times, finally a vapor is
produced, which is almost pure in the more volatile component, and a liquid which is
almost pure in the less volatile component; thus giving a total separation of liquid
solution. As it is seen, distillation gives complete separation of the solution. For that, it
is the most commonly used separation operation in chemical engineering practice,
when liquid solutions are to be separated. In order to understand distillation operation,
the equilibrium between liquid and vapor must be known very well.
5.2 Liquid-Vapor Equilibria: Let us start with considering the behaviour of a binary
solution of A+B, which is kept under constant pressure in a closed container. Let us
assume that component A is more volatile than the component B. When the vapor
pressure of a component at all the temperatures is greater than that of other
component, this component is then named as more volatile component (MVC in
short), while the other is being named as less volatile (LVC in short). Assume that x
and y are the mole fractions of component A in liquid and vapor phases respectively,
and tA and tB show the boiling point temperatures of pure A and pure B at the
prevailing pressure. Typical liquid-vapor equilibrium of this solution is shown in
Fig.5.1. Consider the liquid solution whose temperature and composition are tK and xk
and represented by point K. If this solution, which is a cold liquid, is heated slowly,
the first vapor bubble forms at temperature tH and its composition yJ is read from point
J. As expected, yJ is greater than xk. xk and yJ are the compositions of liquid and vapor
phases which are in both mass and thermal equilibrium. Temperature tH is known as
the bubble point temperature of the liquid solution whose composition is xk. The line
HJ, which relates two equilibrium phases, is named as tie-line. If more heat is added to
the mixture, both temperature of the mixture and the quantity of the vapor in the
mixture increase at the expense of liquid. For example, point M represents the vapor-
liquid mixture at temperature tL, which separates in equilibrium liquid and vapor
phases represented by the points L and G, the line LG being a tie-line. As it is seen, the
composition of liquid drops from xk to xL ,and that of vapor from yJ to yG with
increasing vaporization, but yG is again greater than xL. The ratio of the moles of vapor
Mole fraction of the MVC in vapor, y

0 yR= xk yG yJ 1
P=cons.
tR
R
Temperatures, t
Temperatures, t
tB Dew point
N temperature curve
tS
S
tL G
L M Tie-lines
J
tH
H
tA
Bubble point
temperature curve
0 xS xL xH =xK 1
Mole fraction of the MVC in liquid, x
Fig.5.1 Typical temperature-composition diagram (t-xy) of a binary solution
to the moles of liquid in the mixture is given by the lines ratio of LM/GM, which is
known as inverse lever-arm rule. If the mixture is further heated, both the
temperature and vapor quantity increase further, and finally to a point N is reached at
which the last liquid drop, whose composition is read as xs from point S vaporizes at
temperature ts. As it is noticed, the liquid solution has started boiling at temperature tH
and ended up at temperature ts. It follows from this that, liquid solutions unlike the
pure liquids have no constant boiling point temperatures but have boiling temperature
ranges, which is tH-ts for a liquid solution of composition xk. Hence, the curve given by
the points tB-S-L-H-tA is named as bubble-point-temperature curve, as it shows the
saturated liquid solutions. If the vapor represented by point N is further heated, it
becomes superheated vapor, as in this case only its temperature increases. Let us
consider the phenomena in the reverse direction. If the superheated vapor mixture
whose temperature and composition are tR and yR and represented by point R is cooled
slowly, no phase change is observed until the temperature drops to tN=ts, at which first
liquid drop (dew) forms, whose composition is read as xs from point S. By further
cooling, the quantity of liquid increases at the expense of vapor during which both
liquid and vapor compositions alter. For example, when point M is reached, the
compositions of the equilibrium liquid and vapor are read from points L and G as xL
and yG. As it is seen, while the composition of liquid increases from xs to xL, the
composition of vapor rises from yR to yG. If the cooling is further continued, when the
temperature tH is reached, the last vapor bubble whose composition is yj, condenses
giving a saturated liquid mixture represented by point H. Further cooling sub- cools
the liquid bringing it back to the condition represented by point K. As it is seen,
superheated vapor represented by point R first becomes saturated vapor at point N
(temperature tN) then starts condensing, and condensation continues until the
temperature drops to tJ (point J) during which its composition enriches in the MVC
and finally the last vapor bubble, which is richest in the MVC condenses at point J
with composition yJ. The condensation process takes place at a temperature range of
tN-tJ ,not at a constant temperature. Since the curve given by the points tB-N-G-J-tA
represents saturated vapor mixtures (vapor mixtures at their dew points), it is known as
dew-point-temperature curve. Hence, any point between bubble-point-temperature
curve and dew-point-temperature curve
1 represents a liquid-vapor mixture, which
P=cons.
upon separation gives two equilibrium
mole fraction of the MVC in vapor, y
yJ equilibrium
yG
(H,J)
curve
phases: saturated liquid and saturated vapor,
(L,G) which are located on the bubble-point-
tH
y= x temperature curve and on the dew-point-
yN (S,N)
temperature curve by drawing the tie-line
tL through the point representing the mixture.
Their amounts are found by applying the
tS
inverse lever-arm rule to the tie-line. Any
point just on the bubble-point-temperature
curve represents saturated liquid, and on the
0
dew-point-temperature curve represents
0 xS xL xH 1
mole fraction of the MVC in liquid, x
saturated vapor. Points above dew-point-
temperature curve and below the bubble-
Fig.5.2 xy-diagram of a binary mixture point-temperature curve represent
superheated vapor and sub-cooled liquid
respectively.
If the liquid represented by point K is heated in an open vessel, it starts boiling at
temperature tH represented by point H. Since the vapor escapes from the vessel, the
remaining saturated liquid becomes poorer in the MVC; hence its temperature and
composition shift toward left along the bubble-point-temperature curve with the
vaporization.
The equilibrium or t-xy diagram shown in Fig.5.1 is peculiar to each binary mixture
and it is only obtained experimentally for the real solutions. Various experimental
techniques have been developed for the measurements, most of which are given by
E.R.Gilliland and C.S. Robinson in their book “Elements of Fractional Distillation”
Mc Graw-Hill, 1950. The experimentally measured vapor-liquid equilibria for many
binary solutions are given in the literature. The book written by Hirata et. al contains
large number of binary solutions’ vapor-liquid equilibria (“Computer Aided Data
Book of Vapor-Liquid Equilibria” Elsevier Scientific Publishing Company, 1975).
Sometimes, the vapor-liquid equilibria are given on simple xy-diagrams as shown in
Fig.5.2. Although the relationship between liquid and vapor compositions can easily
be seen, temperature information is not normally given in these diagrams (to the
Figure these were added for the explanation purpose).
5.2.1 Ideal Solutions: Vapor-liquid equilibria of ideal solutions can be computed
directly from the vapor pressures of the pure components without resorting to the
experimentation. The criteria for ideality have already been given in Section 4.2.1 For
ideal solutions, Raoult’s law and for ideal gas (vapor) mixtures Dalton’s law are
applicable. Raoult’s law for a binary solution of A+B is written as:
p A = p oA x
t = cons.
p B = p oB (1 − x) (5-1)
P-x p oA
p oB
By summing up these two equations;
P-y
P = p A + p B = p x + p (1 − x)
o
A
o
B (5-2)
pressure
pA − x pB − x
is obtained. From these, it is understood that
partial and total pressures change linearly
with the mole fraction as shown in Fig.5.3.
0 x,y 1
By solving x from these two equations, (B) (A)
P − p oB
x= o (5-3) Fig.5.3 Ideal solution
pA − pB o
and from the combination of Raoult

and Dalton laws,
p po
y= A = A x (5-4)
P P
are obtained. Now, with the help of these two equations, liquid-vapor equilibrium can
be computed as follows: arbitrary temperatures between the boiling point temperatures
of pure components at the specified total pressure are selected and vapor pressures of
the components at these temperatures are calculated from the Antoine equations of the
components. Then, from equation (5-3) x, and from equation (5-4) y are computed.
With the so-calculated x and y values, t-xy and xy-diagrams are plotted. The accuracy
of the plots depends on the number of the temperatures selected.
Example-5.1) Plotting of xy- and t-xy Diagrams of an Ideal System
Solutions of benzene- toluene obey Raoult’s law.

a) Compute the vapor-liquid equilibrium of this system at 760 mmHg.
b) Plot t-xy and xy- diagrams at 760 mmHg for this system.
Vapor pressure of benzene and toluene can be calculated from Antoine equation which is written as:
b o
log p io = a − where p io in mmHg, and t in C. Antoine constants a, b and c for benzene
c+t
and toluene are given in the table below:
Component tbp (oC) a b c t range ( oC)
Benzene(A) 80.1 6.90565 1211.033 220.79 7-135
Toluene(B) 110.6 6.95334 1343.943 219.38 7-135
Solution :
Select t = 85 oC, then ;

1211.033
log p oA = 6.90565 − = 2.9453 p oA = 881.7 mmHg
220.79 + 85
1343.943
log p oB = 6.95334 − = 2.538 p oB = 345.1 mmHg
219.38 + 85
760 − 345.1 881.7
From equations (5-3) and (5-4) x= = 0.773 y= (0.773) = 0.897
881.7 − 345.1 760
By selecting various temperatures and repeating the steps given above, the following table is obtained.
Select C a l c u l a t e
t (oC) p oA (mmHg) p oB (mmHg) x y
80.1 760.0 292.3 1.0 1.0
85.0 881.7 345.1 0.773 0.897
90.0 1021.0 406.8 0.575 0.773
95.0 1176.8 476.9 0.405 0.626
100.0 1350.5 556.4 0.256 0.455
105.0 1543.2 646.0 0.127 0.258
110.6 1783.4 759.5 0.0 0.0
With the data in the table above t-xy and xy-diagrams of the system can easily be plotted on the
millimetric papers as shown below.
t-xy Diagram xy-Diagram
115
1
mole fraction of benzene in
0.9
0.8
105
temperature (oC)
0.7
vapor,y
0.6
95 0.5
0.4
0.3
85 0.2
0.1
0
75 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
mole fraction of benzene,x,y mole fraction of benzene in liquid,x
5.2.2 Deviation from Ideality: Real and Azeotropic Solutions: In real solutions, the
total pressure measured over the solution may be greater or smaller than the total
pressure calculated from equation (5-2). If the measured pressure is higher than the
calculated pressure, this solution is said to deviate from Raoult’s law in positive
direction, if the reverse happens, deviation is said to be in negative direction. The
partial pressures of the components in such systems do no longer change linearly with
the composition. In Fig.5.4, the changes of total and partial pressures with the
compositions are shown for positive and negative deviations. As it is seen from the
figures, system approaches ideal system when the mole fraction of the component in
the liquid nears 1.
For the real (actual) solutions;
p A = γ A p oA x
p B = γ B p oB (1 − x) (5-5)
are written, where γ A and γ B are the liquid phase activity coefficients of the
components and they show the direction and the degree of deviation of the solution
from ideality. When they are 1, the solution is ideal, as expected and when they are
greater than 1, deviation is positive, and smaller than 1, the deviation is negative. If
t=cons. P-x
t =cons.
p o P-x p oA
A o
p oB P-y p B
P-y
pA − x pB − x pB − x pA − x
pressures
pressures
0 1 0 x,y 1
x,y
(B) (A) (B) (A)
(a) (b)
Fig.5.4 Deviation from idealty (a) in (+), (b) in (-) direction
the activity coefficients, which are dependant both on temperature and composition are
close to 1, deviation from ideality is small. In Fig.5.5, the changes of activity
coefficients with compositions are shown for two different systems, one deviating
positively, and the other deviating negatively. When the deviation from ideality is
great and the difference between the vapor pressures of the two components is small,
the total pressure versus mole fraction curve may pass through a maximum or
minimum. This type of solutions are said to form azeotropic solutions or constant
boiling solutions. Passing through a maximum results in minimum boiling
azeotropism, whereas passing through a minimum gives maximum boiling
azeotropism. Constant temperature, constant pressure and xy-diagrams of minimum
and maximum boiling azeotropic systems are all shown in Fig.5.6. As are seen from
(a) propanol-water (b) acetone-chloroform
Fig.5.5 Change of activity coefficients with composions (a) at positive, (b) at negative deviation
the figures, at point Az saturated vapor and liquid curves touch each other. The liquid
solution corresponding to this composition boils at constant temperature as if it were a
pure liquid, and the vapor formed has the same composition with the liquid. While a
component is more volatile on the left of point Az, it becomes less volatile on the right
of the point, hence the volatilities of the components change at point Az. The solutions
behaving in this way cannot be separated completely by using classical distillation
methods. Minimum boiling azeotropism is more common than the maximum boiling
azeotropism, and there is large number of binary and ternary solutions showing
azeotropism. The books written by L.E. Horsly contain almost all the azeotropic
systems (Azeotropic Data-I,II, Am. Chem. Society, 1952-1962). In some systems
azeotropic point, hence the azeotropic composition may change or even completely
disappears with changing pressure. Ethanol-water solution, which is an industrially
important solution, has a minimum boiling azeotropism, which occurs at 78.2 oC with
a composition of 95.6 mass percent ethanol at 1 atm. The azeotropism of this system
disappears at pressures below 70 mmHg.
Example-5.2) Check for Ideality
Equilibrium partial pressure of acetone in vapor over a liquid solution of acetone-methanol,

containing 30 mole percent acetone and saturated at 65.9 oC is measured as 398 mmHg. Find out
whether this solution is ideal or not. State the direction of deviation from Raoult’s law, if exist.
1279.9
The vapor pressure of acetone is given as: log p oA = 7.24 − where p oA in mmHg and t in oC.
237.5 + t
Solution :
1279.9
Vapor pressure of acetone at 65.9 oC : log p oA = 7.24 − = 3.0215
237.5 + 65.9
p oA =10 3.0215 = 1050.7 mmHg
398
From equation (5-5) : γA = =1.26
(1050.7)(0.30)
as γA greater than 1, the solution is not ideal and positively deviates from Raoult’s law.
Az
t =cons. t =cons.
P-x p oA
P-x
Az
p o
A
p oB
P-y
P-y
o
pressures
p B
pA-x
pressures
pA-x pB-x pB-x
0 1.0 0 x,y 1.0

(B) x,y (A) (B) (A)
Az
t-y
P= cons.
P= cons.
tB G t-x
L G
L
temperatures
G tB
L t-y
tA
temperatures
G
L
t-x tA
Az
0 x y y x 1.0 0 y x x y 1.0
(B) x,y (A) (B) (A)
x,y
1.0 1.0
P= cons. P= cons. y>x
y y<x y Az
Az
y>x
y=x
y=x
y<x
0 0
0 x 1.0 0 x 1.0
a b
Fig.5.6 (a) Minimum and (b) maximum boiling azeotropism
5.2.3 Partial Solubility and Insolubility of the Components in Liquid Phase: In
some special cases, components A and B are partially soluble or even completely
insoluble within each other. Vapor-liquid equilibria of such systems are quite different
than the normal systems’ vapor-liquid equilibria. Let us consider first the system that
forms two liquid phases because of incomplete solubility of the components. In such a
system each component exerts its own vapor pressure in the vapor phase and then the
total pressure is written as,
P = p oA + p oB (5-6)
If such a liquid mixture is heated in an open vessel, it starts boiling when the pressure
given by equation (5-6) reaches the outside pressure and the temperature and pressure
remain constant until the MVC of the mixture is completely consumed up (first
period). As soon as the MVC is removed completely, the pressure of the system drops
to the vapor pressure of the LVC at the prevailing temperature. If heating is continued,
the boiling starts again when the vapor pressure of the LVC rises to the outside
pressure and then the temperature remains again constant until this component
vaporizes completely (second period). The mole fractions of the more and less volatile
components in the vapor at the first period at which the two components vaporize
together are calculated from the equations below,
p oA p oA
y= = o (5-7)
P p A + p oB
p oB p oB
and 1− y = = o (5-8)
P p A + p oB
These values remain constant throughout the first period. This special case forms the
basis of steam distillation, which is frequently used to separate a high boiling organic
material, which is insoluble in water, from the non-volatile impurities. For that, water
is added to the mixture and then heating is started. The mixture starts boiling at
relatively low temperature (less than 100 oC for atmospheric pressure) due to the high
vapor pressure of water and as long as water exists in the mixture, this temperature
does not change. Steam consumption per unit mass of organic material distilled can be
computed from,
kg steam mA 18 y 18 p oA
= = = (5-9)
kg organic vapor mB M B (1 − y) M B p oB
where, y is the mole fraction of water vapor (steam) in the vapor mixture, MB is the
molecular weight of vaporizing organic material. Hence, energy required qs as kJ per
mB kg of organic material distilled is given by;
18 p oA
qs
= [cLA (t − t o ) + λ A ]+ [cLB (t − t o ) + λ B ] (5-10)
m B M B p oB
where, to and t are the initial and boiling point temperatures as oC, λA and λB are latent
heats of vaporization of water and organic material at temperature t as (kJ/kg), cLA and
cLB are the mean specific heats of water and organic material as ( kJ/kg oC).
As the water and organic material do not dissolve within each other, they separate in
two phases in a decanter upon the condensation of vapor. By using steam distillation
the organic materials, which normally boil at high temperatures and thus have the risk
of decomposition, can be separated at low temperatures without decomposition. But
the cost of separation by steam distillation may be very high especially for low
molecular weight organics, due to the high rate of steam requirement.
Example-5.3) Steam Distillation
500 kg ortho-nitrotoluene (M.W=137; b.p.= 222 oC) at 25 oC, will be purified from very small
quantity of non-volatile impurities, with steam distillation in a jacketed vessel equipped with a
condenser and a decanter. Water at 25 oC will be continuously supplied to the vessel to maintain a
liquid water level. Distillation is to be carried out at 760 mm Hg pressure.
Calculate:
a) The temperature at which distillation will proceed,
b) The amount of water to be used,
c) The heating steam requirement. Steam is saturated at 40 kN/m2 gauge pressure and
condenses in the jacket.
d) The loss of ortho-nitrotoluene with water,
e) The energy requirement for direct vaporization of ortho-nitrotoluene.
f) What other way may be used to purify the ortho-nitrotoluene at the same temperature?
Compare this with steam distillation.
Temperature ( oC) 60 62.3 99 99.5 100 110 123.5 222

Water p oA (mmHg) - - 733.5 746.8 760 1060 - -
(A)
cLA(kJ/kgK) 4.182
λA(kJ/kg) 2267 2238
o-Nitro p o (mmHg) 12.8 13.1 13.4
B
toluene
cLB(kJ/kgK) 1.57 1.75
(B)
λB(kJ/kg) 389.6 340
Solution:
a) When p oA + p oB = P = 760 mmHg distillation starts.
Assume, t = 99 oC , from table above, p oA + p oB = 733.5 + 12.8 = 746.3 mmHg < 760 mmHg
Assume, t = 99.5 oC
p oA + p oB = 746.8 + 13.1 = 759.9 mmHg ≅ 760 mmHg
Then, distillation starts and proceeds at 99.5 oC
m B18 p oA (500)(18)(746.8)
b) From equation (5-9) mA = = = 3 745 kg water
M B p oB (137)(13.1)
c) The steam requirment is obtained from equation(5-10). c LA and c LB must be taken at,
t o + t 25 + 99.5
= ≅ 62.3 o C
2 2
qs
=
18 (746.8)
[(4.182) (99.5 − 25) + 2267] + [(1.57) (99.5 − 25) + 389.6]= 19 820.1
m B (137)( 13.1)
Then, required heat energy : qs= (19 820.1) mB= (19 820.1)(500) = 9.91*106 kJ
Absolute pressure of the heating steam ; Ps=Poutside + Pgauge= 760+760(40/101.3) =1 060 mmHg
From the table ; ts = 110 oC and λs =2 238 kJ/kg
q s 9.91 *10 6
Then, required heating steam amount : ms = = = 4 428 kg
λs 2238
d) In the Perry’s Handbook, the
solubility of o-nitrotoluene in water at 30 oC is given as : 0.07 kg o-nitrotoluene per 100 kg water.
(3 745)(0.07)
Then, loss of o-nitrotoluene = = 2.62 kg
100
e) Direct vaporization at 760 mmHg takes place at 222 oC , c BL is taken at (25+222)/2=123.5 oC.
Then, energy requirment:
q s = m B [c LB (t − t o ) + λ B ] = (500) [1.75 (222 − 25) + 340]= 3.43 * 10 5 kJ
5
As it is seen, only 3.43 *10 .100 = 3.46 % of the energy for steam distillation would be enough
in this case. 9.91 *106
f) As other way, vacuum evaporation at the same temperature, which corresponds to 13,1 mmHg
absolute pressure (760-13.1≈747 mmHg vacuum), may be considered.
q s = (500) [1.57 (99.5 − 25) + 389.6] = 2.53 * 10 kJ

5
In this case;
2.53 *105
In other words; only .100 = 2.55 % of the energy for steam distillation would be
enough. 9.91 *106
Saving in the heating energy is compared with the energy required for creating vacuum. Decision is
then given.
Some systems deviate from the ideality so much that components A and B have only
partial solubility within each other in liquid state. The vapor-liquid equilibria of such
systems are rather interesting within partial solubility range. The vapor-liquid
equilibrium of water/n-butanol system, which has industrial importance and behaves in
this way, is shown in Fig.5.7. The area below points D and E shows the concentration
range at which partial solubility in liquid phase occurs. The binary mixture represented
by a point in this area is heterogeneous and separates in two insoluble liquid phases.
For example, the mixture which has 82 mole percent water and at 85 oC and shown by
point M separates in two equilibrium liquid phases one containing 58 mole percent
water and 42 mole percent n-butanol and being represented by point C, the other
containing 98 mole percent water and 2 mole percent n-butanol and being represented
by point K. These equilibrium liquid phases are found by drawing the liquid tie line
passing through point M, and the compositions of the phases change with temperature.
If a liquid mixture represented by a point in this region is heated up slowly, when the
temperature reaches boiling point temperature, which is about 93 oC, vapor forms. The
composition of this vapor, which is represented by point Az, remains constant at
azeotropic composition of 77 mole percent water and 23 mole percent n-butanol until
one of the components is depleted. In the regions outside this region (left of point D
and right of point E) liquid solutions are homogeneous and behave as normal systems.
P =cons.
tB vapor
N t-y
temperature,t
S
J
H tA
t-y
t-x t-x
AZ E
D
K
F liquid C
M
two liquid phase
0 mole fraction of water in liquid and vapor, x,y 1.0
1.0
mole fraction of water in vapor, y
AZ E
H,J y =x
0
0 mole fraction of water in liquid, x 1.0
Fig.5.7 Vapor-liquid equilibrium diagrams of water / n-butanol
For example, if the liquid solution represented by point F is heated up, it starts boiling
at point H and the first vapor bubble formed, is represented by point J. As the
vaporization proceeds, the composition of liquid shifts toward S, and the composition
of vapor toward N.
5.2.4 Volatility and Relative Volatility: The volatilities of A and B in a binary
solution are defined as;
pA pB
αA = αB = (5-11)
x 1− x
The relative volatility of A to B is then given as,
α p A /x
α= A = (5-12)
α B p B /(1 − x)
From Dalton’s law p A = y P and p B = (1 − y) P can be written. If these are
substituted into equation (5-12);
y (1 − x)
α= (5-13)
x (1 − y)
and solving for y,
αx
y= (5-14)
1 + (α − 1) x
is obtained. This equation is used to express the vapor-liquid equilibria of binary
solutions in functional way, when the relative volatility is a constant or does not
change much within the operating temperature range. For ideal system, equation (5-
14) reduces to equation below after substituting from Raoult’s law,
α = p oA / p oB (5-15)
Although the vapor pressures change with temperature, their ratio remains almost
constant in ideal solutions. Thus, equation (5-14) can be used to express vapor-liquid
equilibriums in functional way in ideal solutions. In many real solutions, the change of
relative volatility within the temperature range involved is not so great. Thus, equation
(5-14) can still be used in the real solutions, when the difference between the relative
volatilities calculated at the top and bottom conditions of the column is not greater
than 15%, in which case geometric mean of the two relative volatilities is
recommended for equation (5-14). Table.5.1 contains the relative volatilities of some
binary solutions calculated at the boiling point temperatures of the pure components of
the solutions.
For the separation of a binary solution by the classical distillation methods, the relative
volatility of the solution should nowhere be 1, and greater the value of α easier the
separation of solution by distillation. Note that at azeotropic composition α =1.
Example-5.4) Calculation of Relative Volatility
Calculate the relative volatilities of benzene to toluene at x = 0.1 , 0.3 , 0.5 , 0.7 and 0.9 and compare
the values.
From xy-diagram of benzene/toluene at 760 mmHg plotted in Example-5.1, corresponding y values

are read and from the equation (5-13) α values are computed. Results are given in the table below;
x 0.1 0.3 0.5 0.7 0.9

y 0.205 0.51 0.72 0.855 0.96
α 2.32 2.43 2.57 2.53 2.67
As expected, α values do not change much with the composition.
5.2.5 K-Values: The relationship between liquid and vapor compositions of

component-i in a binary or a multi-component solution at equilibrium may be
expressed as,
yi = Ki xi (5-16)
where, Ki is known as the K value or distribution coefficient of component-i. This

equation is especially useful for the computation of vapor-liquid equilibria of multi-
component solutions. For ideal solutions, Ki = p io /P and for real solutions
Ki = p io γ i /P . It follows from here that K value of a component depends on
(K)
Fig.5.8 K-Values of Some Hydrocarbons at 1 atm.
temperature and pressure. The K values for many components were measured
experimentally and are given either in the classical diagrams such as shown in Fig.5.8,
or in nomographific diagrams developed by C.L. DePriester.
Table 5-1. The relative volatilities of some binary solutions computed at the boiling
points of the pure components of the solutions
Boiling p. of Boiling p. of
Solution component-1 α component-2 α
(oC) (oC)
Benzene-ethylene dichloride 80.1 1.113 83.48 1.109
Benzene-toluene 80.1 2.61 110.7 2.315
n-Butyl chloride-n-Butyl bromide 77.5 2.08 101.6 1.87
Chloroform-carbon tetra chloride 61.1 1.71 76.6 1.60
Ethanol-isopropanol 78.3 1.18 82.3 1.17
Ethanol-propanol 78.3 2.18 97.2 2.03
Ethyl chloride-Ethyl bromide 12.5 3.23 38.4 2.79
Ethyl ether-benzene 34.6 5.16 80.2 3.95
Ethylene dibromide-propilen dibromide 131.7 1.30 141.5 1.30
Ethylene dichloride-trichloroethane 83.5 2.52 113.7 2.33
n-Heptane-methylcyclohexane 98.4 1.058 100.3 1.056
n-Hexane-n-heptane 69.0 2.613 98.4 2.33
Methanol-ethanol 64.7 1.73 78.1 1.64
Methanol-isobutanol 64.6 6.1 107.5 4.4
Methanol-propanol 64.6 3.89 97.2 3.15
Methyl acetone-ethyl acetate 56.8 2.036 77.1 1.923
Phenol-o-cresol 181.2 1.30 190.6 1.275
Phenol-m-cresol 181.2 1.768 201.5 1.699
Phenol-p-cresol 181.2 1.793 202.2 1.728
Toluene-benzyl chloride 110.7 7.75 178.0 4.45
Toluene-chlorotoluene 110.7 4.76 162.0 3.65
Water-ethylene glycol 100.0 49.8 197.0 13.2
Water-ethylene glycol(150 mm Hg) 60.1 98.0 150.2 21.0
Water-ethylene glycol (50 mm Hg) 38.1 76400 202 244
5.2.6 Bubble Point Temperature: In order to find the bubble point temperature and
the composition of the first bubble to be formed from a known composition of a liquid
solution at a specified pressure, the equation,
∑ yi = 1 =∑ Ki xi (5-17)
can be used. Since P and xi are known, an arbitrary temperature is selected and at this
temperature and the specified pressure the K value of each component is found and
then product of Kx for each component is computed. If the summation of these
products is 1 or very close to 1, the selected temperature is the bubble point
temperature of the solution and the product Kx for any component gives its mole
fraction in the first vapor bubble formed. If the summation deviates considerably from
unity, a new temperature is selected and steps are repeated with this temperature. The
temperature selection is repeated until the summation gives 1.
5.2.7 Dew Point Temperature: The dew point temperature of a known composition
vapor mixture at constant pressure, and the composition of the first liquid drop to be
formed, can be computed from;
yi
Σ xi = 1 = Σ (5-18)
Ki
The calculation is done by trial and error by selecting a temperature. At this
temperature and given pressure the K value of each component is read and then the
ratio of y/K is found. If the summation of these ratios is 1 or very close to 1, the
selected temperature is the dew point temperature of the vapor mixture and y/K ratio
for each component gives its mole fraction in the first liquid drop that will form. If the
summation deviates substantially from 1, with new temperature selections the steps are
repeated until the summation can be accepted as 1.
Example-5.5) Calculation of Dew Point Temperature of a Ternary Mixture
Ternary solutions of benzene/toluene/o-xylene are ideal.

a) Calculate the dew point temperature of a vapor, containing 20 mole percent benzene, 30 mole
percent toluene and 50 mole percent o-xylene at 760 mmHg total pressure.
b) What is the composition of the first liquid droplet formed?
c) What is the temperature range at which all the vapor will condense
(condensation range) ?
Antoine constants for the components are given in the table below:
Component tbp (oC) a b c t range ( oC)

Benzene(A) 80.1 6.90565 1211.033 220.79 7-135
Toluene(B) 110.6 6.95334 1343.943 219.38 7-135
o-Xylene(C) 144.4 6.99891 1474.679 213.69 7-145
Solution :
yA P yBP yCP
From equation (5-18); xA + xB + xC = + o + o =1
p oA pB pC
(0.20)(760) (0.30)(760) (0.50)(760)
= + +
p oA p oB p oC
152 228 380

= + o + o
p oA pB pC
Solution is by trial & error : Assume td =110 oC
log p oA = 6.90565 −
1211.033
= 3.2446 p oA = 1756.4 mmHg
220.79 + 110
1343.943 p oB = 746.7 mmHg
log p oB = 6.95334 − = 2.8731
219.38 + 110
1474.679
log p oC = 6.99891 − = 2.4431 p oC = 277.4 mmHg
213.69 + 110
152 228 380

xA + xB + xC = + + =1.762 As this is greater than 1, the selected temperature is
1756.4 746.7 277.4
too low.
New assumption : td =132 oC. Then, from Antoine equations; p oA = 2971.1 mmHg ; p oB = 1344.6 mmHg
p oC = 540.8 mmHg are calcualated. Then;
152 228 380
xA + xB + xC = + + = 0.924
2971.1 1344.6 540.8
As the summation is smaller than 1, the assumed temperature is high.
New assumption : td =129 oC. At this temperature, p oA = 2776.4 mmHg ; p oB = 1246.4 mmHg
p oC = 496.2 mmHg are calculated. Then;
152 228 380

xA + xB + xC = + + =1.004
2776.4 1246.4 496.2
a) As this is almost 1, the selected temperature 129 oC is the dew point temperature of the vapor
mixture.
b) The composition of the first liquid droplet formed is :
152 228 380
xA = = 0.055 xB = = 0.183 xC = = 0.766
2776.4 1246.4 496.2
c) The condensation range of the vapor (td - tb) : The vapor starts condensing at 129 oC. As the
condensation proceeds the temperature drops. The condensation temperature of the last vapor bubble
is the bubble point temperature of the liquid, whose composition is equal to the composition of the
vapor at the start.
Then, find the bubble point temperature of the liquid, whose composition is : xA = 0.20 ; xB=0.30 ;
xC=0.50. For this, equation (5-17) is used.
p oA (0.20 p oB (0.30) p oC (0.50)

yA + yB + yC = + + = 1.0
760 760 760
= (2.63 p oA + 3.95 p oB + 6.58 p oC ) *10 −4 =1.0
Assume tb =110 oC, then , p oA = 1756.4 mmHg p B = 746.7 mmHg p oC = 277.4 mmHg
o
Then; yA + yB + yC = [(2.63)(1756.4)+(3.95)(746.7)+(6.58)(277.4)]*10-4 = 0.94

As the summation is less than 1, the assumed temperature is low, but it is rather close to the bubble
point temperature.
New assumption ; tb=113 oC, then ; p A = 1894.6 mmHg ; p B = 812.7 mmHg ; p C = 305.4 mmHg
o o o
yA + yB + yC =[(2.63)(1894.6)+(3.95)(812.7)+(6.58)(305.4)]*10-4 = 1.02
Since this is almost 1, the assumed temperature is the bubble point temperture.
Hence, the condensation range : 129 - 113 oC
5.2.8 Enthalpy-Composition Diagrams: In some distillation operations, the energy

difference between vapor and liquid phases is important and is to be known. Enthalpy-
composition diagrams, which are obtained by plotting saturated liquid and saturated
vapor enthalpies against the compositions, are in this case proved to be very useful.
The specific enthalpy, h (kJ/k-mol) of a liquid solution is given as:
h = cL (t L − t o ) + ∆H s (5-19)
where, ∆Hs (kJ /k-mol solution) is heat of solution at to temperature and at given
concentration, to is reference temperature, tL is the temperature at which enthalpy is
calculated and cL (kJ/k-mol oC) is the molar heat capacity of the solution calculated at
the arithmetic mean of to and tL. If temperature tL equals the bubble point temperature
of the solution, then h is the specific enthalpy of the saturated solution. The heat
capacity of the solution is related to the heat capacities of pure components by
cL = x cLA + (1 − x) cLB (5-20)
Hence, specific enthalpy of the saturated liquid solution can be written as:
h = [ x cLA + (1 − x) cLB ] (tb- to) +∆Hs (5-21)
The sign of ∆Hs is negative, if heat is released during mixing. For ideal solutions,
∆Hs= 0.
The specific enthalpy of a saturated vapor mixture, H is obtained by assuming that
each component of the mixture is separately heated up to the dew point temperature of
the mixture, td where it is vaporized totally and mixed with the other component.
Hence,
H = y [cLA (t d − t o ) + λ A ] + (1 − y) [cLB (t d − t o ) + λ B ] (5-22)
can be written.
A typical enthalpy-composition diagram obtained by plotting equations (5-21) and
(5-22) is shown in Fig.5.9. As it is seen, xy-diagram is also plotted with this diagram.
The lower curve in the diagram shows the specific enthalpies of the saturated liquid
solutions and the upper curve the specific enthalpies of saturated vapor mixtures. Any
point above the saturated vapor enthalpies curve, such as point R represents
superheated vapor, whereas the points below the saturated liquid solution enthalpies
curve such as point K show the cold liquid solutions. The point between two curves
such as point M represents a vapor-liquid mixture, which upon separation, gives a
saturated liquid solution shown by point L and a saturated vapor mixture represented
by point G, which are in equilibrium, and locations of them are found by drawing the
tie-line passing through point M by trial and error with the help of xy-diagram below.
P =cons.
superheated vapor
R saturated vapor
HR
G HG
G1
Specific enthalpies h,H

liquid-vapor
hM M mixture
hL
cold L
liquid
hK K L1 saturated liquid
0 yR x zM xk y x1 y1 1.0
x,y
1.0
y1
L1,G1
y y =x
L,G
y
0
0 x x1 1.0
x
Fig.5.9 A typical enthalpy-composition diagram
Similarly, the saturated vapor mixture G1, which will be in equilibrium with saturated
liquid solution represented by point L1, can easily be found by drawing the tie line
passing through point L1. The vertical distance between two curves gives the energy
required to vaporize the saturated liquid solution totally. Hence, the vertical distances
at x = 0 and x = 1 give the latent heats of vaporization of the pure components B and A
respectively.
An important characteristic of enthalpy-composition diagrams is the application of
graphical addition and subtraction rules along with so-called inverse lever-arm rule.
If a liquid solution given by point K is added to a vapor mixture shown by R, the
resultant mixture is always represented by a point on the straight line (point M) joining
the two original mixtures (graphical addition), and its exact location depends on the
relative amounts of the phases added and is found by applying inverse lever-arm rule
to the line as:
Amount of liquid * length of KM line = Amount of vapor * length of RM line
Since amounts of liquid and vapor are both known, by measuring the length of KR line
and dividing it with the ratio of (amount of liquid/ amount of vapor), point M can
easily be located. Similarly, if a mixture shown by point R is subtracted from a
mixture given by point M, the mixture that will be left behind is always on the
extension and behind the point M of the line joining the two original mixtures
(graphical subtraction). This is shown by point K in the figure. The position of point K
is now found by applying again the inverse lever-arm rule, point K being the support
point. The proof of these can be made as follows:
Total material balance : K+R=M (5-23)
Component A balance : K xk + R yR = M zM (5-24)
Enthalpy balance : K hk + R HR= M hM (5-25)
If M is eliminated between equations (5-23) and (5-24),
K yR − zM
=
R zM − x k
Similarly by eliminating M between equations (5-23) and (5-25)
K H − hM
= R is obtained. From these two equations,
R hM − hk
yR − zM H − hM
= R (5-26)
zM − x k hM − hk
is found. This equation represents a straight line on enthalpy-composition diagram
passing through the points K(xk;hk) , M( zM;hM) and R(yR;HR).
5.3 Methods of Distillation: After seeing liquid-vapor equilibria, now the distillation
methods used in practice can be considered. There are three basic methods of
distillation used in industry, from simple to complicated these are:
- Equilibrium or Flash Distillation
- Simple or Differential Distillation
- Rectification or Fractionation
Let us consider these methods in some details. In the calculations, the solution is
assumed to be consisting of A and B. However, from time to time the multi-
component mixtures are to be considered too.
5.3.1 Equilibrium or Flash Distillation: The simplest of all the three distillation
methods is known as flash or equilibrium distillation. This method is carried out
continuously as a single stage operation in two different ways in practice:
5.3.1.1 Equilibrium or Flash Distillation under Constant Pressure: As shown
schematically in Fig.5.10, the feed liquid, F is continuously pumped through a heat
top product
D, yD, HD, P, t
vapor
vapor-liquid
feed P, t, hF1 separator
partial vaporizer
F, xF, hF, P, tF
liquid liquid-vapor
liquid
qS W, xw, hw, P, t
bottom product
Fig.5.10 Flow diagram of continuous flash distillation under constant pressure
exchanger, where part of it, is vaporized by adjusting the energy qs(kJ/k-mol) given.
The vapor-liquid mixture then passes to a vapor-liquid separator from where vapor is
taken as top and liquid as bottom products, which are in equilibrium with each other.
The top product vapor later may be condensed in a condenser, if it is needed. As heat
exchanger, double-pipe or shell and tube type heat exchanger is used. When the
temperature is high, the partial vaporizer is placed into a direct- fired oven.
A simple cyclone type separator may be used as vapor-liquid separator. It is obvious
that the top product vapor is richer in the MVC than the bottom product, which is a
liquid. For the whole system:
Total material balance : F= D+W (5-27)
MVC balance : FxF = DyD + Wxw (5-28)
Enthalpy balance : FhF + qS = FhF1= DHD + Whw (5-29)
can be written, where F, D and W are the molar flow rates of the feed , top and bottom
products (k-mol/s), xF, yD, xW are the mole fractions of the MVC in the feed, top and
bottom products respectively and, hF, HD and hW show their specific enthalpies (kJ/k-
mol).
If a fractional vaporization is defined by ε ≡ D/F, then with the elimination of W
between equations (5-27) and (5-28) and between equations (5-27) and (5-29),
x − x W (h F − h W ) + q S /F
ε= F = (5-30)
yD − xW HD − hW
is obtained. The left hand side of this equation can also be written as;
1− ε x
yD = − xW + F (5-31)
ε ε
As it is seen, this equation gives the relationship between the compositions of top and
bottom products, another relationship between these two is given by the equilibrium
distribution curve of the system, as these two streams are in equilibrium. Equation
(5-31) is a straight line on xy-diagram and passes through point F(xF;xF) for a fixed є.
Computation of yD and xW is generally made on the graph as the equilibrium
relationship is usually given in graphical form. For that, the line given by equation
(5-31) is drawn on the diagram, which already contains the equilibrium distribution
curve. From the intersection point Q(xW;yD) xW and yD are read. If, in addition, the
enthalpy-composition diagram of the system is available, the heat energy needed for
the operation can easily be calculated as shown in Fig.5.11. For the determination of
temperature of the mixture, the t-xy diagram of the system at operating pressure is also
needed. It is obvious that if the equilibrium distribution curve of the system can be
expressed in functional way such as given by equation (5-14), xW and yD are then
calculated directly from equations (5-14) and (5-31). In any mass transfer operation,
the recovery of the product next to the purities is also important. Hence, percentage
recovery of the MVC into the top product from the feed is calculated from;
DyD y
P.R.= 100 = ε D 100 (5-32)
F xF xF
As it is seen from Fig.5.11, the purity of the top product, which is shown by yD
decreases with increasing fractional vaporization, but the percentage recovery of the
MVC increases.
P =cons. Example-5.6) Flash Distilation at
D
HD Constant Pressure
An aqueous acetone solution, containing
40 mole percent acetone is to be flash
specific enthalpies h,H

distilled at 760 mmHg pressure. Calculate
hF1=hF+qs/F M the compositions of top and bottom
products and percentage recovery of
acetone for the following fractional
hw
W vaporizations: 0.2, 0.4, 0.5, 0.66.
xy-diagram of acetone-water system at
hF F 760 mmHg is given in Table.App.5.1.
0 xw xF yD 1.0 By substituting the xF and є values into

x,y equation(5-31);
1.0
N
For ε =0.20 yD = - 4 xw+ 2
y For ε =0.40 yD = - 1.5 xw+ 1
Q y =x For ε =0.50 yD = - xw+ 0.8
yD
For ε =0.66 yD = - 0.515 xw+ 0.6
F
are obtained. All these lines, when drawn
on xy-diagram, pass through point
F(0.40;0.40). Another points are found as
0 (0.25;1.0), (0.0;1.0), (0.0;0.8),(0.0;0.6) for
0 xw xF 1.0 the first and following lines. With the help
x
of these points, the lines are drawn and
Fig.5.11 Flash distillation at constant pressure from the Q points xw and yD values are
read from the diagram as shown below.
Percentage recoveries are then computed
from equation (5-32). The results are given in the table below.
Vapor-Liquid Equilibrium of Aqueous Acetone at 760 m m Hg

1
0.9
Mole fraction of acetone in vapor,y
ε =0.4
0.8
0.7
ε=0.2 yD= - 4xw + 2
0.6 ε=0.5
0.5 yD= - 1.5xw + 1
ε=0.66
0.4 yD= - xw + 0.8
F
0.3
0.2
yD=- 0.515xw+0.60
0.1
xF
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction of acetone in liquid,x
yD
ε yD xw P.R. = ε .100 = %
xF
0.20 0.80 0.30 40.0
0.40 0.76 0.16 76.0
0.50 0.72 0.075 90.0
0.66 0.58 0.04 95.7
As it is seen, when fractional vaporization is increased, purity of top product decreases but the
percentage recovery of the MVC increases.
5.3.1.2 Flash Distillation by Reducing the Pressure of the Heated Liquid Solution:
In this type of operation as shown in Fig.5.12, the liquid solution, which is heated up
to an elevated temperature in a heat exchanger, is passed through a pressure reducing
valve where flash vaporization takes place. The vapor-liquid mixture is then directed
top product
D, yD, HD, P, t
vapor
P1, tF1 Liquid-vapor

feed He ater hF1 P, t separator
F, xF, hF, P1, tF
liquid liquid
liquid-vapor
pressure reducing liquid

qS valve
W, xw, hw, P, t
bottom product
Fig.5.12 Flow diagram of continuous flash distillation at reducing pressure
to a vapor-liquid separator from where top product as vapor, bottom product as liquid
are withdrawn. This type of operation is more common than the first type of operation
in practice and the name “flash distillation” is more appropriate for this type of
operation than the first type of operation, as the superheated liquid really flashes at the
outlet of the pressure reducing valve. As in this case fractional vaporization є is also
not known, the solution requires trial and error. Next to the enthalpy-composition
diagram, t-xy diagram of the system is also needed. As shown in Fig.5.13, first a
temperature is selected and the composition of top and bottom products, xw, yD are
read from t-xy diagram and from the first term on the right hand side of equation
(5-30) є is calculated. Then these compositions are carried to the enthalpy-composition
diagram and hW, HD and hF1 are read from this diagram; and substituting these values
into the second term on the right hand side of equation (5-30), the є is once more
calculated. If the two є are the same, the selected temperature and the calculations are
correct. If the difference between two є is great, then the calculations are repeated with
the new temperature selections until the є s are almost the same.
As it is seen from the figures, although certain degree of separation is achieved by
using flash distillation, obtaining complete separation and hence pure products is
almost impossible, although the purities are relatively high when the relative volatility
is great. In practice, the flash distillation is generally used to divide the multi-
component feed into two rough products, which are then purified by more
sophisticated distillation techniques. In some cases, working in this way is more
economic than using sophisticated
distillation methods directly.
P =cons.
H-y For multi-component solutions, the
D
HD following equations can be written:
Total material balance:
specific enthalpies h, H
F= D+W (5-27)
hF1=hF+qs/F Component-i balance:
M
FxFi = DyDi + Wxwi (5-33)
hw Enthalpy balance:
W FhF+qs =FhF1= DHD + Whw (5-29)
h-x
hF F xFi = ε yDi + (1-ε) xWi
is obtained from equations (5-27)
xw xF yD 1.0 and (5-33), by noting that ε = D/F.
x,y If the vapor-liquid equilibrium is
given as:
yDi = Ki xWi (5-34)
tB
t-y then,
x Fi
temperature
D
t x Wi = (5-35)
W M ε K i + (1 − ε)
t-x tA
is found. Between equations (5-27)
yD 1.0
and (5-29),
0 xw xF
x,y
hF1 = ε HD + (1-ε) hw (5-36)
Fig.5.13 Flash distillation by pressure reduction
is obtained. This equation can also
be written in terms of latent heat of
vaporization, heat capacities and temperatures as,
c FL t F1 = ε (λ o + cG t) + (1 − ε) c wL t (5-37)
where, reference temperature has been taken zero, λ o (kJ/k-mol) is the latent heat of
vaporization of the mixture at reference temperature, c FL and c wL are the heat
capacities of the liquid feed and bottom product (kJ/k-mol K) and cG is the heat
capacity of vapor mixture (kJ/k-mol K). All the heat capacities are calculated at
average temperatures. Note that temperature tF1 is the temperature of the feed after the
heater. In a flash distillation of a multi-component solution ε, P and xF are known. The
solution is done as follows: a temperature t is selected and the K value for each
component is read from the graph at this temperature and given pressure. Then the
mole fraction of each component in the bottom product is computed from equation
(5-35). If the summation of these mole fractions is one, then the selected temperature
is the temperature of the vapor-liquid mixture after flashing and the mole fraction of
each component in the top product is then calculated from equation (5-34). If the
summation is different than one, with new temperatures the calculations are repeated.
If the flash distillation is conducted by pressure reduction, equation (5-37) must also
be used for the solution, as in this case ε is also unknown. Solution is again started
with a temperature selection. With the help of this temperature first ε is computed
from equation (5-37). Then the K values are read and the mole fractions in the bottom
product are calculated from equation (5-35). If the summation of xwi values gives 1,
then the selected temperature is the temperature of the vapor-liquid mixture after
flashing and the calculations are correct; if not, the calculations are repeated by
selecting new temperatures until this condition is satisfied.
Example-5.7) Flash Distillation by Pressure Reduction
The bottom product from a distillation column is a binary liquid solution of composition 0.5 mole
fraction. It is supplied continuously at 135 oC and 5 bar pressure. Calculate its fractional vaporization
on adiabatic pressure reduction to atmospheric pressure and the compositions of vapor and liquid
products. The latent heat of vaporization at 0 oC is 38 000 kJ/k-mole, molar specific heat of the liquid
feed and bottom product is 250 kJ/k-mole K, the molar specific heat of vapor is 180 kJ/k-mole K and
the relative volatility is 3. The system obeys Raoult’s law and the variation of vapor pressure of the
LVC with temperature is as follows:
t(oC) 60 65 70 75 80 85 90
p oB ( mbar) 280 340 410 486 570 670 780
Top product
(vapor)
D,yD,HD,P,t
Distillation
column c G = 180 kJ / k − mol K
vapor-liquid
P1 =5 bar separator
liquid-
∆ vapor
W,xw,hw,P,t
Bottom product t
(binary) Bottom product c w L = 250 kJ/k - mol K
(liquid)
xF =0.5 P=1.013 bar
tF1=135 oC h
t
c FL = 250 kJ/k - mol K
Pressure reducing
valve
Solution
xF − xW 0.5 - x w
From equation (5-30) ε= = (1)
yD − x W yD − x w
c wL (t F1 − t ) 250(135 − t )
From equation (5-37) ε= = (2)
λ o − (c wL − cG )t 38 000 − (250 − 180) t
For ideal solutions equations (5-3), (5-4) and (5-15) are also valid. Solution is by trial and error.
Select t = 78 oC. Then from the given table p oB = 533 mbar is read.
From equation (5-15) p oA = α p oB = (3)(533 ) =1599 mbar
From equations (5-3) and (5-4) P − p oB 1013 − 533

xw = = = 0.45
p oA − p oB 1599 − 533
pA po 1599
yD = = A xw = (0.45) = 0.71
P P 1013
0.5 - 0.45
Then from equation (1) ε= = 0.192
0.71 − 0.45
250(135 − t ) 250(135 − 78)

From equation (2) ε= = = 0.438
38 000 − (250 − 180) t 38000 − (70)(78)
Since no check is available, selected temperature is not correct.

Select t = 81 oC. From table above, p oB = 590 mbar
P − p oB 1013 − 590
From equations (5-3) and (5-4) xw = = = 0.359
p oA − p oB 1770 − 590
p A p oA 1770
yD = = xw = (0.359) = 0.627
P P 1013
0.5 - 0.359
0.627 − 0.359
250(135 − t ) 250(135 − 81)

38 000 − (250 − 180) t 38000 − (70)(81)
So, t is between 79 and 81 oC. Select t = 80 oC. From table above p oB = 570 mbar
P − p oB 1013 − 570
From equations (5-3) and (5-4) xw = = = 0.389
p oA − p oB 1710 − 570
p A p oA 1710
yD = = xw = (0.389) = 0.657
P P 1013
0.5 - 0.389
0.657 − 0.389
250(135 − t ) 250(135 − 80)
38 000 − (250 − 180) t 38000 − (70)(80)
Since two є are almost equal, trial and error is stopped. Hence flash temperature is 80 oC,
fractional vaporization є =(0.414+0.424)/2= 0.419, mole fractions of the MVC in the vapor and
liquid are 0.657 and 0.389.
5.3.2 Simple or Differential Distillation: Simple distillation, which is a single-stage

operation, is conducted batch-wise. The equipment, which is named as batch-still,
consists mainly of a boiler and a condenser connected to each other as shown in
Fig.5.14. The boiler of batch-still is a fairly large vessel containing heating coils
through which heating medium is circulated. Vessel is charged with liquid solution up
to 70-75 % of its volume and then heating medium is set to circulation. When the
temperature of the solution reaches its bubble point temperature, vaporization starts
and the vapor formed rises through the pipe connecting boiler and condenser and upon
condensing there the liquid, which is called top product, flows into a receiver. By
adjusting the heat energy in the boiler, slow and constant rate vaporization is achieved,
which results in attaining equilibrium at any time between rising vapor and remaining
liquid during the operation. Since the vapor formed is always richer in the MVC than
the remaining liquid, liquid becomes poorer in the MVC as the distillation proceeds.
As a result of this, the forming vapor steadily becomes poorer also in the MVC. It
follows from this that the vapor formed at the start of the vaporization is the richest
and the vapor formed at the end of vaporization is the poorest in the MVC. The
operation is stopped when the amount of liquid in the vessel or its composition drops
Condenser
Cooling
medim
Vapor Top product
Charge
Heating Boiler
Receiver
medium
Bottoms
Fig.5.14 Batch-still
to a predetermined value. Then, heating is stopped and the vessel content is discharged
(bottom product) and the vessel is now ready for a new charge with fresh batch of
solution. It is important to note that during the operation although the rising vapor is
always in equilibrium with the remaining liquid, the liquid, which is collected in the
receiver (top product) at the end of operation, is not in equilibrium with the bottom
product. As the composition of the vapor steadily changes, using more than one
receiver and hence collecting more than one top product, which are named as cuts are
also possible. It is obvious that the cut collected in the first receiver will be richer in
the MVC than the cuts collected in the subsequent receivers. The analysis of simple
distillation was first made by Rayleigh as follows: Suppose that the liquid charged to
the vessel consists of A and B and quantity of the initial charge is F k-mole and the
mole fraction of the MVC in this charge is xF, and at the end of operation W k-mole
liquid is left in the vessel whose composition is xw. Consider the MVC balance at any
moment during the vaporization, at which quantity of liquid in the vessel, is L k-mole,
the mole fraction of the MVC in this liquid is x, the amount of vapor rising is dL k-
mole and its composition is y*,
y* dL = d (L x) (5-38)
Where (*) shows that the rising vapor is in equilibrium with the remaining liquid,
whose composition is x. Then;
y* dL = L dx + x dL
dL (y*-x) = L dx
F xF
⌠ dL ⌠ dx
⎮ = ⎮ ∗
⌡ L ⌡y − x
W xw
xF
F ⌠ dx
and finally, ln = ⎮ ∗ (5-39)
W ⌡y − x
xw
is obtained. With the help of this equation, any one of the F, W, xF and xw variables, of
which any three are known at the start of the operation, can be calculated. It is obvious
that in order to perform the integral, y* must be expressed in terms of x. In most of the
cases this relationship, which is equilibrium relationship of the system, is given in
graphical form and hence, the solution of the problem is then accomplished by
graphical integration. For that, as shown in Fig.5.15, y* values at arbitrarily selected x
values, which are between xF and xw, are read from the equilibrium diagram and then
the calculated 1/( y*-x) values are carried against the corresponding x values on a mill
metric paper. The area under the curve between the limits of xw and xF gives the value
of the integral. If the relationship between y* and x can be expressed in functional way,
the integration can be conducted directly. For example, when the relative volatility of
the system is constant, y* can be substituted from equation (5-14) and upon
integration,
F 1 x (1 − x w ) 1− xw
ln = ln F + ln (5-40)
W α −1 x w (1 − x F ) 1− xF
1.0
P =cons.
1
y ∗
y −x F
y =x Area= ln
y W
0 0
1.0 0 xw xF
x
0 x
x
Fig.5.15 Graphical integration
or
F xF F (1 − x F )
ln = α ln (5-41)
W xw W (1 − x w )
is obtained.
In addition to these equations,,
Total material balance : F = D+W (5-42)
MVC balance : F xF = D xD,av. + W xw (5-43)
can also be written from which the average composition of the top product
(composited composition), xD,av. can be computed.
Percentage recovery of the MVC is given as,
D x D,av.
P.R. = 100 (5-44)
F xF
If the solution is a multi-component ideal solution, one of the components (let’s say
component j) is selected as key component and the relative volatilities are defined to
this component. Hence, αij shows the relative volatility of component i to the
component j. In this case equation (5-41) is written as,
F x Fi F x Fj
ln = α ij ln (5-45)
W x wi W x wj
If this equation is to be used to compute the composition of the bottom product, it
must be solved simultaneously with the equation below by trial and error,
n
∑x
1
wi =1 (5-46)
The heat energy requirement in the simple distillation can be calculated from,
q T = q S + q L = F cFL (t − t F ) + D λ (5-47)
where, qT (kJ) is the total heat energy required, qS (kJ) is the sensible heat needed to
bring the solution from initial temperature tF (oC) to the average distillation
temperature t (oC), qL (kJ) is the latent heat required to distill D k-mol distillate, c FL
( kJ/k-mol oC), is the molar heat capacity of the solution calculated at the arithmetic
mean of t and tF, and λ (kJ/k-mol) is the latent heat of vaporization of the mixture
calculated at the mean boiling point temperature.
The time for one batch operation can be calculated by adding the heating (sensible heat
transfer) and distillation (latent heat transfer) times to the time required for charging
and discharging the batch-still.
Heating of the solution from initial temperature tF to the average distillation
temperature t is an unsteady-state operation and the time needed is given by,
⎡t − t ⎤
ln ⎢ H F ⎥
t −t ⎦
θS = ⎣ H (sec) (5-48)
UA / FcFL
for isothermal heating fluid such as saturated steam at tH (oC) temperature, and by
⎡t − t ⎤
ln ⎢ H1 F ⎥
θS = ⎣ t H1 − t ⎦ (sec) (5-49)
m& HcH ⎛ K − 1 ⎞
⎜ ⎟
FcFL ⎝ K ⎠
for non-isothermal heating fluid whose inlet temperature is tH1. K is given by
UA
K = e m& c . In the equations above, m
H H
& H (kg/s), and cH (kJ/kg oC) are the mass flow
rate and mass specific heat of heating fluid, A is the heat transfer area in the batch-still
(m2) and U is the overall heat transfer coefficient (kW/m2 oC).
For the distillation time,
qL
θL = (sec) (5-50)
U b A( t H − t ) ln
can be used. Where, Ub is the overall heat transfer coefficient of boiling solution
(kW/m2 oC).
Then, total time for one batch operation;
θBT = θS + θL + θCD (sec) (5-51)
where, θCD is the time (sec) for charging and discharging the batch-still.
Although a better separation is achieved in the simple distillation than the flash
distillation operating at the same conditions, a complete separation is still not possible.
However, high relative volatility may give high purity top products as shown in the
examples below.
Example-5.8) Simple Distillation
123.1 k-mole acetone-water solution at 20 oC and containing 20 mole percent acetone will be distilled
in a batch still at 760 mmHg. Distillation will be stopped when the mole fraction of acetone in the
batch still drops to 0.04.
Calculate:
a) The amount of distillate to be produced,
b) The mole fraction of acetone in the distillate (purity),
c) The percentage recovery of acetone,
d) Estimate the time of one batch operation for the conditions: Heat transfer area in the still is A =10
m2, heating is supplied by the saturated steam condensing inside the tubes of the still at 1.05 bar gauge
pressure. Over-all heat transfer coeffients for the heating and vaporization periods are estimated as
U=200 W/m2K and Ub= 1 000 W/m2K.
e) If the same fractional vaporization is realized in a single stage by flash distillation at the same
pressure, what will be the purity and percentage recovery of acetone?
Molar specific heat of the solution at mean temperature is 83 kJ/k-mol oC, and molar latent heat of
vaporizations for acetone and water at 71.4 oC are 28 880 kJ/k-mol and 42 000 kJ/k-mol respectively.
Vapor-liquid equilibrium for acetone-water system at 760 mmHg is given in Table.App.5.1.
Solution:
First, plot xy- and t-xy diagrams of the system and then evaluate the integral given by eqn.(5-39) by
selecting arbitrary x values between xF and xW and reading the corresponding y* values as shown in
table below:
select read c a l c u l a t e
1 ⌠
0.20
dx
x y* ∗
y −x ⎮
⌡0.04 y − x
∗
0.04 0.55 1.961 -
0.08 0.71 1.587 [(1.961+1.587)/2]*(0.08-0.04) = 0.07096
0.12 0.742 1.608 [(1.587+1.608)/2]*(0.12-0.08) = 0.0639
0.16 0.765 1.653 [(1.608+1.653)/2]*(0.16-0.12) = 0.06522
0.20 0.780 1.724 [(1.653+1.724)/2]*(0.20-0.16) = 0.06754
(The value of integral) Total = 0.2676
0.20
F ⌠ dx 123.1 0.2676
ln =⎮ = 0.2676 =e = 1.307 W = 94.19 k-mol
W ⌡0.04 y − x
∗
W
a) From equation (5-42), D = 123.1 - 94.19 = 28.91 k-mol
b) From equation (5-43), (123.1)(0.20) = (28.91) xD,av + (94.19)(0.04) xD,av = 0.721
Dx D ,av (28.91)(0.721)
c) From equation (5-44), P.R. = .100 = .100 = 84.7 %
Fx F (123.1)(0.20)
d) As it is seen from the t-xy diagram of the system, distillation starts at 64.8 oC and ends at 78 oC.
Then, take the mean temperature 71.4 oC as the distillation temperature.
From equation (5-47), the sensible heat required, qS = (123.1)(83)(71.4 - 20) = 525 170 kJ
As λ = (28 880)(0.721) +( 42 000)(1 - 0.721) = 32 540 kJ/k-mol,
The latent heat required, qL = (28.91)(32 483) = 940 732 kJ
From equation (5-48), the time required to heat the solution from 20 oC to 71.4 oC ;
ln[(121 − 20) / (121 − 71.4)]

θS = = 3 997 sec . ≈ 1 h 07 min
(0.200)(10) / (135.41)(83)
Vapor-Liquid Equilibrium of Aqueous
Acetone at 760 mmHg t-xy diagram of Aqueous Acetone at 760
mmHg
1
0.9 100
tem perat ure,t (o C)

0.8
0.7 90
0.6
y
0.5 80
0.4 70
0.3
0.2 60
0.1
0 50
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x Mole fraction of acetone, x,y
To account for heating of the batch-still itself (metal), F is taken as (1.1)(123.1) =135.41 k-mol .
From steam tables, temperature of the saturated steam at Ps=1.05+1.013 = 2.063 bar absolute pressure
is read as tH =121 oC.
From equation (5-50), the time required for distillation;
940 732
θL = = 1 897 sec ≈ 32 min
(1.0)(10)(121 − 71.4)
So, from equation (5- 51); the time required for one batch operation, with 1 h charging and
discharging time;
θBT = 1 h 07 min + 32 min + 1 h = 2 h 39 min
e) Fractional vaporization, ε = 28.91 = 0.235

123.1
Then, from equation (5-31) y D = − 1 − 0.235 x W + 0.20
0.235 0.235
y D = − 3.26 x W + 0.85
is obtained. By drawing this line on
xy-diagram, and reading the coordinates of point Q ; yD = 0.67, xw = 0.065 are obtained.
(0.67)
From equation (5-32) P.R. = (0.235) .100 = 78.7 %
(0.20)
As it is seen, simple distillation gives higher purity and higher P.R. than the flash distillation under
identical operation conditions.
Example-5.9) Simple Distillation: Effect of Relative Volatility on Purity
123.1 k-mole (12 000 kg) chloroform-toluene solution at 20 oC and containing 20 mole percent
chloroform will be distilled in a batch still at 760 mmHg. Distillation will be stopped when the mole
fraction of chloroform in the batch still drops to 0.04.
Calculate:
b) The mole fraction of chloroform in the distillate (purity),
c) The percentage recovery of chloroform,
d) Heat energy requirement for the operation.
e) Estimate the time of one batch operation for the conditions: Heat transfer area in the still is A=10
U=200 W/m2K and Ub= 1 000 W/m2K.
f) Compare the purity of distillate with the Example-5.8 and comment on the results.
Assume that specific heat and latent heat of solution remain constant at 140 kJ/k-mol oC and
32 000 kJ/k-mol. Mchloroform= 119.4 , Mtoluene= 92
Vapor-liquid equilibrium of the system at 760 mmHg is given in Table.App.5.2.
Solution:
a) First, plot xy- and t-xy diagrams of the system and evaluate the integral given by equation (5-39) by
selecting arbitrary x values between xW and xF as in the previous example.
c a l c u l a t e
select read
0.20
1 ⌠ dx
x y* ⎮
∗
⌡0.04 y − x
∗
y −x
0.04 0.155 8.696 -
0.08 0.275 5.128 [(8.696+5.128)/2]*(0.08-0.04) = 0.27648
0.12 0.358 4.202 [(5.128+4.202)/2]*(0.12-0.08) = 0.1866
0.16 0.430 3.704 [(4.202+3.704)/2]*(0.16-0.12) = 0.15812
0.20 0.500 3.333 [(3.704+3.333)/2]*(0.20-0.16) = 0.14074
Total = 0.76194
0.20
F ⌠ dx 123.1 0.76194
ln =⎮ = 0.76194 =e = 2.142 W = 57.47 k-mol
W ⌡0.04 y − x
∗
W
From equation (5-42), D= 123.1 – 57.47 = 65.63 k-mol
b) From equation (5-43), (123.1)(0.20) = (65.63) xD,av + (57.47)(0.04) xD,av = 0. 34
(65.63)(0.34)
c) From equation (5-44), P.R. = .100 = 90.6 %
(123.1)(0.20)
d) It is seen from the t-xy diagram of the system, distillation starts at 94.5 oC and ends at 106.5 oC
Then, take the mean temperature 100.5 oC as the distillation temperature.
From equation (5-47), the sensible heat required, qS = (123.1)(140)(100.5 - 20) = 1 387 337 kJ
The latent heat required, qL= (65.63)(32 000) = 2 100 160 kJ
Total heat required, qT= 3 487 497 kJ
e) From equation (5-48), the time required to heat the solution from 20 oC to 100.5 oC ;
ln[(121 − 20) / (121 − 100.5)]

θS = = 15 116 sec . ≈ 4 h 12 min
(0.200)(10) / (135.41)(140)
To account for heating of the batch-still itself (metal), F is taken as (1.1)(123.1) =135.41 k-mol.
From steam tables, temperature of the saturated steam at Ps=1.05+1.013 = 2.063 bar absolute pressure
is read as tH=121 oC.
From equation (5-50), the time required for distillation;
2 100 160
θL = =10 245 sec ≈ 2 h 51 min
(1.0)(10)(121 − 100.5)
t-xy diagram of chloroform-toluene at 760
mmHg
xy-diagram of chloroform-toluene at 760
tB mmHg
1
0.9
Temperature, t (OC)
0.8
t-y 0.7
0.6
0.5
y
t-x 0.4
tA 0.3
0.2
0.1
0
Mole fraction of chloroform, x,y
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x
So, from equation (5-51); the time required for one batch operation, with 1 h charging and
discharging time;
θBT = 4 h 12 min + 2 h 51 min + 1 h = 8 h 03 min
f) As it is seen, the purity of the top product is much less than the purity of the top product of the
previous example. In order to understand this, look at the relative volatilities of the two systems. From
xy-diagrams of the two systems, the relative volatility of acetone to water and the relative volatility of
chloroform to toluene over the concentration range involved were calculated with the help of equation
(5-13) as follows:
x 0.04 0.08 0.12 0.16 0.20

αAcetone-Water 29.33 28.16 21.09 17.09 14.18
αChloroform-Toluene 4.4 4.36 4.09 3.96 4.0
As it is seen, there is great difference between the relative volatilities of the two system. Flash and
simple distillations can produce high purity top products only when the relative volatility of the
system is great. So, it is obvious from these examples that flash or simple distillation techniques can
not be used to separate solutions such as chloroform -toluene whose relative volatilities are not great.
As will be considered in the next sections, rectification is the only technique to separate such
solutions.
5.3.3 Rectification or Fractionation: None of the above given distillation techniques

produces complete separation of the solution. Another distillation method, which is
known as rectification and which is more complicated and expensive than the previous
ones, must be used for high purity products and high percentage recoveries. For that,
the rectification is the most widely used separation method in chemical industry.The
equipment used is multi-stage column, which may be either packed or plate type.
Although continuous operation is more common, batch-wise operation is not also very
seldom. A typical rectification column is shown in Fig.5.16. Although this column is a
plate column it could also be a packed column. As it is seen, the liquid solution to be
separated (the feed) is introduced centrally to the column. As the liquid flows down, it
comes in contact with rising vapor on the plates where mass transfer between the
phases takes place in both directions. The vapor and liquid contacting on a plate try to
come equilibrium. For that, part of the LVC passes from vapor to liquid by partial
condensation. This enriches the liquid in the LVC and the remaining vapor in the
MVC. The heat of condensation given by the condensing LVC is taken up by the
MVC and part of it vaporizes. While this enriches the liquid in LVC further, the vapor
is also enriched in the MVC further. As a result of these, while the liquid leaving the
plate and flowing to the plate below becomes richer in the LVC than the liquid
entering the plate, the vapor leaving the plate and going to the plate above becomes
richer in the MVC than the vapor incoming the plate. These partial vaporizations and
partial condensations are repeated on
vapor each plate. As a result of these, the
liquid solution flowing down from
qC plate to plate continuously enriches
in the LVC. By providing sufficient
condenser number of the plates (or packing
height) in this region of the column,
1 the liquid reaching bottom of the
Reflux
liquid
column can be made almost pure in
Top
product
the LVC. Part of this liquid is
Enriching
section
vaporized in a reboiler and returned
back to the bottom of the column as
reflux vapor, thus a vapor phase,
Feed which is required for interphase
mass transfer is formed in the
column. Notice that as this vapor is
Stripping formed from a liquid, which is
section almost pure in the LVC, itself is also
almost pure in the LVC. The
remaining part of the liquid is
withdrawn as bottom product. This
N vapor
liquid is the liquid, which is richest
in the LVC in the column. If we
qs follow the vapor given back to the
column; this vapor enriches in the
reboiler MVC as it passes from plate to plate
liquid
up by repeated partial vaporizations
Bottom
product
and condensations taking place on
the plates as explained above. It has
Fig.5.16 A plate rectification column the highest MVC composition at
leaving the plate to which the feed is
introduced (the feed plate).
However, although this vapor is enriched in the MVC considerably, it is not pure in
the MVC, as it still contains some LVC. This vapor must be brought in contact with a
liquid, which is richer in the MVC in order to remove the remaining LVC. This
contact is provided on the plates (or in the packing) placed above the feed plate. As the
rising vapor comes in contact with a liquid which is richer in the MVC on a plate, the
LVC of the vapor passes from vapor to liquid by partial condensation and the MVC of
the liquid passes from liquid to vapor by taking this heat of condensation. By
providing sufficient number of plates (or packing height) above the feed plate, the
vapor leaving the column can be made almost pure in the MVC. The vapor, leaving
the column is directed to a condenser, where it condenses totally and part of the
condensate (liquid) is returned back to
G1,y1,H1 the top of the column as reflux liquid to
provide the liquid phase rich in the MVC
condenser
on the plates above the feed plate. The
qC remaining part of the condensate is
withdrawn as top product or distillate.
If we look at the liquid and vapor phases
1 Lo,xo
flowing inside the column, we see that
ho the vapor, which enters the column at the
L1,x1 G2,y2 D,xD,hD
h1 H2 bottom as almost pure in the LVC, turns
Top to MVC as it rises in the column and
2
product
L2,x2
leaves the column as almost pure in the
G3,y3
h2 H3 MVC at the top. The liquid, which is
given at the top of the column as almost
Ln-1,xn-1 Gn,yn pure in the MVC, turns to the LVC as it
hn-1 Hn flows down and with joining the feed at
n the feed plate leaves the column at the
Ln,xn
bottom as almost pure in the LVC. As it
Gn+1,yn+1
hn Hn+1 is seen, all the streams leaving the
column at the top and bottom are not
taken as products, but parts of them, after
Feed
phase changes, are returned back to the
F,zF,hF column as reflux. If this is not done,
production of pure products is not
possible. The liquids in the column are
m
always at their bubble point temperatures
Lm,xm Gm+1,ym+1 and the vapors are at their dew point
hm Hm+1 temperatures. Hence, the lowest
temperature in the column is always at
the top and the highest temperature is at
N the bottom. As it is seen, the feed divides
the column in two sections. The section
LN,xN GN+1,yN+1
hN HN+1 below and including the feed plate is
named as stripping section of the
reboiler column as in this section the rising vapor
qS strips off the MVC from the liquid. The
section above the feed plate is known as
Bottom enriching section of the column as the
product
vapor in this section is further enriched in
W,xw,hw the MVC.
The purities of the top and bottom
Fig.5.17 Notations in a continuously operating
products do not only depend on the
plate rectification column
number of the plates in each section but
also on the ratio of liquid to vapor in each section. Typical rectification system as
shown in Figure does not consist only of the column, but it contains also a reboiler and
a condenser as inseparable part of the system. In many applications, in order to reduce
the heating cost, a heat exchanger between bottom (sometimes top) product and the
feed is placed. The coolers, which cool the products to storage temperatures, are
frequently added to the product lines.
The column itself and all the hot lines are insulated against the heat losses. The
column, which is the main part of the system may be plate or packed column. Below,
first the design principles of a plate rectification column will be given.
5.3.3.1 Continuous Rectification in a Plate Column: The first step in the design of a
plate rectification column is to determine the numbers of the plates required in
enriching and stripping sections. All the plates in the column are first assumed as ideal
or equilibrium or theoretical plates, as in gas absorption, although they are not, and
then numbers of the ideal plates required in each section are computed. By using plate
or column efficiencies, numbers of the theoretical plates are then converted to the
numbers of the real plates. The plates are numbered from top to the bottom and n and
m show any plate in the enriching and stripping section respectively. N is the last plate
of the column. L and G are the total molar flow rates of the liquid and vapor phases
respectively as k-mol/s. x and y show the mole fraction of the MVC in liquid and
vapor. Since these change from plate to plate, the number of the plate from which
these streams come, is given as subscript. Hence, L5, y4 and H7 show the liquid leaving
the 5th plate, mole fraction of the MVC in the vapor leaving the 4th plate and the
specific enthalpy of the vapor leaving the 7th plate respectively. F, D and W are the
molar flow rates of the feed, top and bottom products and zF, xD and xw are the mole
fraction of the MVC in the feed, top and bottom products and hF, hD and hw are the
specific enthalpies of the feed, top and bottom products respectively.
The total and MVC balances and the enthalpy balance equations around the plate n at
steady-state are written as,
Total material balance :
Gn+1 + Ln-1 = Gn + Ln (5-52)
MVC balance :
Gn+1 yn+1 + Ln-1 xn-1= Gn yn + Ln xn (5-53)
Enthalpy balance :
Gn+1 Hn+1+ Ln-1 hn-1 = Gn Hn+ Ln hn (5-54)
where, Hn+1 and hn are the specific enthalpies of the saturated vapor and saturated
liquid. From equations (5-21) and (5-22),
Hn+1 = y n+1 cLA (t n +1 − t o ) + (1 − y n +1 ) cLB (t n+1 − t o ) + y n+1 λ A + (1 − y n+1 ) λ B
h n = x n cLA (t n − t o ) + (1 − x n ) cLB (t n − t o ) + ∆H s
can be written. In many cases, t n ≅ t n+1 and λ A , λ B > ∆ Hs and hence ∆ Hs can be
neglected and then by subtracting the second equation from the first,
H n +1 − h n = y n+1 λ A + (1 − y n+1 ) λ B (5-55)
is obtained. It is known that the molar (not the mass) latent heats of vaporization of
some liquids are almost equal. Then λA ≈ λB(= λ ) and it follows from equation (5-55)
Hn+1-hn = λ = constant
This means that the heat liberated upon the condensation of 1 mole of vapor on a plate
is just enough to vaporize only 1 mole of liquid. It follows from here that Gn+1= Gn and
from equation (5-52) Ln-1 = Ln . Hence, if the molar latent heats of vaporization of the
components forming the solution are almost equal (a deviation up to 25% is assumed
equal from engineering calculations point of view) the molar (not the mass) flow rates
of liquid and vapor remain constant throughout, provided that there is no stream
entering and leaving the column in the section considered. In this special case, which
is known as “constant molar over-flow case” the subscripts are not needed to be used
and hence with G and L in the enriching section and with G and L in the stripping
section the molar flow rates of vapor and liquid can be shown. As a stream (the feed)
is added to the column in somewhere, the flow rates of vapor and liquid are not
expected to be the same in the enriching and stripping sections. The calculation of the
number of the ideal plates (and also the height of packing) is simplified considerably
when constant molar over-flow case applies, as in this case the knowing of xy-diagram
of the system at the operating conditions is sufficient. On the contrary, if constant
molar over-flow case does not apply, enthalpy-concentration diagram next to the xy-
diagram is also needed as in this case flow rates of vapor and liquid, even expressed in
molar units, do not remain constant and change from plate to plate. Below,
rectification under constant molar over-flow is to be first considered.
Rectification under Constant Molar Over-Flow: At steady-state, the following
equations between top and any plate of the enriching section (envelope-1) of the
column, as shown schematically in Fig.5.18, can be written:
Total material balance : G=L+D (5-56)
MVC balance : G yn+1 = L xn + D xD (5-57)
The last equation can also be written as:
L D xD
y n+1 = xn + (5-58)
G G
This equation relates the compositions of the liquid leaving and the vapor entering the
same numbered plate. Hence, this equation is nothing but operating line equation. As
this equation was written in the enriching section then the equation (5-58) is the
enriching section operating line equation. It is represented by a straight line passing
through point D(xD;xD) on xy-diagram. In any rectification operation, the ratio of
liquid rate given back to column at the top to the rate of top product, which is known
as reflux ratio and shown by RD , is the most important operating parameter. The
equation (5-58) is then preferred written in terms of reflux ratio. By dividing both
nominator and denominator of equation (5-58) by D and by noting that RD = L/D,
RD xD
y n+1 = xn + (5-59)
1+ RD 1+ RD
is obtained. This equation is represented by a straight line passing through point
D(xD;xD) with a slope of RD/(1+RD) on xy-diagram.
Similarly, in the stripping section of the column between any plate and bottom of the
column (envelope-2);
G,y1 Total material balance :
L= G + W (5-60)
Envelope-1 qC MVC balance :
L x m = G y m+1 + W x w (5-61)
are written. The last equation can
also be written as,
1 L W xw
LG L,xo
y m+1 = xm − (5-62)
2 D,xD G G
This equation gives the relationship
n between vapor entering and liquid
xn yn+1 leaving the same numbered plate.
Hence, it is an operating line
F,zF equation. Since it was written in the
L G stripping section, it is then stripping
section operating line equation.
m Envelope-2
This line cuts the diagonal at point
xm ym+1 W(xw;xw). For the whole column; the
following equations can also be
N G yN+1 written:
Total material balance
qS
:F = D + W (5-63)
MVC balance
L xN
F zF = D xD + W xw (5-64)
and percentage recovery of the MVC
W,xw
D xD
: P.R. = .100 (5-65)
F zF
Fig.5.18 Constant molar over-flow rectification
Let us now find the intersection
point of the two operating lines,
which is given as Q(xq;yq). Since this point lies both on enriching and stripping section
operating lines, the coordinates of this point must satisfy the equations (5-57) and (5-
61). Hence,
G yq = L x q + D x D
G yq = L x q − W x w
are written. By subtracting the second from the first,
(G − G) y q = (L − L) x q + D x D + W x w (5-66)
is obtained. If the value of D xD + W xw is substituted from equation (5-64) and then
both sides of the equation is divided by F:
⎛G − G ⎞ ⎛L − L⎞
⎜ ⎟ yq = ⎜ ⎟ x + zF (5-67) L G
⎝ F ⎠ ⎝ F ⎠ q
is found. On the other hand, total material balance around F
the feed plate is written as F + L + G = L + G . By rearranging
L G
this equation,
⎛L − L⎞ ⎛G − G⎞
⎜ ⎟=⎜ ⎟+1 (5-68)
⎝ F ⎠ ⎝ F ⎠
is obtained. Upon substitution of (G − G) /F from this equation into equation (5-67),
⎡ ⎛ L − L ⎞⎤ ⎛L − L⎞
⎢1 − ⎜⎝ F ⎟⎠⎥ y q = ⎜⎝ F ⎟⎠ x q + z F (5-69)
⎣ ⎦
is found. If a q-parameter is defined by
L−L
q≡ (5-70)
F
finally, equation (5-71) is obtained from equations (5-69) and (5-70)
q zF
yq = xq − (5-71)
q −1 q −1
This equation, which is known as q-line equation, is represented by a straight line
passing through point F(zF;zF) with a slope of q/(q-1) on xy-diagram. Since the two
operating lines cut each other always on this line, equation (5-71) is then the locus of
intersection points of the two operating lines. For the drawing of q-line, the q-
parameter defined by equation (5-70) must be known. It follows from equation (5-70)
that the value of q-parameter depends on the thermal condition of the feed. The feed
may be introduced to the column in one of the 5 thermal conditions. These are: a) Cold
liquid; as in this case the feed is below its saturation temperature, it causes to the
condensation of the part of the vapor coming from stripping section on the feed plate
in order to become saturated liquid. The change of quantities of vapor and liquid
phases around the feed plate is schematically shown in Fig.5.19 a, from which q > 1 is
seen. An equation for the calculation of exact value of q, which will be greater than 1,
L G L G L G
F F F
L G L G L G
(a) (b) (c)
L L G
G
F F
L G L G
(d) (e)
Fig.5.19 The change of quantities of vapor and liquid around the feed plate according to
the thermal conditions of feed
can easily be derived by considering enthalpy balance around the feed plate as will be
done later. b) Saturated liquid : since the feed is saturated liquid solution, it simply
joins the liquid coming from the enriching section of the column as shown in Fig.5.19
b, and q in this case equals to 1. c) A mixture of vapor-liquid: in this case vapor part of
the feed joins the vapor coming from stripping section and liquid part joins the liquid
coming from the enriching section as shown in Fig. 5.19 c. q-parameter, which is
0 <q <1, is simply the mole fraction of the liquid in the feed mixture. d) Saturated
vapor: as the feed is saturated vapor, it joins the vapor coming from stripping section
as shown in Fig.5.19 d and the value of q-parameter equals to zero. e) Super-heated
vapor: in this case the super-heatedness of the feed vapor is given up to the liquid
coming from the enriching section on the feed plate and as a result of this, part of the
liquid vaporizes as shown in Fig.5.19 e and the value of q is smaller than zero.
The appearances of the q-lines on xy-diagram at these 5 different thermal conditions of
the feed are schematically shown in Fig.5.20.
An enthalpy balance around the feed plate gives,
L,hL G,HG
Fh F + Lh L + GH G = Lh L + GH G (5-72)
Assuming h L ≅ h L and H G ≅ H G this becomes
F,hF
Fh F + H G (G − G) = h L (L − L) L, h L G, H G
By dividing both sides of this equation with F and
substituting the values from equations (5-68) and
(5-70) finally,
HG − h F H − hF
q= = G (5-73)
HG − h L λ
is obtained. This equation is another definition of q-parameter in terms of enthalpies.
Since HG and hL are the enthalpies of saturated vapor and liquid, the difference
between them is simply latent heat of vaporization.
For the cold liquid feed, H G − h F = cFL (t Fb − t F ) + λ can be written, where tF and tFb
are the entering and bubble point temperatures of the feed and cFL is the molar heat
capacity of the feed liquid, calculated at the arithmetic mean of tF and tFb. By
substituting this into equation (5-73),
c (t − t )
q = 1 + FL Fb F (5-74)
λ
is obtained.
For superheated vapor feed, H G − h F = c FG ( t Fd − t F ) can be written, where, tF and tFd
are the entering and the dew point temperatures of the feed vapor and c FG is the molar
heat capacity of the feed vapor calculated at arithmetic mean of tF and tFd . By entering
this into equation (5-73),
c (t − t )
q = FG Fd F (5-75)
λ
is found.
After seeing the operating and q-lines, we can now start with the calculation of the
1.0 P=cons. q>1

q=1
0<q<1 (b) y=x
y (a)
(c)
q= 0 (d)
F
(e)
q< 0
0
0 zF x 1.0
Fig.5.20 The appearances of q-lines on xy-diagram
number of the ideal plates required for a given separation. But before this, let us write
the knowns. They are: F, zF, thermal condition of the feed, xD and xw (or percentage
recovery of the MVC). The designer then selects the operating pressure and obtains the
xy-diagram of the system at this pressure. The designer also decides on the reflux ratio
to be used in the operation by considering the criteria, which will be given later. Of
course, he must also check whether the constant molar over-flow case applies or not
by obtaining the latent heats of vaporization of the components at the operating
conditions.
Plate to Plate Calculation Method or Lewis-Sorel Method: First xy-diagram of the
system is plotted at the operating pressure, and then q-line is drawn on the same
diagram after calculating the q value from the thermal condition of the feed. The
operating lines for stripping and enriching section are then written by substituting the
known values into equations (5-59) and (5-62) and by drawing the enriching section
operating line on the same diagram point Q hence xq is found. The calculations are
now started at the top of the column. Since the condenser is a total condenser (there
are cases where condenser operates as partial condenser, this case will be dealt with
later), y1 = xo = xD. Hence, the composition of the vapor y1 leaving the first plate is
known then the composition of the liquid x1 leaving the same plate is read from
equilibrium curve by entering this y1 into the diagram. Now by substituting this x1 into
enriching section operating line equation y2, the composition of the vapor leaving the
second ideal plate is computed. Returning back to the equilibrium curve x2 is read
from the diagram by entering the y2 value. After reading each x value from the
equilibrium diagram, it is compared with the known xq to check whether the feed plate
is reached or not. If the last calculated x value is equal to or smaller than xq then for
the calculation of y values the stripping section operating line equation is used instead
of enriching section operating line equation, as we have entered the stripping section
of the column. Calculation is continued in the stripping section in the same way as in
the enriching section; once using equilibrium curve and once using operating line
equation, but this time comparing the calculated x values with the given xw. When the
last calculated x value is equal to or smaller than xw, the calculation is stopped as we
have reached the bottom of the column and the subscript on the last x value gives the
total number of the ideal plates that must be in the column to achieve the specified
separation.
Graphical Calculation Method or McCabe-Thiele Method: In the calculation of the

number of the ideal plates by plate to plate calculation method, equilibrium curve and
operating lines are alternately used, starting at the top of the column. McCabe and
Thiele, seeing this, have drawn the operating lines on the diagram on which
equilibrium curve and q-line had already been plotted, and then they have drawn the
right angle triangles between equilibrium curve and operating lines starting at the top
conditions of the column as shown in Fig.5.21. Each triangle represents an ideal plate
in the column, as the compositions around which are the compositions around each
ideal plate. Around q-line a switch from enriching section operating line to the
stripping section operating line is done. The numbers of the right angle triangles above
and below q-line give the required numbers of the ideal plates in enriching and
stripping sections.
1.0
y1 P=cons.
1
y2 D
2
y y3 q-line y=x
3
y4
4
y5
5
Enric.sec.op.line
y6 Q
K 6
F
y7
xD 7
1+ RD Strip.sec.op.line
y8
8
0 W
0 xw x7 x6 x5 x4 zF x3 x2 x1 xD=xo 1.0
x8
x
Fig.5.21 Determination of number of ideal plates by McCabe-Thiele method
The Importance of Reflux Ratio: It was stated above that the reflux ratio is an
important operating parameter, and the designer does its selection. Let us consider the
effect of reflux ratio on the number of the ideal plates. It follows from Fig.5.21 that if
the reflux ratio is decreased keeping everything else constant, the operating lines
approach the equilibrium curve and as a result of this, more right angle triangles are
drawn between them. This means that more ideal plates are needed to make the same
separation than before. It is understood from this that the number of the ideal plates is
inversely proportional to the reflux ratio. If the reflux ratio is further decreased as
shown in Fig.5.22a, point Q further approaches the equilibrium curve, finally coming
on to it (point Q'). In other words, the two operating lines and the q-line cut each other
on the equilibrium curve. Construction of right angle triangles starting at the top
conditions results in a pinch at or around the Q' point showing that number of the
triangles, hence the ideal plates is infinite at this reflux ratio which is named as
minimum reflux ratio and shown by RDm. So, the minimum reflux ratio is defined as
the reflux ratio at which desired separation can only be done in a column containing
infinite number of the ideal plates. In some systems, the enriching section operating
line may cut the equilibrium curve before cutting the q-line as shown in Fig.5.22b. In
this case, the tangent drawn from point D is taken as enriching section operating line at
minimum reflux condition. The minimum reflux ratio depends on the thermal
1.0 P=cons. 1.0 P=cons.

q-line
y D y q-line T D
'
Q
y′q
K' Q
Enr.sec.op.line at y′q Q' Enr.sec.op.line at
min. reflux ratio min. reflux ratio
Q K'
y=x y=x
xD xD F
F
1 + R Dm 1 + R Dm
Strip.sec.op.line at Strip.sec.op.line at
min.reflux ratio min.reflux ratio
0 W 0 W
0 xw x′q zF xD 1.0 0 xw x ′q zF xD 1.0
x x
(b)
(a)
Fig.5.22 Determination of minimum reflux ratio
condition of the feed for a given system. It is obvious that reflux ratios greater than
minimum reflux ratio are to be selected by the designer. In practice operating reflux
ratio, which is always greater than minimum reflux ratio, is given in terms of
minimum reflux ratio in the form of RD= β RDm. The value of β, which is always
greater than 1, is selected with economic considerations as will be explained later.
At minimum reflux ratio, the enriching section operating line is written as,
R Dm xD
y n+1 = xn + (5-76)
1 + R Dm 1 + R Dm
Hence, it can easily be calculated either by equating the slope of DQ' line (for Fig.5.22
b the slope of tangent) to RDm/(1+RDm) or equating its intercept value (point K') to
xD/(1+RDm). From the first,
x D − y′q
R Dm = (5-77)
y′q − x ′q
is obtained.
Underwood has derived a series of analytical equations from which minimum reflux
ratio can be computed without resorting to drawing. He first found the coordinates of
the intersection point of enriching section operating line and q-line at minimum reflux
conditions as,
x (q − 1) + z F (1 + R Dm ) q x D + R Dm z F
x ′q = D y′q =
q + R Dm R Dm + q
then he substituted these coordinates into the definition equation of relative volatility
y′q /(1 − y′q )
written at point Q' which is α = and obtained the following equation,
x ′q /(1 − x ′q )
R Dm z F + q x D α [x D (q − 1) + z F (R Dm + 1)]
= (5-78)
R Dm (1 − z F ) + q(1 − x D ) (R Dm + 1) (1 − z F ) + (q − 1) (1 − x D )
RDm can be computed from this equation only by trial and error for a given value of q.
However, equation (5-78) simplifies to the following equations for
1 ⎡ xD α (1 − x D ) ⎤
R Dm = −
α − 1 ⎢⎣ z F (1 − z F ) ⎥⎦
q =1 (5-79)
1 ⎛α xD 1− xD ⎞
q =0 R Dm = ⎜ − ⎟ (5-80)
α − 1 ⎝ zF 1 − zF ⎠
The α in the equations must be taken at the intersection point (point Q') of the two
operating lines.
Let us consider now another limit of reflux ratio, which is known as total reflux. The
reflux ratio, which is defined by RD = L/D becomes infinite at D = 0. When no top
product is withdrawn from the column, no bottom product must be withdrawn and
hence no feed is introduced. Hence, certain quantity of solution charged to the column
is vaporized in the reboiler and then condensed in the condenser and returned back to
the column. In this type of operation, which is known as operation under total reflux,
the slopes of both operating lines become 1 and hence the diagonal between points D
and W becomes operating line, as no feed is introduced to the column only one
operating line exists. As shown in Fig.5.23, the number of the ideal plates needed for a
given separation is a minimum under total reflux. It is obvious that operation under
total reflux cannot be a normal operation, but the columns operate under total reflux
for a certain time to reach the steady-state, when they are first taken in operation, after
which is passed to normal operation slowly. The operation time under total reflux
depends on both the size of the column and the system.
Fenske has derived an analytical equation for the calculation of the number of the
ideal plates under total reflux, when the relative volatility is constant or near constant.
From the definition equation of relative volatility for the last plate of the column,
yN xN
=α (5-81)
1− yN 1− xN
can be written. But at total reflux yN = xN-1 and then this equation becomes;
x N−1 xN
=α (5-82)
1 − x N−1 1− xN
1.0
P=cons. 1 D
2
y
3
y =x
F
4
5
0 W
0 xw zF xD 1.0
x
Fig.5.23 Determination of ideal plates under total reflux
Similar equation for the plate (N-1) is,

y N−1 x N−1 xN
=α = α2 (5-83)
1 − y N−1 1 − x N−1 1− xN
If similar equations are written for the other plates until reaching the first plate,
y1 xN
= αN (5-84)
1 − y1 1− xN
is obtained. For a column equipped with a total condenser y1 = xD, and if the bottom
product is taken from the last plate of the column, xN = xw. Then, equation (5-84)
becomes,
xD xw
= αN (5-85)
1− xD 1− xw
By taking the logarithm of both sides and solving for N,
x (1 − x w )
log D
x w (1 − x D )
Nm = (5-86)
log α
is finally obtained. As in this case the required ideal plate number is minimum, N = Nm
is written. If relative volatility changes along the column, but if this change is not
great, geometric mean of the α values calculated at the top and at the bottom of the
column is used in the equation above.
Optimum Reflux Ratio: The total cost of separation by rectification is the sum of the
fixed capital cost of the system and the operating cost, as in many other engineering
operations. The fixed capital cost of the system consists mainly of the costs of column,
reboiler, condenser, coolers and other heat exchangers and the pumps. The column
cost, which is probably the greatest of all, is proportional to the diameter and the
height (or number of the plates) of the column. Since at RD=RDm the column cost is
infinite (why?), the fixed capital cost is also infinite. With increasing RD, the cost of
column decreases due to the drop in the height, and hence the fixed capital cost of the
system also decreases. Although with increasing RD the sizes and hence the costs of
reboiler and condenser increase (why?), these are much offset by the savings in the
column cost due to the sharp drop in the height of the column at RDs near the RDm. But
after certain value of RD, this tendency reverses and the fixed capital cost of the system
increases with increasing RD. This can be explained as follows: At RDs which are
fairly greater than RDm, drop in the height of column, although exists, is not
significant, but increase in the diameter is rather high due to the increased vapor and
liquid flows in the column, and as a result of this the cost of column increases with
increasing RD in this region. Not only this, but the costs of reboiler and condenser rise
also due to the increase vapor loads. Hence fixed capital cost of the system increases
with increasing RD in this region as shown qualitatively in Fig.5.24. As for the
operating cost, this cost arises when the system operates. The operating cost in a
rectification operation consists mainly of the costs of heating and cooling duties (or
loads) of reboiler and condenser which are given by qs = G λ and qc = G λ respectively.
As it is seen, these costs are directly proportional to the vapor flow rates in the column.
Total cost
Operating cost
Annual cost, YTL
min.
Fixed capital cost
RD
RDm (RD)op
Fig.5.24 Determination of optimum reflux ratio
A material balance around the condenser gives G = D(1+RD), which shows that cost of
condenser load increases with increasing RD. On the other hand, since for a saturated
liquid feed G = G = D(1 + R D ) can be written, the cost of reboiler duty also increases
with RD. It follows from here that operating cost increases always with reflux ratio as
shown in Fig.5.24. The total cost is obtained by adding these two costs as shown in
Fig.5.24. The minimum of this total cost curve gives the optimum value of the reflux
ratio. The optimum reflux ratio does not only change from system to system but also
from time to time for a system. The best example of the change with time was lived at
the petrol crisis in 1973. Suddenly soaring petrol prices brought the RDopvalues much
nearer to the RDm.values almost overnight. Many operating plants then tried to balance
the sharply rising operating cost by adding more plates to their columns and operating
them under reflux ratios, which are much closer to the minimum reflux ratios than
before. For many systems the optimum reflux ratio lies somewhere around 1.25RDm
Optimum Feed Plate: The plate to which feed is introduced is known as feed plate
and it is the first plate of the stripping section. As shown in Fig.5.25, in the drawing of
right angle triangles, which represent the
1.0
P =cons. plates, starting from point D it cannot be
q-line E D passed from enriching section operating line
to the stripping section operating line before
y point E. Similarly, it must be passed from
Q y=x
enriching section operating line to the
R stripping section operating line at last at point
F R. So, it follows from this that from one
operating line to the other can be passed at
anywhere between E and R. The best passing
0 W point is the point at which the number of the
0 xw zF xD 1.0 ideal plates needed for a given separation is a
x
minimum. If it is noticed the figure, it is seen
Fig.5.25 Optimum feed plate that the maximum enrichments in the vapor
phases (hence maximum mass transfer
between the phases) occur on the plates, which are close to the intersection point of
two operating lines. It follows from this that minimum number of the plates is
obtained, if the switch from enriching section operating line to the stripping section
operating line is done at or near the intersection point (point Q), although the column
operates at any feed introduction point between points E and R. So, the optimum feed
plate is at or near the intersection point, Q. In the feed plate, the feed and the vapor
and liquid coming from stripping and enriching sections mix together and adjust
themselves to the new conditions. Hence, the enrichment that will be obtained on the
feed plate is usually ignored as design safety and one additional ideal plate is added to
the number of the ideal plates calculated for stripping section. Notice the locations of
feed introduction nozzles in the column for cases of liquid, vapor or mixture of vapor-
liquid feed. For possible changes in the feed plate location that might occur in future
due to the changes in the composition and/or in the thermal condition of the feed,
opening of additional introduction nozzles during the construction stage of the column
and closing them with blind-flanges are strongly advised (why?).
Condensers: The vapor leaving the column must be condensed. Condensation is
carried out in a shell and tube type heat exchanger usually located outside the column.
Vapor coming from the column is condensed either in the tubes or in the shell
depending upon the conditions. The cooling medium is then circulated in the shell in
the first case or in the tubes in the latter case.
In some cases, shell and tube condenser is placed inside the column vertically as
shown in Fig.5.26a. In this type of condenser, liquid returns back as the vapor rises
through the tubes and hence, flooding of the condenser must be prevented by
observing the following equation in the design of the condenser:
[u 0.5
G L ρ L ] < 0.6 [g d i (ρ L − ρ G )]
ρ G0.25 + u 0.5 0.25 0.25
(5-87)
where, uG and uL are the velocities of vapor and liquid in the tubes as m/s, based on
empty cross sectional area of the tubes, ρG and ρL are the densities of vapor and liquid
Vent Top product
Condenser
Condenser
Cooling liquid
Cooling
liquid
Receiver
Reflux liquid
1.plate
Column Column
Top product
1.plate ( c)
x 1.0
slope=-L/D
(a)
yD D
C
y1 y
Vent
1
Condenser
xD= yD
x1 xo
Cooling liquid Enr sec.op.line
y=x
Receiver
Reflux liquid (d)
1.plate
Top product
Column
(b)
Fig.5.26 Types of condensers : (a) built-in condenser, (b) total condenser, (c) partial
condenser, (d) enrichment in the partial condenser
as kg/m3, di is the inside diameter of the tubes in m. In small capacity systems, the
condenser, which is placed outside the column, must have sufficient elevation to
permit the return of the condensate to the column top under the gravity. If this is not
observed, the condenser is filled with condensate partly or totally and it does not fulfil
the design duty. In large capacity plant, the condenser is located at or near ground
level and the reflux liquid is pumped to the top of the column. Wherever the condenser
is located, only the latent heat of vaporization of the vapor must be removed in it and
hence, the condensate produced must be a saturated liquid. If it is sub-cooled, not only
the cooling medium is wasted but also undue condensation of some vapor on the first
plate occurs. The part of the condensate, which will be taken as top product, is cooled
in a cooler before flowing into storage vessel. In some special cases, only the part of
the vapor, which will be returned back to the column as reflux liquid, is condensed and
remaining part is taken as top product in vapor form. This is resorted to, when the
capacity of the available condenser is not sufficient or the top product is used in vapor
form in a subsequent process. This condenser is then known as partial condenser and if
the partial condensation takes place slowly, the vapor and liquid reach in equilibrium,
as they will remain in contact long time. As in this case partial condenser makes
enrichment equals one ideal plate as shown in Fig.5.26d, the number of the ideal plates
in the enriching section may be decreased one. But, in practice this is not done with the
assumption that the equilibrium will not be attained in the condenser. In the condenser,
usually the cooling water coming from the cooling tower is used as cooling medium.
At low condensation temperatures cooling medium may be chilled water or cooled
ethylene glycol solution. If the condensation temperature is sufficiently high,
atmospheric air can also be used as cooling medium. Condenser load qc(kW); in a
total condenser is calculated from qc=G λ and in a partial condenser from qc=(G-D) λ =
L λ , where λ (kJ/k-mol) is the average latent heat of condensation.
Reboilers: The reboiler, which is an important part of the rectification system, is
essentially a heat exchanger and, depending upon the heat load and the properties of
the liquid solution, in different types are constructed and at different modes are
operated. It is generally placed outside the column as a separate piece of equipment.
But when heat load is low and the fouling is not a problem, it can be located in the
column as shown in Fig.5.27a. For large capacities, kettle-type (b) and vertical thermo-
syphon types (c, d) are widely used. To prevent the fouling of the tubes, thermo-
syphon type reboilers are generally operated on partial vaporization principle; the
mixture issuing from the reboiler comprises both liquid and vapor. For heat sensitive
components, thermo-syphon type reboilers take the liquid from the last plate of the
column. This type is known as once-through type (d). But as in this type of reboilers
heat transfer is by natural convection, when the viscosity of solution is still high at the
operating temperature, over-all heat transfer coefficient becomes rather low. In order
to increase the heat transfer coefficient, a pump between the column and reboiler is
installed and this reboiler is then called as forced circulation reboiler.
As in the kettle-type reboiler, vaporization is slow and low, the vapor formed reaches
in equilibrium with the liquid in the reboiler and then reboiler becomes equivalent to
one ideal plate. Hence, the number of the ideal plates in the stripping section can be
decreased one. However, in practice this is taken as design safety and plate number is
not reduced in the stripping section. The diameter of kettle-type reboiler must be so
Column Column
last plate last plate
heating medium
∇ Reboiler
heating medium
Reboiler
bottom product
bottom product
(a) (b)
Column Column
last plate last plate
∇ ∇
heating heating
Reboiler
Reboiler
medium medium
bottom product
bottom product
(c) (d)
Fig.5.27 Types of reboilers : (a) built-in reboiler, (b) kettle-type reboiler, (c) thermo-
syphon type reboiler, (d) once-through thermo-syphon type reboiler
chosen that the velocity of vapor at liquid-vapor interface, uG (m/s) satisfies the
following equation;
0.5
⎡ ρ − ρG ⎤
u G < 0.2 ⎢ L ⎥ (5-88)
⎣ ρ G ⎦
Otherwise, excessive liquid entrainment cannot be evaded.
In the reboilers, the following heating media, which are listed in the order of
increasing temperature, can be used: hot water, steam, hot oil and Dowtherm vapor.
The reboiler load or duty, qs ( kW) is calculated from qs = G λ , where λ ( kJ/k-mol)
is the latent heat of vaporization of solution.
Example-5.10) Rectification under Constant Molar Over-flow
A 15 000 kg/h methanol/n-propanol solution at 20 OC, containing 22.3 mass percent methanol will be
rectified in a plate column at 760 mmHg to produce top and bottom products containing 91 mass
percent methanol and 97.8 mass percent n-propanol respectively. A reflux ratio 1.87 times the
minimum reflux ratio is selected for the operation. The column is equipped with a total condenser and
a kettle-type reboiler.
a) Calculate the flow rates of top and bottom products,
b) Write the q-line and the operating line equations for enriching and stripping section of the column.
Calculate :
c) Number of the ideal plates in each section by McCabe - Thiele method,
d) The amounts of methanol and n-propanol transferred between liquid and vapor phases on the 2nd
and 6th ideal plates.
e) Condenser and Reboiler loads.
Vapor-liquid equilibrium of the system at 760 mmHg is given in Table.App.5.3 and some physical
data for the components are given below.
Methanol n-Propanol
Boiling point, b.p. (oC) at 760 mmHg 64.5 97.2
Molecular weight 32 60
Latent heat of vaporization, λ (kJ/kg) at b.p. 1 100 693
Specific heat, cL (kJ/kg oC) at 50 oC 2.70 2.65
Solution :
First, check whether “Constant Molar Over-flow” approximation is applicable

For methanol : λA= (1 100)*(32) = 35 200 kJ/k-mol
For n-propanol : λB = (693)*(60) = 41 580 kJ/k-mol
As the difference is not much, “Constant Molar Over-flow” case is applicable.

a) Then work with molar units,
(15 000 )( 0 . 223 ) (15 000 )(1 − 0 . 223 )
F= + = 298 . 78 k − mol / h
32 60
(0.223 / 32) (0.91 / 32 )

zF = = 0.35 xD = = 0.95
(0.223 / 32) + (1 − 0.223) / 60 (0.91 / 32 ) + (1 − 0.91) / 60
(1 − 0.978) / 32
xw = = 0.04
(1 − 0.978) / 32 + (0.978/ 60)
From equations (5-63) and (5-64),
F(z F − x w ) 298 . 78 ( 0 . 35 − 0 . 04 )
D = = = 101 . 78 k − mol / h
(x D − x w ) ( 0 . 95 − 0 . 04 )
W = 298.78 - 101.78 = 197 k-mol/h
b) To find the thermal condition of the feed, bubble point temperature of the feed (tFb) must be known.
Plot t-xy diagram and read the bubble point temperature of the feed as tFb = 80.5 oC.
As tF= 20 oC , the feed is sub-cooled liquid and for the calculation of q-parameter eqn.(5-74) must be
used. Mean temperature for the cFL is 50 oC.
Then, molar specific heat of the feed and average latent heat of vaporization;
c = (0.35)(2.70)(32) + (1 − 0.35)(2.65)(60) =133.6 kJ / k − mol o C
λFL= (35 200 + 41 580) / 2 = 38 390 kJ / k − mol
(133.6)(80.5 − 20)
q =1+ = 1.21
38 390
Then, from eqn.(5-71);
y q = 5 . 762 x q − 1 . 667
After drawing this line on xy-diagram, point Q' is marked. By joining point D with Q' and extending
the line until cutting y-axis K' = 0.56 is read.
xD 0.95
Then from, −1= R Dm = − 1 = 0.696 minimum reflux ratio is computed.
K′ 0.56
Operating reflux ratio, RD = (1.87)(0.696) = 1.30
t-xy diagram of methanol/n-propanol at 760 mmHg

100
tB
temperatures , t (0C)
90
t-y
80
tFb=80.5 oC
70
t-x
tA
zF=0.35
60
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
mole fraction of methanol in liquid and vapor,x,y
xy-diagram of methanol/n-propanol a t 760 mmHg
1
y1
yq= 5.762 xq + 1.667 1 D
0.9 y2
2
0.8 y3
Q' 3
mole fraction of methanol in vapor,y
0.7 y4
4
y5 Q
0.6
5 y n +1 = 0.565 x n + 0.413
'
K =0.56 y=x
0.5
y6
0.4
6
K=0.413
y7 F
0.3
7
0.2
y8 y m + 1 = 1 . 685 x m − 0 . 0274
8
0.1
y9
x5
W x7 x6 x4 x3 x2 x1
9
y10
0
x90 xw x0.1 zF xD
8 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
mole fraction of methanol in liquid,x
L = D RD= (101.78)(1.30) = 132.3 k-mol/h and G = D(1+RD) = (101.78)(1+1.30) = 234,1 k-mol/h
L = L + qF = 132.3 + (1.21)(298.78) = 493.84 k − mol / h G = L − W = 493.84 − 197 = 296.84 k − mol / h
Then, from eqn.(5-59) enriching section And from eqn.(5-62) stripping section
operating line; operating line;
1.30 0.95 493.84 (197)(0.04)
y n +1 = xn + y m +1 = xm −
1 + 1.30 1 + 1.30 296.84 296.84
y m +1 = 1.664 x m − 0.0266
y n +1 = 0.565 x n + 0.413
c) Mark K = 0.413 on y-axis and by joining it with point D draw the enriching section operating line.
Mark point Q and by joining it with point W draw stripping section operating line. Then, step off the
right angle triangles between equilibrium curve and enriching section operating line starting at point
D, and do the same after point Q between equilibrium curve and stripping section operating line until
reaching point W. Total number of the ideal plates needed is found as 9( a close examination shows
that exact number is 8.5), 3 needed in the enriching section, 6 needed in the stripping section.
Although the reboiler is kettle-type, as design safety provide 6 ideal plates in the stripping section of
the column.
d) 2nd ideal plate is in the enriching section, and the composition of the liquid and vapor phases
entering and leaving this plate are read from the diagram as, x1=0.834 ,x2=0.665 ,y3 =0.79, y2 =0.885.
Then, L (x1 - x2) = (132.2)(0.834-0.665) = 22.34 k-mol methanol/h
Or G (y2 - y3) = (234.1)(0.885-0.79) = 22.24 k-mol methanol/h
As it is seen these are vey close to each other, take the average value 22.29 k-mol methanol/h
In mass units, this makes = (22.29)(32)= 713.3 kg methanol/h
For “ Constant molar over-flow” rectification; on each plate,
“Moles of methanol transferred from liquid to vapor = moles of n-propanol transferred from vapor to
liquid” is valid.
Then, n-propanol transferred from vapor to liquid = 22.29 k-mol/h = (22.29)(60) =1 337.4 kg /h
6th ideal plate is in the stripping section, and x5=0.288 , x6=0.195 , y7 =0.300 , y6 =0.455 are read
from the diagram.
Then , L ( x 5 − x 6 ) = (493.84)(0.288-0.195) = 45.93 k-mol methanol/h
Or, G ( y 6 − y 7 ) = (296.84)(0.455-0.300) = 46.01 k-mol methanol/h.
Take the mean value = 45.97 k-mol methanol/h
As it is seen, transferring quantities (rate of mass transfers) are quite different even on mole basis on
the 2nd and 6th plates. ⎛ 234 . 1 ⎞
e) As the condenser is total condenser; q c = G λ = ⎜⎜ ⎟⎟ (38 390 ) = 2 496.4 kJ/s (=kW)
⎝ 3 600 ⎠
⎛ 296 .84 ⎞
Reboiler load, q S = G λ = ⎜⎜ ⎟⎟ (38 390 ) = 3 165.5 kJ/s (= kW)
L
⎝ 3 600 ⎠
Use of Open Steam: Slightly superheated steam at column pressure may be directly
injected to the bottom of the column eliminating the reboiler, when the bottom product
is water. In this case, although the component balance along the column does not
change, the total material balance changes and becomes,
F + G = D+W (5-89)
as seen from Fig.5.28 a. Here, G is the flow rate of steam as k-mol/s. As yN+1= 0 in
this case, point W lies on the x-axis and the required number of the ideal plates
q-line
y
equilibrium curve
yN-1
Q
N-1 y=x
yN-1 F
xN-1 yN N-1
N
Steam yN strip.sec.op.line
xN N
∇ G , yN+1 =0
yN+1
xw xN-1 zF
Bottom product xN x
W
L , xw =xN
(a) (b)
Fig.5.28 Use of open steam in the column
increases in the stripping section as shown in Fig.5.28 b. This increase is mostly
limited with one ideal plate and hence a certain saving in the fixed capital cost of the
system is obtained as the cost of one ideal plate is generally much smaller than the cost
of reboiler. But use of open steam is much costlier than the use of closed-looped steam
as in the latter case condensed steam is returned back to the boiler house for reuse and,
demineralized water is used for the production of steam. Hence, by comparing the
saving that will be obtained by elimination of reboiler with the cost increase due to the
open steam use, a decision is made whether the use of open steam should be preferred
or not.
Side Streams: In some applications, a product other than the top and bottom products
is also withdrawn from the column, which is usually a liquid product. Although this
application is more common in multi-component rectification, it is also used in some
binary rectifications. Let us show the flow rate of intermediate product with S as k-
mol/s and the mole fraction of the MVC in it with xs as shown in Fig.5.29. As it is
seen, the column is divided in three sections: upper, middle and lower section. In the
middle section, the flow rates of liquid, vapor and any plate are shown with Ls, Gs and
k respectively. By writing the MVC balance between the top of the column and any
plate in the upper section, the operating line equation for the upper section can be
written as,
RD xD
y n+1 = xn + (5-59)
1+ RD 1+ RD
Between any plate in the middle section and top of the column,
Total material balance : Gs = Ls + S + D (5-90)

MVC balance : Gsyk+1 = Lsxk + Sxs + DxD (5-91)
can be written. From the last equation,
L Sx s + Dx D
y k+1 = s x k + (5-92)
Gs Gs
is obtained. This is operating line equation of the middle section of the column and the
Sx + Dx D Sx s + Dx D
coordinates of its intersection with the diagonal is found as U( s ; )
S+ D S+ D
with the help of equation (5-90).
If in this case a qS-parameter is defined by
L −L
qS = S (5-93)
S
qS-line, which is the locus of intersection points of upper and middle section operating
lines is obtained as;
qS x
yq = xq + S (5-94)
S
qS + 1 S
qS + 1
This is a straight line passing through point S(xS;xS). For a saturated liquid side
product, qS = -1 and the qS-line is a vertical line from point S, and for a saturated
vapour side product, qS = 0 and the qS-line is a horizontal line from point S.
In this case q-parameter is defined by,
qC
G L
1 L,xo
Upper section D,xD
Top product
n P=cons.
Side product 1.0
yn+1 xn qs-line
S, xS q-line D
GS LS y
k
Middle section U
yk+1 xk Q
op.line for upp.sec.
Feed S
F,zF K op.line for middle sec.
G L
xD F
m
Lower section 1+ R D op.line for lower sec.
ym+1 xm
N W
G yN+1 0
0 xw zF xs xD
qS x
L xN
Bottom product
W,xw (b)
(a)
Fig.5.29 Withdrawal of side product
L − LS
q= (5-95)
F
and the q-line given by equation (5-71) and passing through point F(zF;zF) is then the
locus of intersection points of middle and lower section operating lines.
The operating line equation of the lower section becomes;
L W xw
y m+1 = xm − (5-62)
G G
Considering the whole column, three more equations as;
Total material balance : F=D+W+S (5-96)

MVC balance : FzF = DxD + WxW + SxS (5-97)
Dx D + Sx S
Percentage recovery of the MVC : P.R. = .100 (5-98)
Fz F
can be written.
The required number of the ideal plates can now be easily obtained by first locating
points F, D, W and S, then drawing qS-, q- and three operating lines as shown in
Fig.5.29b, and finally constructing the right angle triangles between equilibrium curve
and the operating lines starting at point D (For simplicity sake this is not shown in the
Figure).
Example-5.11) Withdrawal of Side Product
An aqueous methanol solution containing 25 mole percent methanol will be rectified in a plate column
equipped with a total condenser, at 760 mmHg to produce a 10 k-mol/h saturated liquid side product
containing 60 mole pecent methanol , a top product containing 95 mole percent methanol and a bottom
product containing 4 mole percent methanol. The feed, which is at 20 oC, will be introduced at a flow
rate of 173 k-mol/h. Operating reflux ratio is selected as 1.235. Assuming constant molar over-flow;
a) Write the operating line equations for each section of the column.
b) Calculate the number of the ideal plates needed and the locations of the feed and side product
Vapor - liquid equilibrium for methanol-water system at 760 mmHg is in Table.App.5.4.
Molar specific heat of the feed at mean temperature and the latent heat of vaporization of the solution
are 76.5 kJ/k-mol oC and 38 000 kJ/k-mol respectively.
Solution :
First, plot t-xy and xy-diagrams as shown below. Read the bubble point temperature of the feed from
t-xy diagram as tFb= 81 oC. Hence the feed is subcooled liquid, then calculate the q-parameter from
eqn.(5-74)
(76.5)(81 − 20)
q =1 + = 1.123
38 000
1.123 0.25
q-line from equation (5-71); yq = xq −
1.123 − 1 1.123 − 1
yq = 9.13 xq – 2.03
From equations (5-94) and (5-95); (173)(0.25) = (0.95)D + (10)(0.60) + (0.04)(173-10-D)

D = 33.77 k-mol/h
W= 173-10-33.77 = 129.23 k-mol/h
L = DRD = (33.77)(1.235) = 41.71 k-mol/h
G = L + D = 41.71 + 33.77 = 75.48 k-mol/h
As side product S is saturated liquid, GS = G = 75.48 k-mol/h
From equation (5-90); LS = 75.48 – 10 - 33.77 = 31.71 k-mol/h
From equation (5-97); L = 31.71 + (1.123)(173) = 225.99 k-mol/h
From equation (5-60); G = L − W = 225.99-129.23 = 96.76 k-mol/h
1.235 0.95
Then, upper section operating line from equation (5-59); y n +1 = xn +
1 + 1.235 1 + 1.235
yn+1 = 0.553 xn+ 0.425
31.71 (10)(0.60) + (33.77)(0.95)

Middle section operating line from equation (5-92); y k +1 = xk +
75.48 75.48
yk+1 = 0.42 xk + 0.505
Temperature (oC)
tFb
zF
Mole fractions of methanol, x,y
t-xy diagram of aqueous methanol solution at 760 mmHg
225.99 (129.23)(0.04)
Lower section operating line from equation (5-62); y m +1 = xm −
96.76 96.76
ym+1 = 2.43 xm - 0.0535

First, mark the points F, W, D, S on xy-diagram. Then, draw q-line and qS-line. By marking K1=0.425
on y-axis and joining it with D, upper section operating line is first drawn and point E is located. Then,
qS-line 1
y q = 9.13 x q − 2.03 2 D
3
mole fraction of methanol in vapor, y
4
5 E
6
7
8 Q S
K2
K1
9
F
10
W xS
xw zF xD
mole fraction of methanol in liquid, x
xy-diagram of aqueous methanol solution at 760 mmHg

by marking K2=0.505 on y-axis and joining it with E, middle section operating line is drawn. Finally,
by joining W with Q, lower section operating line is drawn. Upper section operating line has meaning
between D and E, middle section operating line between E and Q, and lower section operating line
between Q and W. Stepping off the right angle triangles between equilibrium curve and the operating
lines gives the required number of the equilibrium plates, which is found as 10. It follows from the
figure that, feed must be introduced on the 6th , and the side product must be withdrawn from the 4th
ideal plate.
High Purity Products: When the purities of the products are high, the values of xD
and xw are very close to 1.0 and 0.0 respectively, and the calculation of number of the
ideal plates according to McCabe and Thiele method cannot be done accurately near
the points D and W. The equilibrium curves of almost all the systems are linear near
the x =0 and x= 1. Let us show the slopes of these linear parts of the curve with K1 and
K2 at the bottom and top respectively. In this case, drawing of right angle triangles is
started at the feed plate and is continued in both sections until accurate drawings can
be done and numberings are started from the plate above the feed plate for enriching
section and from the feed plate for stripping section. Suppose n and m show the last
drawn plates in enriching and stripping section respectively. After plates n and m, the
numbers of the plates in the remaining parts are calculated from the equations given
below. The enriching section of the column may be considered as an absorption
column for the LVC and hence an equation similar to the equation (4-54) can be
written for the calculation of number of the ideal plates, ne in this part.
⎡ (1 − y n ) − (1 − x o ) / K 2 ⎛ α − 1 ⎞ 1 ⎤
log ⎢ ⎜ ⎟+
⎣ (1 − y1 ) − (1 − x o ) / K 2 ⎝ α ⎠ α ⎥⎦
ne = (5-99)
log α
where, α is absorption factor defined by α = L/K2G, yn is the mole fraction of the

MVC in the vapor leaving the last drawn plate (plate n) in the enriching section.
Number of the total ideal plates in the enriching section then becomes NE = n + ne.
Similarly, since the stripping section of the column works as a stripper (desorber) for
the MVC, an equation similar to equation (4-55) can be written for the calculation of
the number of the ideal plates after plate m in the stripping section of the column.
⎡ x − x w /K 1 ⎤
log ⎢ m (1 − α ) + α ⎥
ms = ⎣ x w − x w /K 1 ⎦ (5-100)
log (1 / α)
where, α = L / GK 1 and xm is the mole fraction of the MVC in the liquid leaving the
last drawn plate (plate m) in the stripping section. The number of the total ideal plates
in the stripping section of the column is then obtained from Ns = m + ms.
Rectification under Varying Over-flow: When the latent heats of vaporization of the
components are not equal and/or the heat of solution is very great, the flow rates of the
phases do not remain constant even expressed in molar units. In this case, the methods
given above cannot be used for the calculation of the number of ideal plates. Enthalpy
balances next to the total and MVC balances are required to compute the flow rates of
vapors and liquids, which change from plate to plate. By considering the plate column
shown in Fig.5.30a, the following equations can be written between any plate (plate n)
in the enriching section and the top of the column (envelope-1):
Total material balance : Gn+1 = Ln + D (5-101)

MVC balance : Gn+1 yn+1 = Ln xn + D xD (5-102)
Enthalpy balance : Gn+1 Hn+1 = Ln hn + D hD + qc (5-103)
If the energy removed per unit mole of top product in the condenser is shown by
QCD=qc/D, the last equation can also be written as;
Gn+1 Hn+1 = Ln hn + D (hD + QCD) (5-104)
Now let us imagine that we subtract the quantity of the liquid leaving plate n from the
quantity of the vapor entering the same plate and show this difference with ∆e then,
Gn+1- Ln = ∆e (5-105)
is written. So-defined ∆e is named as difference flow or total net flow. If equations
(5-101) and (5-105) are compared, it is seen that ∆e = D, hence there is a total net flow
in the enriching section which is in upward direction, constant and equals the flow rate
of the top product. Similarly, if we imagine the subtraction of the quantity of the MVC
in the liquid leaving plate n from the quantity of the MVC in the vapor entering the
same plate we write,
Gn+1yn+1- Lnxn = ∆e x∆e (5-106)
where, x∆e shows the mole fraction of the MVC in the ∆e. By comparing equation 5-
106) with equation (5-102) x∆e= xD is obtained. Hence, it is said that in the enriching
section, there is a net flow of MVC in the upward direction, which is constant and
equals the quantity of the MVC in the top product. Similarly, if the enthalpy of the
liquid leaving plate n is subtracted from the enthalpy of the vapor entering the same
plate,
Gn+1 Hn+1- Ln hn = ∆eh∆e (5-107)
can be written. Where, h∆e is the specific enthalpy of the ∆e. Comparison of this
equation with equation (5-104) gives,
h∆e = hD + QCD (5-108)
Since both hD and QCD are positive h∆e is also positive. Hence, there is an enthalpy net
flow in the enriching section in the upward direction, which is constant and equals the
sum of the enthalpy of the top product and energy removed in the condenser.
In the stripping section, between any plate (plate m) and bottom of the column
(envelope-2);
Total material balance : Lm = Gm+1 + W (5-109)
MVC balance : Lmxm = Gm+1ym+1 + Wxw (5-110)
Enthalpy balance : Lmhm + qs = Gm+1Hm+1 +Whw (5-111)
can be written.
By defining Qsw=qs/W , equation (5-111) becomes,
Lmhm - Gm+1Hm+1 = W (hw- Qsw) (5-112)
Now let us assume that we subtract the quantity of vapor entering the plate m from the
quantity of the liquid leaving the same plate and show this difference with ∆s then,
Lm- Gm+1 = ∆s (5-113)
is written. So-defined ∆s is named as difference flow or total net flow. If equations
(5-109) and (5-113) are compared, it is seen that ∆s = W, hence there is a total net flow
in the stripping section which is in downward direction, constant and equals the flow
rate of the bottom product. Similarly, if we subtract the quantity of the MVC in vapor
entering plate m from the quantity of the MVC in the liquid leaving the same plate we
write,
Lmxm- Gm+1ym+1 = ∆s x∆s (5-114)
where, x∆s shows the mole fraction of the MVC in the ∆s. By comparing equation
(5-110) with equation (5-114) x∆s= xw is obtained. Hence, it is said that in the stripping
section, there is a net flow of MVC in the downward direction, which is constant and
equals the quantity of the MVC in the bottom product. Similarly, if the enthalpy of the
vapor entering plate m is subtracted from the enthalpy of the liquid leaving the same
plate,
Lmhm - Gm+1Hm+1 = ∆sh∆s (5-115)
can be written. Where, h∆s, is the specific enthalpy of ∆s stream. If this equation is
compared with equation (5-112),
h∆s = hw – Qsw (5-116)
is obtained. Both Qsw and hw are positive and since Qsw is always greater than hw, h∆s
is then always negative. Hence, in the stripping section, there is a constant enthalpy
net flow in upward direction equals in magnitude the value, which is obtained from the
subtraction of enthalpy removed by bottom product from the energy given in the
reboiler.
Summarizing, in the enriching section of the column total net flow, component net
flow and the enthalpy net flow are all in upward direction. But, in the stripping section
while total net flow and component net flow are in downward direction, the enthalpy
net flow is in upward direction. So, it can be said that in a rectification column, there is
always an enthalpy net flow, which carries the MVC from reboiler to the condenser of
the column.
Now, let us write total material, the MVC and enthalpy balances for the whole column:
Total material balance : F= D+W (5-63)
or : F = ∆e + ∆s (5-117)
MVC balance : F zF = D xD + W xw (5-64)
Enthalpy balance : FhF + qs = DhD + Whw+ qc (5-118)
or : FhF = ∆e h∆e + ∆s h∆s (5-119)
In a rectification operation, the reflux ratio, which is defined as (RD=Lo/D) is an
important operating parameter and the relationship between RD and h∆e must be
known. By writing total material and enthalpy balances around the condenser, this can
be found as follows:
G1 = Lo + D (5-120)
G1H1 = Loho + D hD + qc (5-121)
If the value of G1 is substituted from equation (5-120) into equation (5-121) and the
definitions of RD , QCD and h∆e are remembered then,
h − H1
R D = ∆e (5-122)
H1 − h O
is obtained.
G1,y1,H1
Condenser
qC
Envelope-1
1 Lo,xo Top product

ho
L1,x1 G2,y2 D,xD,hD
h1 H2
2 ∆e
P =cons. h∆e
L2,x2 G3,y3 G6 H-y
G5
h2 H3 G4
Specific enthalpies, H,h

G3
G2
G1
Ln-1,xn-1 Gn,yn 6 H1
hn-1 Hn 5
L6 4
n 3
2 1
Ln,xn Gn+1,yn+1 W h-x

L5
hn Hn+1 L4
L3 L2 L1 D hD
hF F
Feed
xW x5 x4 zF x3 x2 x1 xD=y1
F,zF,hF x6
x,y
h∆s
∆S
m
Lm,xm Gm+1,ym+1 y
hm Hm+1 y=x
Envelope-2
N
0
LN,xN GN+1,yN+1 0 x 1.0
hN HN+1
Reboiler (b)
qS
Bottom product
W,xw,hw
(a)
Fig.5.30 Varying over-flow rectification
With the help of the equations above, the number of the ideal plates required for a
varying over-flow rectification can be calculated by using Ponchon and Savarit
Method, which involves the graphical drawing of the ideal plates on enthalpy-
composition diagram of the system as shown in Fig.5.30 b.
At the start of the design F, zF, hF, xD and xw (or percentage recovery) are known. The
operating pressure and reflux ratio are selected by the designer and then enthalpy-
composition; xy- and t-xy diagrams are obtained at the operating pressure. If the
condenser is a total condenser then y1= xo= xD and ho = hD. Points F, W, D and G1 are
first located on the enthalpy-composition diagram as their compositions and thermal
conditions are all known (remember that all the vapors and liquids leaving the plates
and the top and bottom products are saturated vapors and liquids). Then point ∆e,
which will be on the vertical from x = xD is located by calculating its enthalpy
coordinate h∆e from equation (5-122). H1 and ho, which are required for the calculation
are read from enthalpy-composition diagram. Equation (5-117) indicates that points F,
∆e and ∆s must lie on a straight line. Thus, by joining points ∆e and F and extending it
until cutting the vertical from x = xw, ∆s is located.
Now the drawing of the ideal plates on enthalpy-composition diagram is started. Since
the composition of the vapor leaving the first ideal plate is known, the composition of
the liquid leaving the same plate can be found by carrying the y1 value to the xy-
diagram below. Then, this x1 composition is carried to the enthalpy-composition
diagram and point L1 is located.
The tie line joining G1 and L1 represents the first ideal plate in the column. Equation
(5-105) indicates that L1, G2 and ∆e must lie on the same straight line. In addition, G2
should be on the saturated vapor curve. Thus, L1 joined with ∆e will locate the G2, the
vapor leaving the second ideal plate. Then the composition of the liquid leaving the
second plate, x2 is read from xy-diagram below by carrying the y2 value from diagram
above. With the help of this x2, point L2 is located on enthalpy-composition diagram.
The tie line joining L2 with G2 shows the second ideal plate in the column. G3 is then
easily located by joining L2 and ∆e according to equation (5-105). The calculation is
thus continued by alternate drawing of tie lines and operating lines issuing from point
∆e as explained above. On the left of ∆eF∆s line, ∆e losses its meaning as into the
stripping section of the column is entered. From now on, point ∆s is joined with points
L’s in order to find points G’s. The calculation is continued in the same way until
reaching x = xw. The number of the tie line, which cuts the ∆eF∆s line gives the ideal
plate number to which the feed should be introduced (in Fig.5-30 b this is the 4th ideal
plate). While the number of the tie lines on the right of ∆eF∆s line gives the number of
the ideal plates that must be in the enriching section, the number of the tie lines on the
left of the ∆eF∆s line, including the feed gives the number of the ideal plates in the
stripping section of the column. The lines issuing from ∆e and ∆s points are known as
operating lines. It follows from here that the operating line of each plate is different as
the quantities of both liquid and vapor are different for each plate. The simultaneous
solution of total material, component and enthalpy balances around each plate gives
the quantities of liquid and vapor entering and leaving the plate.
The condenser and reboiler duties are calculated,

From equation (5-108) QCD = qc/D = h∆e- hD (5-123)
and from equation (5-116) Qsw = qs/W = hw- h∆s (5-124)
As it is seen, RD, qc and qs are all interrelated. If any one of these three is specified, the
other two are automatically fixed. If, instead of RD, qc is selected, ∆e is located with
the help of equation (5-123). When qs is selected, then first ∆s is located for which h∆s
is calculated from equation (5-116).
Minimum Reflux Ratio: When a tie line coincides with an operating line during the
drawing, this means that required number of the ideal plates at this reflux ratio is
infinite. Hence, this reflux ratio is known as minimum reflux ratio. To find the
minimum reflux ratio, arbitrary tie lines between points F and D are drawn and
extended until cutting the vertical from x = xD. The tie line, which when extended, cuts
the vertical at the farthest point from the diagram gives ∆em. Hence, by inserting the
ordinate value of this point h∆em into equation (5-122), RDm is found as;
h − H1
R Dm = ∆em (5-125)
H1 − h O
The tie line which gives the minimum reflux ratio is usually the tie line of which
extension passes through point F as shown in Fig.5.31.
Total Reflux: at total reflux no products are withdrawn from the column. Since
RD = ∞ at D = 0, it follows from equation (5-122) that h∆e is also infinite. As a result
of these, both ∆e and ∆s go to infinity. Hence, determination of the number of the ideal
plates under total reflux, which is a minimum, by drawing on enthalpy-composition
diagram is done as shown in Fig.5.32. As it is seen from the figure, the operating lines
in this case are parallel to ordinate.
∆em h∆em P=cons.
P=cons.
H-y H-y ∆e ∞
4
3
2
W
h-x 1
W
9
3
h-x D
D
h∆sm
∆sm ∆s - ∞
0 xw zF xD 1.0 0 xw xD 1.0
x,y x,y
1.0 1.0
y
y
y=x y=x
0 0
0 1.0 0 1.0
x x
Fig..5.31 Determination of Minimum Reflux Ratio Fig.5.32 Number of Ideal Plates at Total Reflux
Partial Condenser: if the condenser is a partial condenser and the reflux liquid and
the top product vapor reach in equilibrium, the condenser then makes an enrichment
which is equivalent to one ideal plate as shown in Fig.5.33. Since in this case, top
product D is a saturated vapor, point D lies on saturated vapor curve and then its
∆e
h∆e
H-y
G1
G1,y1,H1 H1
D
HD
qC C
1
D,yD,HD h-x
L1
Top product Lo
L,xo,ho x1 xo y1 yD 1.0
x,y
1
x 1.0
1.0
slope=-Lo/D
yD
C D
y1 y
1
(a) Equilibrium
curve xD= yD
x1 xo
enr.sec.op.line
y=x
(b)
Fig.5.33 Partial condenser
specific enthalpy is shown by HD. Hence, the enthalpy coordinate of point ∆e is then
given by h∆e = HD+QCD.
Use of Open Steam: when the bottom product of the column is water, slightly
superheated steam at column pressure can be directly injected to the bottom of the
column eliminating the use of reboiler. In this case for the whole column;
Total material balance : F + GN+1 = D + W (5-126)
MVC balance : F zF + GN+1(0) = D xD + W xw (5-127)
Enthalpy balance : F hF + GN+1 HN+1 = D hD + qc + W hw (5-128)
can be written. Similarly, for the stripping section of the column;
specific enth.,H,h
GN+1 P=cons.
GN
GN-1
N H-y
∆e
N-1
GN-1 hN=hw
LN=W LN-1 L
N-1 N-2 h-x
GN h∆S
LN-1 ∆S F
N 0 zF x,y
Steam
LN GN+1
∇ yN+1=0
y
N-1
y=x
Bottom
product N
strip.sec.op.line
LN=W E
xN=xw yN+1=0
hN=hw 0 xw x∆S
xN x
(a) (b)
Fig.5.34 Use of open steam
Total material balance : LN- GN+1 = W- GN+1 = ∆s (5-129)

MVC balance : LNxN- GN+1(0) = Wxw- GN+1(0) = ∆sx∆s (5-130)
Enthalpy balance : LNhN- GN+1HN+1 = Whw- GN+1HN+1 = ∆sh∆s (5-131)
are written.
First points F, D, W, G1 and GN+1 are located on enthalpy-composition diagram. Then
with the help of known RD, point ∆e is located. Then the points GN+1 and W and points
∆e and F are joined and extended. The intersection point of these two lines gives point
∆s. Then starting at point G1, the ideal plates are drawn in the known way. In Fig.5.34
b, only the last two plates of the column are shown. The quantity of open steam GN+1
required is calculated from the equations above by first reading the value of x∆s from
the diagram above.
Example-5.12 Rectification under Varying Over-flow
Aqueous ammonia solution containing 25 mass percent ammonia will be rectified in a plate column at
10 bars pressure to produce a top and a bottom product with 95 and 4 mass percent ammmonia. The
feed, which is saturated liquid, will be supplied at a flow rate of 5 500 kg/h. The reflux ratio to be used
is 0.758. The column is equipped with a total condenser and kettle-type reboiler.
Calculate:
a) Flow rates of top and bottom products and P.R. of ammonia,
b) Number of the ideal plates needed,
c) Total net flow, ammonia net flow and enthalpy net flow in each section,
d) Flow rates and composition of each stream entering and leaving the plates,
e) Condenser and reboiler duty
Enthalpy-composition data of the system at 10 bars are given in Table.App.5.12.
Solution:
First plot enthalpy-composition and xy-diagram of the system.
a) From equations(5-63) and (5-64)

z − xw 0.25 − 0.04
D=F F = (5 500) = 1 269.2 kg / h W= 5 500-1269.2 = 4 230.8 kg/h
xD − xw 0.95 − 0.04
(1269.2)(0.95)
From equation (5-65) P.R. = .100 = 87.7 %
(5500)(0.25)
b) From enthalpy-composition diagram λA= 1 200*17 = 20 400 kJ/k-mol and λB= 2 000*18
= 36 000 kJ/k-mol are found. So, varying over-flow case applies. Then, calculation can be conducted
in mass units.
From the diagram hD=ho= 280 kJ/kg and H1= 1600 kJ/kg are read. Hence from equation(5-122)
h∆e= 1 600 + 0.758(1 600-280)= 2 600 kJ/kg is calculated. With the help of this point ∆e is located. By
joinin this with point F and exdending the line point ∆s is located. Then, starting at point G1 tie lines
and operating lines are drawn as outlined above. Number of the ideal plates needed is found as 4, and
the feed must be introduced on the second plate. Allthough kettle reboiler makes a separation equal to
one ideal plate, for design safety 4 ideal plates are recommended for the column.
c) From the diagram, hw = 720 kJ/kg and h∆S = - 320 kJ/kg are read.
Total net flow in the enriching section : ∆e = D = 1 269.2 kg/h
Total net flow in the stripping section : ∆s = W = 4 230.8 kg/h
Ammonia net flow in the enriching section : ∆ex∆e=DxD=(1 269.2)(0.95) = 1 205.7 kg NH3/h
Ammonia net flow in the stripping section : ∆sx∆s=Wxw=(4 230.8)(0.04) = 169.2 kg NH3/h
Enthalpy net flow in the enriching section : ∆h∆e = (1 269.2/3 600)(2 600) = 916.6 kJ/s
Enthalpy net flow in the stripping section : ∆sh∆s= (4 230.8/3 600)(-320) = - 376.1 kJ/s
d) Lo=D RD= (1269.2)(0.758) =962.1 kg/h, G1 = 962.1 + 1269.2 = 2 231.3 kg/h

From the graph, x1= 0.445 and y2 = 0.83 are read.Then, from G2-L1=1269.2 and
0.83G2-0.445L1 =1205.7, L1 = 395.5 kg/h and G2 = 1 664.7 kg/h are calculated.
From the graph, x2=0.195 and y3=0.615 are read. Then, from L2-G3 = 4230.8 and
0.195L2-0.615G3 =169.2, L2= 5 792.2kg/h and G3= 1 561.4 kg/h are found.
From the graph, x3=0.09 and y4=0.22 are read. Then, from L3-G4= 4230.8 and
0.09L3-0.22G4=169.2, L3= 5 858.3 kg/h and G4= 1 627.5 kg/h are found.
e) Condenser duty, qc = D(h∆e-hD) = (1 269.2/3 600)(2 600-280) = 817.9 kJ/s

Reboiler duty, qs = W(hw-h∆s) = (4 230.8/3 600)[720-(-320)] = 1 222.2 kJ/s
Empirical Correlations for Estimating Number of Ideal Plates: First Gilliland later
Erbar and Maddox have given empirical correlations for quick estimate of the number
of the ideal plates for a given continuous rectification. Both empirical correlations as
shown in Fig. 5.35 and Fig.5.36 require only minimum reflux ratio and minimum
number of the ideal plates at total reflux. For quick estimate of the required number of
the ideal plates from these figures, minimum reflux ratio may be obtained from
Underwood equation and the minimum number of the ideal plates from Fenske
equation.
Enthalpy-concentration diagramofofammonia-water
Enthalpy-composition diagram ammonia-water at bars
at 10 10 bars
Mass fraction of ammonia, x,y

mol fraction of ammonia,x,y
2 3200
1.9 2800
G4 ∆e
h∆e
specific enthalpy of solution, H ,h (kJ/kg solution)

1.8 G3 2400
1.7 G2 2000
4 G1
H1600
1.6 1
3
1.5 1200
2 1
L4
1.4 W 800
hw
L2
1.3 L3 400
F hD
D
xw L1
1.2 0
zF xD
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
h
1.1∆s ∆S -400
1 -800
0.9 -1200
0.8 -1600
in vapor,
r,y y
0.7 -2000
monia in vapo
ammonia
0.6 -2400
0.5 -2800
ct ion ofofam
fraction
0.4 -3200
molfra
0.3 -3600
Mass
0.2 -4000
0.1 -4400
0 -4800
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mass fraction
molfraction of ammonia
of ammonia in liquid, x
in liquid,x
Fig.5.35 Gilliland correlation
Fig.5.36 Erbar - Maddox correlation
Example-5.13) Estimation of Number of Ideal Plates from Empirical Correlations
Estimate the number of the ideal plates needed for the Example-5.10 from;
a) Gilliland correlation,
b) Erbar-Maddox correlation.
Compare the results with the result of Example-5.10.
Solution:
From xy-diagram, at Q' x ′q = 0.415 , y′q = 0.73 are read. Then relative volatility at this point, from
equation (5-13) : α = 0.73(1-0.415)/[0.415(1-0.73)] = 3.81
RDm is calculated from Underwood equation [equation (5-78)] by trial and error,
Try RDm= 0.696;
(0.696)(0.35) + (1.21)(0.95) 3.81[0.95(1.21 − 1) + 0.35(0.696 + 1)]
=
(0.696)(1 − 0.35) + (1.21)(1 − 0.95) (0.696 + 1)(1 − 0.35) + (1.21 − 1)(1 − 0.95)
2.716 ≈ 2.715
So, the assumed RDm is correct.
For the calculation of number of the ideal plates at total reflux from Fenske equation average α is
needed. At the top of the column, y = 0.95 , x = 0.834 , αT = 0.95(1-0.834)/[0.834(1-0.95)] = 3.78
At the bottom of the column, y = 0.12 , x = 0.04 , αB = 0.12(1-0.04)/[0.04(1-0.12)] = 3.27
α AV = α T α B = (3.78)(3.27) = 3.52 , then from equation (5-86),
0.95(1 − 0.04)
log
0.04(1 − 0.95)
Nm = = 4.87
log(3.52)
a) R D − R Dm = 1.30 − 0.696 = 0.263 Then, from Fig.5.35 N − Nm

= 0.4 is read. Finally,
1+ RD 1 + 1.30 N+2
4.87 + 0.8
number of the ideal plates, N= = 9.45 is found. A close look at McCabe-Thiele diagram
1 − 0.4
of Example-5.10 reveals that 8.5 ideal plates are needed. Then Gilliland correlation estimates the
number of the ideal plates about [(9.45-8.5)/8.5]*100 = 11 % higher than the actual value.
b) R Dm = 0.696 = 0.41 and RD

=
1.30
= 0.57 then, from Fig.5.36 Nm/N=0.72 is read.
1 + R Dm 1 + 0.696 1 + R D 1 + 1.30
Finally, number of the ideal plates, N = 4.87/0.72 = 6.76 is found.
As it is seen, the Erbar-Maddox correlation estimates the required number of the ideal plates
about [(6.76-8.5)/8.5]*100 = -20.5 % less than the actual value.
In this particular case, Gilliland correlation gives better result than the Erbar-Maddox correlation.
5.3.3.2 Rectification in Batch Operation: When the quantity of the solution to be

separated is small or products at different purities are required, then the rectification
operation is carried out batch-wise. A plate type batch rectification column is shown in
Fig. 5.37. The volume of boiler is selected such that it takes one batch of solution at
70% fullness. Column operates first under total reflux until the top product reaches the
desired composition, from there on top product is withdrawn. During the operation, no
bottom product is withdrawn. The purity of top product depends on the number of the
plates available in the column and the composition of the liquid in the boiler. The
liquid in the boiler becomes poorer in the MVC as the distillation proceeds; as no feed
is given to the column and as the vapor formed is always richer in the MVC. As a
G,y1
qC
Condenser
Reflux
L G
L,xo 1
D,xD
Top product
n
xn yn+1
Column
Charge N
Boiler
Heating
medium
Bottoms
Fig.5.37 Batch rectification column
result of this, top product becomes also poorer in the MVC as the time passes. If the
purity of the top product is to be kept constant, then the reflux ratio must be increased
steadily in the course of distillation. It follows from here that batch rectification can be
carried out in two different ways: either under constant reflux ratio or under increased
reflux ratio.
As the column consists of only enriching section, there is only one operating line,
which is given as;
RD xD
yn+1= xn + (5-132)
1+ RD 1+ RD
While in operations under constant reflux ratio the slope of this line remains constant
but its intercept changes; in operations under increasing reflux ratio, the slope of the
line changes but the intercept remains constant.
Batch Rectification under Constant Reflux Ratio: In this case, xD continuously
decreases as the reflux ratio is kept constant. A MVC balance at any moment during
the rectification can be written as;
Lx = (dL)xD+(L-dL)(x-dx) (5-133)
Where, L and dL are the quantities of the liquid in the boiler and the vapor rising from
the boiler as k-mole respectively at the time considered, and x and xD are the mole
fraction of the MVC in the boiler liquid and in the rising vapor. If the product (dL)(dx)
is ignored,
dL dx
= (5-134)
L xD − x
is obtained from equation (5-133). If this equation is integrated from the start to the
end of rectification;
xF
F
⌠ dL F ⌠ dx
⎮ = ln = ⎮ (5-135)
⌡L W ⌡ xD − x
W xw
is found. Where, F and W are the quantities of the charge and the bottoms as k-mole,
and xF and xw are the mole fractions of the MVC in the charge and bottoms.
As it is seen, this equation is similar to the Rayleigh equation, but here xD is not the
equilibrium value of x.
Total material and the MVC balances can be written at the end of operation as;
F=D+W (5-136)
FxF = DxD,av. + Wxw (5-137)
Dx D ,av
P.R. = .100 (5-138)
Fx F
With the help of equations (5-135), (5-136) and (5-137), the quantity of top product
and its average composition at the end of operation for which F, xF, RD, xw and N
(number of ideal plates) are known, can be calculated as follows: first the slope of
operating line is calculated from equation (5-132) and a line with this slope is drawn
on xy-diagram. Then starting at point F, the given number of right angle triangles (N)
is drawn between this line and equilibrium curve by shifting the line up and down.
Final line is the operating line at the start of distillation and thus xDi is found. Then
arbitrary xD values, which are smaller than xDi are chosen and parallel lines to the first
operating line from the points having these xD s as abscissa are drawn (each line is an
operating line corresponding to the selected xD). The given numbers of the right angle
triangles are again located between these lines and the equilibrium curve starting this
time at points whose abscissa are the selected xD. With thus found x values, 1/(xD-x)
values are calculated and then x values are carried against calculated 1/(xD-x) values
on a millimetric paper. The area under the curve between the limits of xF and xw gives
the value of integral given by equation (5-135) from which W is then found. Finally,
from equations (5-136) and (5-137) D and xD,av. are computed.
The heat energy required in the operation can be calculated from;
q T = q S + q L = F cFL (t − t F ) + (1 + R D )D λ (5-139)
where, qs (kJ) is the sensible heat needed to heat up the solution from initial
temperature tF (oC) to the average distillation temperature, t (oC) and qL (kJ) is the
latent heat required to produce GT (k-mol) vapor which is given as GT=D(1+RD),
cFL (kJ/k-mol oC) is the molar heat capacity of the solution calculated at the arithmetic
mean of t and tF and λ (kJ/k-mol) is the molar latent heat of vaporization of the
solution calculated at mean temperature.
The time for one batch operation can be calculated by adding the heating (sensible heat
transfer) and distillation (latent heat transfer) times to the time required for charging
and discharging the batch-still.
Heating of the solution from initial temperature tF to the average distillation
temperature t is an unsteady-state operation and the time needed is given by the
equations (5-48) and (5-49).
For the distillation time, equation (5-50) and for the total batch time, equation (5-51)
can be used.
Example-5.14) Batch Rectification under Constant Reflux Ratio
A 12 000 kg chloroform-toluene solution containing 24.6 mass percent chloroform will be rectified in
a plate type batch column, which is equivalent to 3 ideal plates for this system. The solution will be
charged to the still at 20 oC and distillation at a reflux ratio of 3.125 and 760 mmHg will be continued
until the mole fraction of chloroform in the still drops to 0.04.
Calculate :
a) Quantity and average composition of the distillate to be produced,
b) Percentage recovery of chloroform,
c) Heat Energy requirement for the operation.
d) Estimate the time of one batch operation for the conditions: Heat transfer area in the still is A=10
U=200 W/m2K and Ub= 1 000 W/m2K.
Assume that specific heat and latent heat of solution remain constat at 140 kJ/k-mol oC and 32 000
kJ/k-mol. Mchloroform= 119.4 , Mtoluene= 92
Vapor-liquid equilibrium of the system at 760 mmHg is given in Table.App.5.2.
Solution :
a) First, plot t-xy and xy-diagrams of the system.

0.246
xF = 119 .4 = 0.20
0.246 (1 − 0.246)
+
119.4 92
F = (12 000)(0.246) / 119.4 + (12 000)(1 − 0.246) / 92 = 123.1 k − mol
Calculate the slope of operating line from eqn.(5-132),
R D 3 . 125
= = 0 . 758
1+ R D 1 + 3 . 125
Draw a line with this slope on xy-diagram and locate 3 right angle triangles between this line and
equilibrium curve, starting at point F(0.20;0.20), by shifting this line up and down. This line is the
operating line at the start of the distillation and xDi is read from the diagram. Select an arbitrary xD
value and draw the operating line from this xD value and starting at this point locate 3 right angle
triangles and then read the corresponding x value. Repeat this step untill reaching or exceding the xW.
In the figure below only initial and final operating lines are shown.
xD x 1 ⌠
0 . 20
dx
xD − x ⎮
⌡ 0 . 04 D − x
x
0.90 0.20 1.429
0.80 0.12 1.471 0.5(1.429+1.471)(0.20-0.12) = 0.116

0.70 0.085 1.626 0.5(1.471+1.626)(0.12-0.085) = 0.0542
0.50 0.05 2.222 0.5(1.626+2.222)(0.085-0.05) = 0.06734
0.40 0.04 2.778 0.5(2.222+2.778)(0.05-0.04) = 0.025
Total = 0.2625
Then, from equation (5-135);
F F 123.1
ln = 0.2625 = e 0.2625 = 1.30 W= = 94.69 k − mol
W W 1.30
t-xy diagram of chloroform-toluene at 760 mmHg
tB
tf = 106.5
ti = 94.5
t-y
Temperature, t (OC)
t-x
tA
xW = 0.04 xF=0.20 Mole fraction of chloroform, x,y
xy-diagram of chloroform-toluene at 760 mmHg

Mole fraction of chloroform in vapor, y
Di
Df
Operating lines
xF=0.20 xDf =0.40 xDi=0.90
xW=0.04 Mole fraction of chloroform in liquid,x
Then from equation (5-136); D = F- W = 123.1- 94.69 = 28.41 k-mol
From equation.(5-137) ; (123.1)(0.20) = (28.41)xD,av+ (94.69(0.04)
xD,av= 0.733
(28.41)(0.733)
b) From equation (5-138) ; P.R. = .100 = 84.6 %
(123.1)(0.20)
c) From equation (5-139) ; Sensible heat required = F c FL (t − t F )
The average boiling point temperature of solution t can be calculated from; t=(ti +tf)/2
From t-xy diagram of the system, ti = 94.5 oC, tf =106.5 oC are read.
Sensible heat required = (123.1)(140)( 100.5- 20) = 1 387 337 kJ
Latent heat required = (1 + R D ) D λ = (1+ 3.125)(28.41)(32 000) = 3 750 120 kJ
Total heat required = 1 387 337+ 3 750 120 = 5 137 457 kJ
d) Heating of solution from 20 oC to 100.5 oC is an unsteady-state operation and the time needed is
calculated from equation (5-48).
To account for heating of the batch-still itself (metal) , take F= (1.1)(123.1) =135.41 k-mol.
From the steam tables, temperature of the saturated steam at Ps=1.05+1 =2.05 bar absolute pressure is
read as ts=121 oC.
ln[(121 − 20) / (121 − 100.5)]
θS = = 15 116 sec . ≈ 4 h 12 min
(0.200)(10) / (135.41)(140)
For the calculation of distillation time, equation (5-50) is used:
(1.1)(3 750 120)
θL = = 20 122 sec ≈ 5 h 36 min
(1.0)(10)(121 − 100.5)
By considering additional 1 h time for charging the feed to the still and discharging the bottom product
from the still at the end of operation, total batch time is found as ;
θBT = 1 h + 4 h 12 min + 5 h 36 min = 10 h 48 min.
Batch Rectification at Constant Top Product Composition: As was said before, if

the composition of the top product is to be kept constant, the reflux ratio must be
increased steadily. In this type of operation, generally N, F, xF, xD and xw (or
percentage recovery) are known. First D and W are calculated from equations (5-136)
and (5-137). Then from point D whose abscissa is xD, an arbitrary line towards F is
drawn and until the N right angle triangles are located between equilibrium curve and
this line between the limits of xD and xF,, the slope of this line is changed. The line
satisfying this is the operating line corresponding to the initial reflux ratio. From its
slope or intercept the initial reflux ratio, RDi is calculated. Then from the same D,
another line but in this case with greater slope is drawn and the slope of this line again
is changed until the given number of the right angle triangles is located between
equilibrium curve and this line between the limits of xD and xw. The reflux ratio, RDf
calculated from the slope of this line gives the reflux ratio at which the operation will
be stopped. It is obvious that the reflux ratio will be increased continuously from the
initial value to the last value.
The heat energy requirement in this case is calculated from;
q T = q S + q L = F cFL (t − t F ) + G T λ (5-140)
GT (k-mol) which is the total amount of vapor to be formed, can be calculated as
follows;
Total material and the MVC balances at any time θ during the rectification can be
written as;
F = Dθ + L (5-141)
FxF = Dθ xD + Lx (5-142)
Where, Dθ is the quantity of top product collected until this time. By eliminating L
between the two equations,
⎡x − x⎤
Dθ = F ⎢ F ⎥ (5-143)
⎣ D
x − x ⎦
is obtained.
G T = ∫0 dG θ = ∫0 (1 + R D ) dD θ
GT D
Then, (5-144)
This equation may be written in different ways, for example with the help of equation
(5-143), or noting that 1 + R D = 1 /[1 − ( L / G )] ;
⌠ 1+ RD
xF xF
⌠ dx
G T = F( x D − x F )⎮ dx = F( x D − x F )⎮ (5-145)
⌡x ( x D − x ) ⌡x [1 − (L / G )]( x D − x )
2 2
W W
The evaluation of GT may be done as follows: from point D arbitrary operating lines
for reflux ratios between RDi and RDf are drawn and then the given number of right
angle triangles are located between the equilibrium curve and the operating lines. By
substituting the x values read from the last triangles into equation (5-143)
corresponding Dθ s and from the slope of the operating lines RD s are computed. Then
carrying (1+RD) values against the corresponding Dθ s on a millimetric paper and
calculating the area under the curve between the limits of RDi and RDf, gives the value
of GT.
Time required for heating of the solution from initial temperature tF to the average
distillation temperature t is calculated either from equation (5-48) or from (5-49).
For the calculation of distillation time;
G
θL = T (sec) (5-146)
G
where, G is the molar flow rate of vapor (k-mol/s), which remains constant during the
distillation and can be calculated from the heat transfer considerations as follows;
q U A( t H − t ) ln
G= = b (5-147)
λ λ
Then, total time for one batch operation is calculated from equation (5-51).
Example 5-15) Batch Rectification at Constant Top Product Composition
The batch of chloroform-toluene solution given in Example 5-14 will be rectified in the same column
but this time under varying reflux ratio. The solution will be charged to the still at 20 oC and
distillation will be continued, keeping the mole fraction of chloroform in the distillate constant at
0.733, at 760 mmHg until the mole fraction of chloroform in the still drops to 0.04.
Calculate :
a) The initial and final reflux ratio to be used,
b) Percentage recovery of chloroform,
c) Heat energy requirement for the operation.
d) Estimate the time of one batch operation for the conditions given in Example-5.14.
e) Compare the result with Example-5.9 and 5.14.
Assume that specific heat and latent heat of solution remain constat at 140 kJ/k-mol oC and 32 000
kJ/k-mol.
Solution :
a) First, points F, D and W are located on the xy-diagram of the system. A line from point D is drawn
and slope of this line is changed until 3 right angle triangles are located between this line and
equilibrium curve within the points D and F. This line is the operating line at the start of distillation.
Reflux ratio calculated from the slope of this line is the initial reflux ratio (RDi). Then another line
from point D with greater slope is drawn and the slope of this line is changed until 3 right angle
triangles but this time between point D and W fit. This line is the operating line at the end of
distillation. Reflux ratio calculated from the slope of this line is the final reflux ratio (RDf).
These are found as RDi = 0.929 and RDf = 25.18
b) As F, xF , D and xD are the same with the previous example, P.R. = 84.6 %. b
c) Sensible heat required is calculated from equation (5-140)
qS = (123.1)(140)( 100.5- 20) = 1 387 337 kJ
For the calculation of latent heat required, first GT must be calculated. For this various operating lines
between initial and final are drawn (not shown in the figure) and after locating three right angle
triangles between each and equilibrium curve starting at point D, x values are read from the diagram.
By calculating RD s from the slopes of these operating lines and Dθs from equation (5-143), and then
carrying the (1+RD) values against corresponding Dθ values, and calculating the area under the curve
between the limits of D = 0 and Dθ = 28.41 GT is obtained.
x Dθ 1+RD GT = ∫
28.41
(1 + R D ) dD θ
0
0.20 0 1,929 -
0.16 8.59 2.443 0.5(1.929+2.443)(8.59-0) = 18.78
0.135 13.38 2.932 0.5(2.443+2.932)(13.38-8.59) = 12.87
0.1 19.45 3.665 0.5(2.932+3.665)(19.45-13.38) = 19.69
0.092 20.74 4.887 0.5(3.665+4.887)(20.74-19.45) = 5.52
0.072 23.84 7.33 0.5(4.887+7.33)(23.84-20.74) = 18.94
0.04 28.41 26.18 0.5(7.33+26.18)(28.41-23.84) = 76.57
GT = 152.37 k-mol
Then, latent heat required, qL = (152.37)(32 000)= 4 875 840 kJ

Total heat required, qT = 1 387 337+ 4 875 840 = 6 263 177 kJ
d) Heating of the solution from 20 oC to the distillation temperature 100.5 oC is an unsteady-state

operation and the time required is the same with the Example-5.12, which was 4 h 12 min.
For the calculation of distillation time, equation (5-146) is used along with equation (5-147).
(1.1)(4 875 840)
θL = = 26 163 sec ≈ 7 h 16 min
(1.0)(10)(121 − 100.5)
(10 % excess energy was taken to account for the heating of the column itself).
xy-diagram of chloroform-toluene at 760 mmHg
Mole fraction of chloroform in vapor, y
Initial operating line
Final operating line
xF = 0.20 xD = 0.733
xW = 0.04
Mole fraction of chloroform in liquid, x
So, one batch time with 1 hour extra time for charging and discharging of the still is found from
equation (5-51);
θBT = 12 h 28 min
e) Comparison of the results of Example-5.9, Example-5.14 and Example-5.15
Example-5.9 Example-5.14 Example-5.15
Operation mode Simple distillation Batch distillation Batch distllation

with RD= constant with xD= constant
Purity of top product
(mole fraction) 0.34 0.733 0.733
P.R. of the MVC (%) 90.6 84.6 84.6
Total heat energy (kJ) 3 348 497 5 137 457 6 263 177
One batch time 8 h 03 min 10 h 48 min 12 h 28 min
It follows from the table that simple distillation is not suitable for this system as the relative volatility
of chloroform to toluene is not great. Batch distillation under constant reflux ratio requires less energy
and batch time than the batch distillation under varying reflux ratio. Hence this mode of operation is
preferred for this system.
Calculation of Number of Real Plates: After determining the number of the ideal
plates needed for a given separation, the number of the real plates can be found by
either applying plate or over-all column efficiency defined in Chapter-4. These
efficiencies are found experimentally in pilot size plate columns. The graphical
correlation giving by O’Connell and shown in Fig.5.38 may be used to calculate over-
all column efficiency for rectification when experimentally obtained value is not
available. Although this correlation was obtained for bubble-cap columns, it can also
Over-all column efficiency, Eo
α µFL
Fig.5.38 Over-all column efficiency at rectification
be used for sieve and valve tray columns for approximate calculations. If the relative
volatility of the system changes along the column, the relative volatility calculated at
the column average temperature is used. The liquid viscosity is taken as the molar
average viscosity of the feed liquid, which is calculated from the viscosities of pure
components (kg/ms) at column average temperature.
Example-5.16 Estimation of Number of Real Plates
Estimate the numbers of the real plates needed in each section of the column given in Example 5-10
from O’Connell correlation.
Viscosities of liquid methanol and n-propanol at 81 OC are 0.298 cP and 0.61 cP respectively
Solution :
From t-xy diagram of the system, temperature at the top of the column, for y1=0.95 is read as 67 oC,
and at the bottom of the column, for x9 =0.04 is read as 95 oC. Then, average column temperature is
81 0C.
At this temperature, from t-xy diagram : x = 0.342 and y =0.658 are read. Then relative volatility of
methanol to n-propanol from equation (5-13),
(0.658)(1 − 0.342)
α= = 3.7
(0.342)(1 − 0.658)
Molar average viscosity of the feed liquid at 81oC,
µ FL = (0.35)(0.298 * 10 −3 ) + (1 − 0.35)(0.61 * 10 −3 ) = 0.50 * 10 −4 kg / ms
Then, αµFL= (3.7)(0.50*10-4) = 1.85*10-4
Now enter this value into Fig.5.38 and read Eo=0.74.
3
Number of the real plates needed in the enriching section = =5
0.74
6
Number of the real plates needed in the stripping section = =9
0.74
Total number of the real plates needed in the column = 14
5.3.3.3 Rectification in Packed Column: Rectification operation can also be carried

out in continuous contact type of equipment. Especially, when the flow rate of solution
to be rectified is small, the packed column is preferred as in this case construction of
plate column is rather difficult due to the small diameter, although the possibility of
cartridge type construction exists. For rectification at fine vacuum, packed columns are
in many cases preferred because of the fact that special structured packings, developed
recently have very low pressure drop along the packing at even fairly high liquid and
vapor loads. To give an idea, for Montz-Pak, type: A3-500 packing element, pressure
drop per meter of packing is given as function of liquid and vapor loads in Fig.5.39.
Another case, at which the packed column is preferred to the plate column, is the
rectification of heat sensitive solution. As the liquid hold-up of a packed column is
L m3/m2h
∆pG mbar/m.
u G ρG Pa0.5
Fig.5.39 Pressure drop at Montz-Pak, type: A3-500
much smaller than the plate column, the residence time of the solution in the packed
column is low and as a result of this, decomposition of heat sensitive components of
solution is rather low. Except these special cases, the choice of column is done by
looking at the economy of the operation. In the construction of packed rectification
column, all the criteria seen in the construction of packed absorption column are valid.
For example, if the feed is a liquid, a liquid distributor must be installed at the feed
introduction section. The calculation of the diameter of a packed rectification column
is accomplished by using the same correlation for flooding or pressure drop per unit
height of packing as for packed absorption column (Fig.4.14), as gas and vapor hydro-
dynamically are the same. But, as the vapor and liquid loads are generally quite
different in enriching and stripping sections of the column, the diameter calculations
must be done for each section separately.
The calculation of the height of packing required for a giving rectification is done by
using the same procedure as used in gas absorption. But here again the enriching and
stripping section must be considered separately. If the constant molar over-flow case is
applicable, then xy-diagram of the system is sufficient for the calculation, otherwise
enthalpy-composition diagram of the system is also required. The total material,
component and enthalpy balance equations written for rectification in a plate column
are also valid for rectification in packed column. But, as in the packed column the
contact of two phases is continuous, the subscripts in the equations denoting the plates
must be omitted.
If the MVC balance is written for a differential height, dhe in the enriching section of
the column as shown in Fig.5.40a
d(Gy) = -d(Lx) = NA dSm (5-148)
where, NA is the total molar flux of the MVC, dSm is the mass transfer area available
in the differential volume dv. If we define an av as the mass transfer area per unit
volume of the packing then, dSm = avAcdhe can be written, where Ac is the cross-
sectional area of the empty column in enriching section. By substituting this into
equation (5-148)
d(Gy) = -d(Lx) = NAavAcdhe (5-149)
is obtained. G and L remain approximately constant even constant molar over-flow

does not apply. Hence NA= - NB and then from Chapter-3 for NA,
N A = k ′y (y i − y) = k ′x (x − x i ) = K ′y (y∗ − y) = K ′x (x − x ∗ ) (5-150)
can be written. By substituting all these into equation (5-148) finally;
( Gy ) 2 ( Lx ) 2 ( Gy ) 2 ( Lx ) 2
⌠ d (Gy) ⌠ d (Lx ) ⌠ d (Gy) ⌠ d (Lx )

∫
Ze
Ze = dh e = ⎮ = ⎮ = ⎮ = ⎮
⌡ k ′y a v A c ( y − y i ) ( Lx⌡) k ′x a v A c ( x − x i ) ⌡ K ′y a v A c ( y − y ) ( Lx⌡) K ′x a v A c ( x − x )
0 ∗ ∗
( Gy ) q q ( Gy ) q q
is obtained. (5-151)
In the case of varying over-flow case, the integral terms are evaluated as follows: as
example consider the evaluation of first integral on the right hand side. From point ∆e
arbitrary lines (operating lines) are drawn on the right hand side of ∆eF∆s line
(enriching section) and points G and L are marked and corresponding y and x values
are transferred to the xy-diagram above (Fig.5.40c). By joining the points having these
x and y values as coordinates, the enriching section operating line of the column is
plotted on the xy-diagram of the system as shown in Fig.5.40c. Then arbitrary P points
on the operating line are chosen and x and y values of these points are read and with
the help of ∆e=G-L and ∆ex∆e= Gy-Lx, the G and L values are computed at the sections
considered. Then by drawing the lines from points P with slopes (- k ′x a v /k ′y a v ), points
M on the equilibrium curve are marked and corresponding yi values are read. The area
under the curve, which is plotted by taking the 1/ k ′y a v A c (y i − y) values against the
Gy, between the limits of (Gy)q and (Gy)2 gives the value of integral hence the ze.
qC
G2,y2 P=cons.
H-y ∆e
G G
G
Specific enthalpies, H, h
G
he=ze L2,x2
D,xD
W
Enriching sec.
Top product
dhe L L F
L
L L L D
h-x
he=o 0
zF xD=x2 1.0
xw=x1
F,zF Gq,yq Lq,xq x,y
∆S
hs=zs (b)
Stripping sec.
dhs 1.0
y2 M
yi D
y q-line P
hs=o G1,y1
y y=x
yq Q
qS
Enr.sec.op.line
Bottom product L1,x1 F
W
xw=x1 Strip.sec.op.line
y1
W
0
0 xq zF xi x xD=x2 1.0
(a) xw=x1
x
(c)
Fig.5.40 Rectification in packed column
The evaluation of equations (5-151) is much simpler in constant molar over-flow case
as in this case G and L are constant through out the enriching section and
consequently;
G L L L
HG = HL = HL = H OL = (5-152)
k ′y a v A c k ′x a v A c k ′x a v A c K ′x a v A c
can be taken outside the integral signs with the names of height of one transfer unit
and the remaining integral terms under the names of number of transfer units
simplify to:
y2 x2 y2 x2
⌠ dy ⌠ dx ⌠ dy ⌠ dx
NG = ⎮ NL = ⎮ N OG =⎮ ∗ N OL = ⎮ (5-153)
⌡ yi − y ⌡ x − xi ⌡y − y ⌡ x − x∗
yq xq yq xq
The solutions of these integrals are again accomplished by using graphical integration
technique by selecting arbitrary P points on the enriching section operating line, which
is a straight line in this case, and drawing the lines with slopes (- k ′x a v /k ′y a v ) and
locating the M points on the equilibrium curve.
If the steps from equation (5-148) are repeated for the stripping section of the column,
the height of packing of this section, (zs) is found. The integral limits in this section
must be taken as (Gy)q - (Gy)1 and (Lx)q - (Lx)1. In the case of varying over-flow, to
plot the operating line on xy-diagram, the required values of x and y are found by
drawing arbitrary straight lines this time from point ∆s on the left hand side of ∆eF∆s
line. For constant molar over-flow case, G and L must be used in the equations
(5-152) along with the cross-sectional area of the stripping section, if this is different
than the area of enriching section.
Heights of transfer units are determined experimentally as in the gas absorption. For
this, pilot size columns filled with the same packing are used. As an example, HOG
values obtained by Furnas and Taylor at atmospheric rectification of ethanol-water
system are given in Table.5.2 for two different packing types.
Table 5-2. HOG values for ethanol-water system
Packings Depth of Liquid flow flux HOG

packing(m) (kg/m2s) (m)
50 mm Raschig rings 3.0 1.06 0.670
25 mm Raschig rings 3.0 1.02 0.366
9.5 mm Raschig rings 2.44 0.416 0.396
9.5 mm Raschig rings 2.44 0.780 0.305
25 mm Berl saddles 2.75 0.195 0.427
25 mm Berl saddles 2.75 1.25 0.335
12.5 mm Berl saddles 3.0 0.25 0.457
12.5 mm Berl saddles 3.0 1.196 0.274
Another method, which is used at the calculation of height of packing, is the height
equivalent to a theoretical plate (H.E.T.P.). As it has been shown, the number of the
theoretical plates required for a given rectification can be calculated by using
McCabe-Thiele or Ponchon-Savarit method depending upon the conditions. If the
height of selected packing, which makes a separation equivalent to one theoretical
plate under the operating conditions, is known; by multiplying this height with the
number of the theoretical plates, the required height of packing is found. H.E.T.P.
values at a rectification column filled with pall rings of 25, 38 and 50 mm sizes were
found in the ranges of 0.4-0.5 m., 0.60-0.75 m. and 0.75-1.0 m. respectively, when the
pressure drop in the vapor is above 17 mm liquid head per meter of packing.
A3-500
Nideal/m. packing
Nideal/m. packing
u G ρG Pa 0.5
u G ρG Pa 0.5
Fig.5.41 The separation powers of two different type of packing
The producers of special packing materials give generally the number of the
theoretical plates that will be achieved per meter of packing (reciprocal of H.E.T.P.) as
function of flow factor, which is defined as uG√ρG. As an example, in Fig.5.41 the
separation powers of two different types of packing produced by Montz GmbH are
shown.
5.3.3.4 Rectification of Azeotropic Solutions: Binary solutions having minimum or
maximum boiling azeotropic points may be subjected to rectification. But as the
azeotropic composition cannot be exceeded, a complete separation of the solution is
not possible. Depending upon the compositions
of the feed and azeotrope, one of the
t-y
tB components may be obtained in pure state. As
an example consider the binary solution having
tA
t
t-x
Az minimum boiling azeotrope at 65% MVC, as
shown in Fig.5.42. If a 100 k-mol/h feed,
containing 30% MVC, is subjected to
rectification, the top product can approach to
0 0.2 zF 0.4 0.6 zF 0.8 1.0
the azeotropic composition (of course, if
x,y sufficient number of the plates or packing
height is provided in the enriching section) and
1.0
with the assumption that all the MVC appears
in the top product, a top product of
y Az
D=(100x30/0.65)= 46.15 k-mol/h is withdrawn
D from the column, leaving behind 100-
y=x
46.15 = 53.85 k-mol/h bottom product which is
F almost pure in the LVC. As it is seen, in this
case a pure product consisting of LVC can be
obtained, the top product being an azeotrope.
0 0.2 zF 0.4 0.6 zF 0.8 1.0
Now, let us assume that the feed flow is again
x 100 k-mol/h, but it contains this time 75%
Fig.5.42 Rectification of a minimum MVC. In this case, the top product may again
boiling azeotrope approach the azeotropic composition. With the
assumption that almost all the LVC is in the top
product, a top product of D = (100x25)/(1-0.65) = 71.43 k-mol/h is obtained, leaving
behind 100-71.43 = 28.57 k-mol/h bottom product which is almost pure in the MVC.
As it is seen, in this case a product, which is almost pure in the MVC is produced,
while the other product is not pure. The azeotropes having maximum boiling point
behave similarly, but in this case bottom products are azeotropes and the top products
are pure products. It follows from these that azeotropic solutions cannot be separated
into pure products by ordinary rectification. As it will be considered later, only by
adding a third component to the solution, complete separation is made possible. But in
this case, another column to recover the added component is necessary.
However, some binary azeotropic solutions can be separated completely without
adding a third component to the solution. These solutions either form hetero-azeotrope
or their azeotropic
azeotropic composition change with pressure. If an azeotropic vapor forms two
liquid phases upon condensation, this type of azeotropism is called as hetero-
azeotropism. The reason for hetero-azeotropism is the limited solubilities of the
components in liquid state. Water/n-butanol is a hetero-azeotropic system, for liquid
water and n-butanol dissolve limitedly within each other as shown in Table.5.3.
Table 5-3. The solubilities of water/n-butanol binary
Temperature(oC) Butanol layer Water layer

(mass % of alcohol) (mass % of alcohol)
5 80.38 9.95
10 80.33 8.92
15 80.14 8.21
20 79.93 7.81
25 79.73 7.35
30 79.38 7.08
35 78.94 6.83
40 78.59 6.60
50 77.58 6.46
60 76.38 6.52
70 74.79 6.73
Water/n-butanol solutions hence can be completely separated in a distillation system

containing two columns as shown in Fig.5.43. As it is seen, the feed is introduced to a
decanter, which is located beneath the condenser. While the bottom layer (water layer)
of the decanter is pumped to the top of a column, the upper layer (butanol layer) is
introduced to the top of another column. As it is seen, both columns consist of only
stripping sections and there is a common condenser for both columns. The vapors
coming from top of the columns have almost azeotropic compositions (approximately
23 mol % butanol) and upon condensing in this condenser, they flow to the decanter,
where they separate in two insoluble liquid phases. The water vapor rising from the
reboiler of the water column stripes off the butanol from the liquid flowing down the
column, giving it the water. By providing sufficient number of the plates or packing
height, the vapor at the top of the column can be brought to the azeotropic
composition. The liquid leaving the column at the bottom is almost pure water and part
of it is vaporized in a reboiler and returned back to the column, while the remaining
part is discarded. In this column, open steam may also be used with the elimination of
the reboiler. The vapor, rising from the reboiler of the other column and which is
almost pure in n-butanol, stripes off the water from down-flowing liquid, giving it the
azeotrope azeotrope
GI yDI ≈0.77 qc GII yDII ≈0.77

condenser
decanter
I II
760
760
mmHg
mmHg
1 LI xoI LII xoII 1
GI LI GII LII
n-Butanol Water column

column Feed
F, zF
N GI GII N
qsI
qsII
reboilers
LI LII
n-Butanol Water
WI xwI WII xwII
WII
1.0
P =760 mm Hg slope=LII/GII N
Az 1
Mole fraction of water in vapor, y
yDII
yDI
1 Water
column
n-Butanol
column
slope=LI/GI y=x
N
0 WI
0 xwI xoI xoII xwII
0.2 0.4 0.6 0.8 1.0
Mole fraction of water in liquid, x
Fig.5.43 Rectification of n-butanol/water solution
n-butanol. Hence with locating sufficient number of the plates or providing sufficient
height of packing in this column, the composition of the vapor is brought to the
azeotropic composition, when it reaches top of the column, and the liquid is made to
reach almost pure butanol composition, when it leaves the column at the bottom. The
design of both columns whether they are plate or packed, can be made with the
methods given above.
In another group of azeotropic solutions, the composition of azeotrope changes with
pressure. In this case, by using two columns, each operating at different pressure,
complete separation of azeotropic mixture is accomplished. Aceto nitrile/water
solution is a typical example of this group. While binary azeotrope contains 73 mole
percent aceto nitrile at 760 mmHg, this rises to 84 mole percent at 150 mmHg.
Aqueous aceto nitrile solution, containing approximately 30 mole percent aceto nitrile,
is mixed with the top product of the second column and is fed to the first column,
which operates at 150 mmHg pressure as shown in Fig.5.44. While the azeotropic
mixture is withdrawn at the top of the column, the excess water is taken from the
bottom and discarded. The top product of this column is then fed to the second
column, which operates at 760 mmHg. The top product of this column, which is an
azeotrope with 73 mole percent aceto nitrile, is mixed with the aqueous solution
coming from the plant to make the feed to the first column as mention before. The
excess aceto-nitrile leaves the second column as bottom product in almost pure state.
The columns, which may be plate or packed can easily be designed by using the
methods giving above.
Azeotrope-I Azeotrope-II qcII

qcI
I II
P=150 mmHg P=760 mmHg
1 xoI 1 xoII DII xDII
FII =DII
zFII = xDII
FEED Aceto nitrile
Water column
column
F, zF FI , zFI
N N
qsI
qsII
Reboilers
WI ,xwI WII , xwII
Water Aceto nitrile
Fig.5.44 Rectification of aceto nitrile/water solution
5.4 Internal Design of Plate Columns for Liquid-Gas (Vapor) Contact: The plate
columns are widely used in gas absorption, desorption and rectification operations.
The first step in the design of these columns is to find the number of the plates needed
for a given separation for which the ratio of the amounts of two phases (not the
absolute values) flowing inside the column along with the equilibrium relationship of
the system is sufficient. Next step constitutes the calculation of the diameter of the
column and the design of plates themselves. The diameter is directly related to the
amounts of the phases flowing inside the column. In the determination of the diameter
of a plate column, the flooding criterion is used as in the packed columns. Of course
flooding relationship in plate columns is quite different and complicated than the
packed columns as the design of the plates themselves play an important role here. The
design is accomplished by compromising various opposing tendencies, which require
large number of trial and error.
Bubble Cap Plate Sieve Plate Valves Tray Valves Tray
Fig.5.45 Types of plates
There are different types of plates, which are used in today’s industry. Some of them
are shown in Fig.5.45. The most commonly used ones are sieve (perforated) plate and
the valves tray (plate). The bubble cap plates, which were once used widely, are now
used in some special cases due to the high cost. The sieve plates are now almost
standard in use, because of very well developed design equations and low cost. The
only disadvantage of these plates is to be prone to the weeping at reduced vapor loads,
which causes the loss of efficiency. If during the operation, vapor load is to be
subjected to low values from time to time, it is then the use of valves trays are
recommended as they adjust the holes area automatically depending upon the vapor
load and hence they operate in a wide range of vapor loads without losing the
efficiency.
Below, design principles of a sieve plate column are to be given as an example.
Although the equations for other types of plates are similar but they are not identical.
A sieve plate is essentially a circular metal plate on part of it, which is called active
area, Aa small diameter holes are drilled for gas flow. Part of the plate area, which is
called down-comer area, Ad is cut off to make a segmental channel for liquid flow as
shown in Fig.5.46. A metal sheet, called down comer apron is fixed to the cut part of
the plate vertically to form the channel and is extended above the plate to create a
weir, which is required to keep a liquid pool on the plate. On the area of the plate,
which is projected area of the down-comer above, holes are not drilled, because no
vapor flow through the down-comer is desired. Thus, the active area of a plate is
Aa=Ac-2Ad, where Ac is the total cross-sectional area of the plate.
In order to keep plate efficiency as high as possible, gas or vapor is dispersed as small
bubbles in the liquid pool formed on the plate. It is obvious that great depth of liquid
on the plate means long contact time between gas and liquid which in turns, means
high plate efficiency. But great liquid depth causes high pressure drop in the gas rising
through the liquid. This results in high operating cost in gas absorbers and in high
temperatures at the bottom of rectifiers, which are both not desired. It follows from
here that height of weir must be kept at a reasonable level, neither too high nor too
Down-comer
apron Projected
down-comer
Vapor
area
Down-comer
area
hd Weir
how
holes
hdc hw Ad LW Ad
liquid
Column
Plate
Aa
Down-comer Active area
Weir
Net area (An)

Plate (Ac)
(a) (b)
Fig.5.46 (a) Vertical cut of a sieve plate column, (b)view of a sieve plate from the top
low. On the other hand, gas must be dispersed in bubbles as small as possible and their
velocities through the liquid pool on the plate must be as high as possible for a high
plate efficiency, as the first increases the mass transfer area and the latter the mass
transfer coefficient, due to the increased turbulence. But high gas velocity through the
liquid pool again means high pressure drop in the gas side. Not only this, high gas
velocity also causes liquid entrainment which in turns decreases the plate efficiency.
So, it follows from these explanations that up to a certain value, increase in gas
velocity increases plate efficiency due to the increased turbulence, but after then
decreases it due to the excessive liquid entrainment. The pressure drop in the gas side
influences the liquid level in the down-comer above; high gas side pressure drop
means high liquid level (back-up) in the down-comer. If the liquid level in the down-
comer reaches the liquid level of the plate above, the whole column is then filled with
the liquid and the gas phase passes through the liquid in fluctuating pulses and the
plate efficiency rapidly drops to a very low value. This condition is known as
flooding. So, the gas velocity in the column must be so selected that no flooding
should be observed. On the other hand, low gas velocity through the holes results in
liquid raining down through the holes which is known as weeping and which reduces
the plate efficiency sharply. It follows from the above explanations that there is a safe
operating region for the column depending upon the gas and liquid flow rates as shown
in Fig.5.47. The conning is observed at low liquid flow rates, in which gas pushes the
liquid around the hole away and it passes as inverted cone through the liquid. This
reduces the plate efficiency drastically as the gas-liquid contact becomes very poor.
The design of plates in the satisfactory operation region is of prime importance and
requires many trial and errors, which are explained below.
Liquid
entrainment
Flow rate of gas
Flooding
Satisfactory
operating
Conning
Limitation of
region down-comer
Weeping
Flow rate of liquid
Fig.5.47 Satisfactory operating region of sieve-plate column
5.4.1 Column Diameter: The diameter of column Dc (m) is computed from equation,
⎡ ⎤
0.5
4G&
Dc = ⎢ ⎥ (5-154)
⎣ πρ G u G (1 − a) ⎦
where, ρG (kg/m3) is density of gas (vapor), uG (m/s) is gas velocity based on net area
(An) and a is the ratio of Ad/Ac. The net area is the area through which gas phase flows
between the plates. Hence, it is given as An=Ac-Ad. Gas velocity uG is taken as some
percent of flooding gas velocity uGF, which was found dependent on
G& , L& , ρ , ρ , P.S., σ, A /A . Here, L& (kg/s) is the liquid flow rate, ρL (kg/m3) is the
G L h a
density of the liquid, P.S.(m.) is plate spacing, σ (N/m) surface tension of liquid and
Ah (m2) is total hole area. The first four of these variables are collected under one
group, which is known as flow parameter, as follows,
L& ρ G
FLG = & (5-155)
G ρL
Dependence of uncorrected capacity factor, K1 on this flow parameter at various plate

spacings has been determined experimentally and the results are given in Fig.5.48. The
capacity factor obtained from this diagram is valid for σ = 0.02 N/m and Ah/Aa ≥ 0.1.
When these values are different, K1 is multiplied by f.(σ/0.02)0.2 and corrected
capacity factor K1c is found. Factor f is obtained from the table below.
Ah/Aa ≥ 0.1 0.08 0.06

f 1.0 0.9 0.8
Then from equation below the gas velocity, which will cause the flooding, is
calculated.
ρL − ρG
u GF = K1c (5-156)
ρG
0.2
Plate spacing, m
0.1
Capacity factor, K1
0.08
0.06
0.04
0.02
0.01
0.01 0.02 0.04 0.06 0.08 0.1 0.2 0.4 0.6 0.8 1.0 2.0 5.0
0.5
L& ⎛ ρ ⎞
Flow parameter, FLG = ⎜⎜ G ⎟⎟
& ρ
G ⎝ L ⎠
Fig.5.48 Capacity factor
By taking some percent of this velocity (usually 60-80 %), normal operating gas
velocity uG (m/s) is found. Finally, inserting this value into equation (5-154) the
diameter of the column is obtained.
It is the property of a circle that once the ratio of Lw/Dc is specified then a = Ad/Ac is
automatically fixed. This relationship is given in the table below for the most
commonly used range in the designs.
Lw/Dc 0.690 0.695 0.700 0.705 0.710 0.715 0.720 0.725 0.730
a = Ad/Ac 0.0833 0.0855 0.0878 0.090 0.0922 0.0945 0.0968 0.0992 0.1016
5.4.2 Plate Spacing (P.S.)(m): The plate spacing, which is the distance between two
consecutive plates, is the most important parameter fixing the height of a column and
hence it must be kept as small as possible, if there are no other reasons such as
construction of manholes etc. In practice, plate spacing is selected 0.45m or smaller for
columns having diameters less than 1.2m and higher plate spacings are employed for
larger diameter columns, although this is not a rule. At cryogenic rectifications such as
the rectification of air, plate spacings as low as 0.15-0.20 m are used.
5.4.3 Liquid Entrainment: The liquid entrainment must be kept at a low value as it
reduces the plate efficiency. The fractional entrainment, which is defined as,
e
E= & (5-157)
L+e
must be kept below 0.1 for a satisfactory design. In the equation above, e is the liquid
as kg/s carried back to the plate above by the gas and L& is the flow rate of liquid as
kg/s. So-defined fractional entrainment was found to be a function of flow parameter
and the percent of flooding gas velocity and these relationships found experimentally
are given in Fig.5.49.
5.4.4 The Holes: The diameters of the holes, dh (mm) punched in the active area
1.0 change from 3 to 15 mm, the 5 mm
0.8
0.6
being the most widely used one. They
are drilled at the corners of either a
0.4
square or an equilateral triangle, the
0.2
Percent of flooding pitch (distance between the hole
centres), PT (mm) being 2.5 to 5 hole
Fractional entrainment, E
0.1 diameters. While smaller pitch causes

0.08 the coalescence of the gas bubbles
0.06
issuing from the holes, greater pitch
0.04
makes the diameter of the column
unduly large. Between down-comer and
0.02
the first row of holes and also between
0.01 the last row of holes and the weir 100
0.008 mm’s un-drilled spaces must be left
0.006
(why?).
0.004 By observing these, the holes must be
distributed evenly in the active area.
0.002
Total holes area accounts for generally
0.001 between 5-15% of the active area. The
0.01 0.02 0.04 0.06 0.1 0.2 1.0 ratio of total holes area to the active
Flow parameter, FLG area is function of the ratio of hole
Fig.5.49 Liquid entrainment diameter to the hole pitch, the constant
being dependent on the holes
configuration. For equilateral hole configuration the relationship is ;
⎡ dh ⎤
2
Ah
= 0.907 ⎢ ⎥ (5-158)
Aa ⎣ PT ⎦
and for square hole configuration,
⎡ dh ⎤
2
Ah
= 0.785 ⎢ ⎥ (5-159)
Aa ⎣ PT ⎦
are given. As it is seen, more holes can be drilled in equilateral configuration than the
square configuration. The total number of the holes drilled, n is then calculated from,
n π d 2h −6
Ah = 10 (5-160)
4
5.4.5 Weir: As explained before, great weir height, hw (mm) increases the plate
efficiency because of the long contact time between gas and liquid but, it also
increases the pressure drop in the gas side. Hence, an optimum height must be found
for the weir. This is as low as 20 mm for vacuum operations and as high as 75 mm for
high-pressure operations and mostly 50 mm for atmospheric operations. The length of
weir, LW (m) is selected such that liquid weir crest, how (mm liquid) is not excessive.
For this, it is recommended that volumetric flow rate of liquid per unit length of weir
is to be less than 0.025 m3/sm.
Liquid weir crest: liquid crest over the weir is proportional to the volumetric flow
rate of liquid and inversely proportional to the length of weir and this relationship after
experimentation was given as;
⎡ L& ⎤
2/3
0.95
h ow = 750 ⎢ ⎥ (mm) (5-161)
⎣ ρL Lw ⎦
Plate Thickness/Hole diameter= χ/dh
0.90 For a reasonable plate efficiency, hw+how
should be no smaller than 50 mm.
5.4.6 Pressure Drop in the Gas along
0.85
the Plate: The pressure drop that the gas
Orifice constant, Co
phase will encounter as it passes the plate,

can be divided in two parts: dry pressure
0.80
drop and the pressure drop that occurs as
the gas passes through aerated liquid. Dry
0.75 pressure drop that occurs during the
passage of gas through the holes of dry
plate can easily be found from very well
and less
0.70 known orifice equation, which for this
case can be written in terms of liquid head
ho (mm) as;
0.65
⎛ 1 ⎞ ρG 2
2
0 5 10 15 20 h o = 51⎜ ⎟ uh (5-162)
(Ah/Aa)*100 ⎝ Co ⎠ ρ L
Fig.5.50 Orifice constant where, uh (m/s) is the velocity of gas
through the holes which can be calculated
from,
&
G
uh = (5-163)
ρG A h
The orifice coefficient, Co is a function of the ratio of plate thickness to the diameter of
hole and the ratio of total holes area to the active area and this relationship is given in
Fig.5.50.
The pressure drop that is due to the passage of gas through aerated liquid, ha is given
as mm liquid head by,
ha = Qp(hw+how) (5-164)
where, Qp is known as aeration factor and can be found from Fig.5.51.
Hence, the total pressure drop in the gas side per plate, hT as mm liquid head is
calculated from,
hT = ho + ha (5-165)
Weeping: the weeping, which is known as the liquid coming down from the holes
must be prevented or at least must be kept at a reasonably low level. To secure this, the
velocity of the gas through the holes, uh must always be higher than the minimum
hole velocity, uhm, which is giving by,
K 2 − 0.90(25.4 − d h )
uhm = (5-166)
ρ 0.5
G
where, K2 is a constant dependent on (hw+how) and the relationship between them is

given in Fig.5.52.
Down-comer back-up: the liquid level in the down-comer, which is also known as
32
31
1.0
30
0.8 K2
Qp
0.6 29
0.4 28
0.0 0.5 1.0 1.5 2.0 2.5 3.0
27
&
G 0 20 40 60 80 100 120
FGa =
A a ρG hw+how , mm
Fig.5.51 Aeration factor Fig.5.52 Constant K2
down-comer back-up, is very important during the operation. This level is obtained by
adding the pressure drops that will occur in the gas and liquid phases as they flow, to
the liquid level on the plate, which is (hw+how). Total pressure drop in the gas side was
obtained as hT. The pressure drop in the liquid side as it flows through the down-comer
and through the contraction formed at the plate entrance can be calculated by using the
hydraulics equations. The pressure drop due to the flow in the down-comer can readily
be neglected as the velocity of the liquid and the distance it travels, are very small. But
the pressure drop encountered during the flow through the restriction at plate entrance
may be significant. The restriction at the plate entrance is created deliberately by
immersing the down-comer apron into the liquid on the plate to prevent the escape of
gas bubbles through the down-comer. Generally an opening corresponding to hdc
(mm) = hw-10 is left on the plate between plate deck and tip of down-comer apron.
Hence, the cross-sectional area through which liquid flows at the plate entrance
Down-comer
hpe
ha
Weir
ho
hda hd
how how
hw hw
liquid
Plate
Column
Vapor
Fig.5.53 Down-comer back-up
becomes Ape= Lw* hdc*10-3 (m2) and the pressure drop in the liquid side due to the
flow through this restriction, hpe (mm liquid) is given as;
2
⎡ L& ⎤
hpe= 166 ⎢ ⎥ (5-167)
⎢⎣ ρ L A pe ⎥⎦
This pressure drop reflects itself in the down-comer back-up too. The liquid flowing
into the down-comer from the previous plate is an aerated liquid and hence, by taking
this into account for design safety, finally liquid level in the down-comer is given as,
h w + h ow + h T + h pe
h da = (5-168)
Qp
So-calculated level must always be smaller than P.S. to evade the flooding. In practice
rather great safety margins are used and columns are designed such that
hda ≤ ½ (P.S)*103 (5-169)

Residence time in down-comer: The liquid flowing into the down-comer is an
aerated liquid. This liquid must be freed from the gas bubbles before it enters the plate
below. The experiments have shown that a residence time of 5 second will be enough
for the bubbles to coalesce and escape back to the gas phase above. The residence time
of liquid in the down-comer can be calculated from the equation below;
A d (P.S. )
θ dr = (5-170)
L& /ρ L
Above; the equations, which are required for the calculation of diameter and some
important parameters of a sieve plate column for gas-liquid contact were listed. Below,
the sequence of the use of these equations under the name of design steps is given.
5.4.7 Design Steps: 1o) First calculate L& and G & as kg/s, which are no longer changed.
2o) Calculate or estimate ρL, ρG and σ at the operating conditions. 3o) Assume a plate
spacing, P.S. 4o) Make a plate lay-out and assume a percent of flooding. From plate
lay-out, selection of Lw/Dc, dh, PT and hw are understood. These can be changed at any
time. 5o) Calculate the diameter of the column as explained above. 6o) Calculate
fractional entrainment, E from Fig.5.49. If the value is greater than 0.1, then reduce the
percent of flooding, which was assumed at step 4. 7o) Check for weeping by
calculating uh and uhm. If weeping occurs, then return back to step 4 and re-assume the
relevant ones in the plate lay-out. 8) Calculate the total pressure drop along a plate. If
this is too high, return back to step 4 and re-assume the relevant ones in plate lay-out.
9o) Calculate the down-comer back-up. If this is greater than half of the plate spacing,
first go to step 4 and renew the relevant assumptions. After trying all the possible
changes in step 4, if down-comer back-up is still greater than half of the plate spacing,
then go to step 3 and increase the plate spacing. 10o) Calculate the down-comer
residence time. If this is smaller than 5 s., then go back to step 4 and change the
relevant ones in the assumed plate lay-out.
Do not forget the fact that you should re-calculate all the steps down from the step to
which you have returned.
As it is seen, internal design of a sieve plate column is accomplished by first making
some assumptions and then checking them one by one.
In the design of absorption and desorption columns, the design is realized at the
section where L& and G & are the greatest. As for the rectification columns, diameter is
calculated at the top and at the bottom of the column. If no great difference is found,
then the greater diameter is selected for both sections, but the plate lay-outs in each
section may be different, if necessary. If the difference between the diameters of two
sections is quite great and/or the construction material of the column is expensive, then
the diameters and the plate lay-outs of each section maybe made different.
Example-5.17) Internal Design of a Sieve-Plate Rectification Column
For the separation of methanol/n-propanol solution given in Example-5.10 , a sieve-plate column with
4 mm plate thickness will be used. Design the stripping section of the column with the values at the
bottom plate.
Solution:
From Example-5.10, L = 493.84 k − mol / h , G = 296.84 k − mol / h , tN= 95 oC, xN=0.022 (mass
frac.), xN = 0.04 (mol frac.), yN = 0.12 (mol frac.)
Mass flow rate of liquid, L& = L M L = (493.84 / 3 600)[(0.04)(32) + (0.96)(60)] = 8.1 kg / s
Mass flow rate of vapor, G & = G M = (296.84 / 3 600)[(0.12)(32) + (0.88)(60)] = 4.7 kg / s
G
ρ meth = 716 kg / m , ρ prop = 735 kg / m 3 , σ meth = 0.016 N / m , σ prop = 0.018 N / m

o 3
At 95 C L L
ρ L = (0.022)(716) + (0.978)(735) = 734.6 kg / m 3 , σ = (0.022)(0.016) + (0.978)(0.018) ≅ 0.018 N / m

Pbottom M G (1.07)(56.64)
ρG = = = 2.0 kg / m 3 (Pressure at the bottom was assumed as 1.07 atm)
RT (0.082)(273 + 95)
Assumptions: P.S.=0.60 m, Lw/Dc=0.69, hw=50 mm, dh=5 mm, PT =2.5 dh(∆), Percent of flooding =70
8.1 2.0
Flow parameter, from equation(5-155) FLG = = 0.09 , Then, uncorrected capacity factor
4.7 734.6
from Fig.5.48 for P.S.=0.60 m is read as K1=0.1
From equation (5-158) Ah/Aa= 0.907(1/2.5)2 = 0.145. Then, as f = 1, corrected capacity factor,
K1c = (0.1)(1.0)(0.018/0.02)0.2 = 0.098
Flooding vapor velocity from equation(5-156); uGF = 0.098[(734.6-2.0)/2.0]0.5 = 1.88 m/s
Operating vapor velocity, uG = (0.70)(1.88) = 1.32 m/s
For Lw/Dc = 0.69 a = Ad/Ac = 0.0833. Then, column diameter from equation (5-154),
0.5
⎡ (4)(4.7) ⎤
Dc = ⎢ ⎥ = 1.573 m . Take Dc = 1.60 m.
⎣ (π )(2.0)(1.32)(1 − 0.0833) ⎦
Total column area, Ac = (0.785)(1.60)2 = 2.01 m2
Down-comer area, Ad = (0.0833)(2.01) = 0.167 m2
Net area, An = 2.01-0.167 = 1.843 m2
Active area, Aa = 1.843-0.167 = 1.676 m2
Total hole area, Ah = (0.145)(1.676) = 0.243 m2
Length of weir, Lw = (0.69)(1.60) = 1.10 m
-Check for liquid entrainment,

From Fig.5.49 for FLG = 0.09 and 70 % of flooding , E = 0.021 is read. As this value is smaller
than 0.1, liquid entrainment is acceptable.
-Check for weeping,
Vapor velocity through the holes from equation (5-153), uh = 4.7/(2.0)(0.243) = 9.67 m/s
Liquid weir crest from equation (5-161), how = 750 [8.1/(734.6)(1.10)]2/3 = 34.87 mm
hw + how = 50 + 34.87 = 84.87 mm. From Fig.5.52 K2 = 30.8 is read.
Minimum vapor velocity through the holes from equation (5-166),
30.8 − 0.90(25.4 − 5)
u hm = = 8.8 m / s
2 .0
Although uh > uhm the difference is very small. It is advisable to increase the uh . This can easily
be accomplished by drilling less holes in the active area. For this, change PT/dh from 2.5 to
2.8. With this new value, Ah/Aa = 0.907 (1/2.8)2 = 0.116 is found. As f is still 1, K1c and hence Dc
will not change. Only, Ah will have new value. This is : Ah = (0.116)(1.676) = 0.194 m2.
Now, vapor velocity through the holes rises to uh = 4.7/(2.0)(0.194) = 12.11 m/s. This velocity is
much secure than the previous one to prevent the weeping.
-Check for pressure drop in the vapor along the plate;
Dry pressure drop at the vapor side along the plate,
For (Ah/Aa)*100 = 11.6 and with χ/dh = 4/5 = 0.8, from Fig.5.50 Co = 0.80 is read. Then, from
2
⎛ 1 ⎞ ⎛ 2 .0 ⎞
equation (5-162); h o = 51⎜ ⎟ ⎜ ⎟(12.11) = 31.82 mm liquid head
2
⎝ 0 . 80 ⎠ ⎝ 734 . 6 ⎠
FGa = 4.7/[(1.676)(2.0)0.5] = 1.98 ≈ 2. From Fig.5.51 aeration factor, Qp = 0.61 is read.
Pressure drop in the vapor through the aerated liquid, from equation (5-164);
ha = 0.61 (84.87) = 51.77 mm liquid head.
Total pressure drop in the vapor through the plate,
hT = 31.82 + 51.77 = 83.59 mm liquid head.
This pressure drop corresponds to (83.59)(734.6)/13 600 = 4.52 mm Hg, which can be
considered reasonable for atmospheric rectification column.
Pressure drop in the liquid at plate entrance;
Clearance at plate entrance, hdc = 50-10 = 40 mm. Then, flow area at plate entrance,
Ape = (1.10)(40*10-3) = 0.044 m2. Hence pressure drop in the liquid at plate entrance from
equation (5-167), hpe = 166[8.1/(734.6)(0.044)]2 = 10.43 mm liquid head.
-Check for down-comer back-up;
Down-comer back-up from equation(5-168),
50 + 34.87 + 83.59 + 10.43
h da = = 293.3 mm
0.61
As hda < ½ (P.S.)*103 , assumptions made are valid.
-Check for down-comer residence time from equation (5-170);
(0.167)(0.60)
θ dr = = 9.1 s
(8.1 / 734.6)
As this value is greater than 5 s, is acceptable.
-Check for pressure at the bottom of the column,
Pbottom= Ptop+ NReal hT = 1 + (14)(4.52)/760 = 1.083 atm. So, the assumed value (1.07 atm) at
the start of the design is quite close to this.
Finalised Design:
P.S. = 0.60 m Percent of flooding = 70

hw = 50 mm E = 0.021
dh = 5 mm uh = 12.11 m/s
χ (thickness of plate) = 4 mm uhm = 8.8 m/s
PT (∆) = 14 mm θdr = 9.1 s
Dc = 1.60 m Pbottom = 1.083 atm
LW = 1.10 m hda = 293.3 mm
hdc = 40 mm
n (number of the holes/plate) = 5 908
NReal = 14
Problems
5.1 The variation of vapor pressure with temperature for n-hexane and n-heptane is as follows:
po(mbar) 13.3 26.7 53.3 80 133 267 533 1013 2026

t ( oC) hexane - 25.0 - 14.1 - 2.3 5.4 15.8 31.6 49.6 68.7 93.0
heptane - 2.1 9.5 22.3 30.6 41.8 58.7 78.0 98.4 124.8
Assuming ideal behaviour, calculate and plot the vapor-liquid equilibrium data for the system at 1 atm.
5.2 a) Calculate the bubble point of a binary liquid solution containing 0.30 mole fraction of the MVC
at 1 bar pressure.
b) What is the dew point of the vapor mixture containing 30 mol percent MVC at 1 bar.
c) Find the compositions of equilibrium liquid and vapor phases at 94 oC and 1 bar
The system obeys Raoult’s and Dalton’s laws and its relative volatility is 3.0. The variation of vapor
pressure of the less volatile component with temperature is given by the expression
1750
log p oB = 7.620 −
T
o
where p B is in mbar and T in Kelvin. [Ans.: a) 90 0C, b) 98 oC, c) x = 0.206, y = 0.438]
5.3 From the vapor-liquid equilibrium measurements of three different binary solutions at 760 mmHg,
the relative volatilities at two different liquid compositions were calculated as follows:
system αAB at x = 0.3 αAB at x = 0.8

1 Ethylacetate(A)-Ethanol(B) 1.49 0.66
2 Methanol(A)-Water(B) 4.63 2.69
3 Etyhlenedichloride(A)-Benzene(B) 0.898 0.902
Which of these three systems shows azeotropism between the given concentrations, why?
5.4 1 200 kg n-propyl benzoate (M.W.= 164 ; b.p.=231 oC) at 20 oC, will be purified from very small
quantity of non-volatile impurities, with steam distillation in a jacketed vessel equipped with a
condenser and a decanter. Water at 20 oC will be continuously supplied to the vessel to maintain a
liquid water level. N-propyl benzoate is insoluble in water. Distillation is to be carried out at 760 mm
Hg pressure.
Calculate:
a) The temperature at which distillation will proceed,
b) The amount of water to be used,
c) The heating steam requirement. Steam is saturated at 40 kN/m2 gauge pressure and condenses in the
jacket.
Temperature ( oC) 97.93 98.62 99.31 99.66 99.83 110

Water p oA (mmHg) 705.69 723.44 741.56 751.47 755.40 1060
(A)
λA (kJ/kg) 2267 2238
n-Propyl p o (mmHg) 7.89 8.17 8.46 8.53 8.68 -

B
benzoate
(B) λB (kJ/kg) - - - 352.2 - -
Over the temperature range of operation specific heats of water and n-propyl benzoate may be taken as
4.18 kJ/kgK and 1.87 kJ/kgK.
5.5 An acetone-water solution containing 60 % acetone by weight is separated by flash distillation at

atmospheric pressure in two equilibrium stages. Half of the solution (by weight) is vaporized in the
first stage, the remaining liquid solution being passed to the second stage, where its temperature is
raised to 80 oC.
a) Determine the temperature in the first stage, and the fractional vaporisation in the second, together
with the compositions of vapor and liquid in each stage.
b) What is the percentage recovery of the acetone in the two vapor products together?
Equilibrium data for acetone-water at atmospheric pressure is given below, where x and y show the
mass fractions of acetone in liquid and vapor respectively. [Ans.: a) 67.5 oC, ε2 = 0.28, b) 94 %]
t(oC) 100 88.2 80 71.9 67.6 65.2 63.4 62.0 60.8 59.7 58.2 56.4
x 0 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.0
y 0 0.623 0.784 0.876 0.91 0.925 0.933 0.94 0.946 0.953 0.963 1.0
5.6 A binary liquid solution containing 36 mole percent MVC is to be flash-distilled at constant
pressure. The flow rate of the feed is 55 k-mol/h and 47 percent of this will be vaporized. The relative
volatility of the MVC to the LVC is constant at 12.5 at the operating concentration range. Calculate:
a) The compositions of top and bottom products,
b) The percentage recovery of the MVC. [ Ans. a) yD = 0.63, xw = 0.12 ]
5.7 Cumen is an important precursor for the production of phenol and acetone. It is produced by the
catalytic reaction between benzene and propylene. Composition of the mixture leaving the catalytic
reactor is given below;
Propane 40.0 mole percent
Propylene 2.0 mole percent
Benzene 27.0 mol percent
Cumen 30.0 mole percent
Less volatile organics 1.0 mole percent
In order to separate cumen from the others, first flash distillation is used to remove the propane and
propylene, later benzene is recovered and recycled.
Calculate the loss of benzene and cumen if the above-given mixture is flash-distilled at 2.4 bar
constant pressure to remove the 90 mole percent of the propane. Assume that Raoult’s and Dalton’s
laws are applicable. The vapor pressures of the components as atm are given at three different
temperatures in the table below:
Temperature,oC 37.8 65.6 93.3

Propan 12.8 23.3 39
Propylene 15.3 27.6 46
Benzene 0.217 0.62 1.45
Cumen 0.013 0.05 0.16
5.8 A 60 k-mol/h liquid solution which is at 25 oC, contains 32 mol percent ethylene glycol (EG) and
68 mol percent water (W). This solution will be flash- distilled at 1.013 bar constant pressure.
For a fractional vaporization of 0.50 calculate:
a) The flash temperature,
b) The compositions of top and bottom products,
c) The percentage recovery of EG. (EG is recovered in bottom product)
5.9 A 40 k-mol liquid solution containing 45 mol percent acetaldehyde (AL) and 55 mol percent
ethanol (ET) will be subjected to differential (simple) distillation at 1.013 bar pressure. Operation will
be stopped when the mol fraction of AL in the still drops to 0.15.
a) Find the temperature of the still at the end of the operation,
b) Calculate the average composition of distillate,
c) Find the percentage recovery of AL.
5.10 a) Derive the following equation for simple (differential) distillation of a binary solution, whose
vapor-liquid equilibrium may be given as y*= mx (m is a constant, x,y are mole fractions) , starting
1
F ⎛ xF ⎞ m −1
=⎜ ⎟⎟
W ⎜⎝ x w
with Rayleigh Equation. where, F and W are the total moles of the feed
⎠
(charge) and bottom product, xF and xw are the mole fraction of the MVC in the feed and bottom
product respectively.
b) A 80 k-mol binary solution containing 23 mole percent MVC will be subjected to simple distillation
at 760 mmHg. Distillation will be stopped when the mole fraction of the MVC in the batch-still drops
to 0.03.
Calculate the average composition of top product (distillate) and percentage recovery of the MVC.
c) If the same solution is subjected to flash distillation under the same conditions with the same
percent of vaporization, what will be the purity of the top product and the percentage recovery of the
MVC?
d) Compare the results in b) and c) and comment on!
Within the concentration range involved vapor-liquid equilibrium at 760 mmHg may be given as
y*=6.5x, where x and y are mole fractions.
5.11 60 k-mole acetone-water solution, containing 40 mole percent acetone will be distilled in a batch
still at 760 mmHg. Distillation will be stopped when the mole fraction of acetone in the batch still
drops to 0.05.
Calculate:
b) The mole fraction of acetone in the distillate (purity),
c) The percentage recovery of acetone,
d) If the same percent of vaporization is affected in a single stage by flash distillation at the same
pressure, what will be the purity and percentage recovery of acetone?
5.12 It is desired to obtain an ortho-cresol product in 95 % purity by mole by simple distillation of a
solution containing 65 mole percent ortho-cresol and 35 mole percent phenol. Show that the ortho-
cresol recovery is trebled by using a partial condenser to condense 75 % of the vapor and continuously
returning this back to the still (reflux liquid), rather than using conventional batch-still.
Assume that the hold-up in the condenser is negligible, and that condensate is in equilibrium with the
remaining vapor. The equilibrium relation at the operating pressure and over range of concentration is
represented by the equation: y = 0.015 x + 0.05 where x and y are mole fractions of phenol in liquid
and vapor.
5.13 A binary liquid solution at 15 oC containing 45 mole percent benzene and 55 mole percent
heptane is to be fed to a rectification column which will operate at atmospheric pressure. It is required
to produce a top product containing not more than 5 mole percent heptane.
a) Calculate the minimum reflux ratio,
b) What will be the composition of the bottom product, if the top product flow rate is 40 % of the feed
rate?
Latent heat of vaporization of the solutions may be considered constant at 23 000 kJ/k-mol. The
average specific heat of the feed over the required temperature range is 185 kJ/k-mol oC.
5.14 A solution of benzene and methylisobutylketone (MIBK) containing 60 mole percent benzene is
to be separated by rectification in a sieve-plate column operating at atmospheric pressure. The feed is
40 mol percent vapor 60 mole percent liquid and 97 % of its benzene content is to be recovered in the
top product, which should contain 95 mole percent benzene. The column is to be equipped with a
partial condenser and a recirculation reboiler in which 25 % of the recirculated liquid is to be
vaporised. The feed rate is 400 k-mol/h and it is suggested to operate the column at a reflux ratio 1.3
times its minimum value. Determine:
a) the composition of the bottom product,
b) the composition of vapor entering the condenser and of the reflux liquid entering the column,
c) the composition of vapor entering the column and of the liquid leaving the bottom plate,
d) the heat loads of the reboiler and condenser.
The molar latent heat of vaporization is constant at 32 000 kJ/k-mol
[Ans.: a) xw = 0.046, b) y1 = 0.905, xo = 0.85 c) yN+1 = 0.092, xN = 0.072]
5.15 An ethyl acetate-acetic acid solution, containing 35 mole percent ethyl acetate will be rectified in
a plate column operating at 760 mmHg. The column will be equipped with a total condenser and a
total reboiler. The feed will be introduced as liquid-vapor mixture in which mole fraction of liquid is
0.65. 96 percent of the ethyl acetate in the feed will be recovered into the top product which will
contain 95 mole percent ethyl acetate. A reflux ratio of 1.50 times the minimum reflux ratio will be
selected as operating reflux ratio.
For a feed flow rate of 220 k-mol/h :
a) Calculate the flow rates of top and bottom products.
b) Write the equations of q-line, and enriching and stripping section operating lines.
c) Find the number of the ideal plates by using McCabe-Thiele Method.
d) Calculate the condenser and reboiler loads (duties) as kW.
Molar latent heats of vaporization of both components are the same at 28 500 kJ/k-mol.
5.16 A plate rectification column is to be designed to separate a 12 500 kg/h ethyl acetate-acetic acid
solution, which is at 25 oC and contains 44 mass percent ethyl acetate. The column will operate at 760
mmHg top pressure. 91 percent of the ethyl acetate in the feed is to be recovered in 96.5 mass percent
purity. A reflux ratio which is 1,50 times the minimum is to be selected for the operation. The column
will be equipped with a total condenser and a kettle-type reboiler.
Average latent heat of vaporization of the solution remains constant at 28 500 kJ/k-mol. Liquid heat
capacities of ethyl acetate and acetic acid at 60oC are 2.06 kJ/kg oC and 2.21 kJ/kg oC respectively.
a) Calculate the flow rates of top and bottom products as kg/h and k-mol/h and their compositions as
mass and mole percent.
b) Find the minimum reflux ratio from xy-diagram and Underwood equation and compare them.
c) Find the minimum number of the ideal plates needed from xy-diagram and Fenske equation and
compare the two values.
d) Find the number of the ideal plates needed by using Mc Cabe-Thiele method.
e) Estimate the number of the ideal plates needed from Gilliland and Erbar-Maddox correlations and
compare these with the value in section d).
f) Find the compositions of liquid and vapor phases around each ideal plate and show them on a
schematically drawn plate column.
g) Find the temperature of each ideal plate and write these on the schematic column above.
h) Calculate the quantities of ethyl acetate and acetic acid transferred between liquid and vapor phases
on each ideal plate as kg/h and make a table with them.
i) Estimate the number of the real plates from O’Connell’s correlation. At column average temperature
viscosities of ethyl acetate and acetic acid are 0.21 cP and 0.47 cP.
j) Calculate condenser and reboiler loads as kW.
5.17 A continuous rectification column is used to separate a binary solution. Enriching and stripping
section operating lines for this operation are given as;
yn+1 = 0.739 xn + 0.226

ym+1 = 1.28 xm - 0.0143
where x and y are the mole fractions of the MVC in liquid and vapor phases and, n and m show any
plate in the enriching and stripping sections respectively.
Feed flow rate is 75 k-mol/h and it contains 42 mole percent MVC. Heat added in the reboiler
(reboiler load) is 1 300 kJ/s. Constant molar over-flow is applicable and latent heat of vaporization of
the solution is 32 000 kJ/k-mol.
Calculate:
a) The mole fraction of the MVC in the top and bottom products and their flow rates,
b) The thermal condition of the feed,
c) Condenser load. Condenser is a partial condenser, it condenses only the part of the vapor required
as reflux liquid. [Ans. : a) xD = 0.866, xw = 0.051, D = 34.05 k-mol/h, W = 40.95 k-mol/h]
5.18 An existing column providing 7 equilibrium plates and equipped with a kettle-type reboiler and a
total condenser is being considered for the separation of 100 k-mol/ h saturated aqueous methanol
solution containing 40 mole percent methanol. Operation will be carried out at atmospheric pressure
and 95 percent of the methanol in the feed is to be recovered in 98 mole percent purity. The feed can
be introduced at any point and the column will be operated at whatever the reflux ratio is required to
produce both the purity and the recovery specified.
Assuming constant molar over-flow,
a) Calculate the necessary rate of vapor production in the reboiler as k-mol/h,
b) What would be the percentage recovery of methanol at the same purity if reboiler capacity were
limited to 90 k-mol vapor/h.
5.19 Fruit juice concentrates are prepared commercially by evaporation. But during the evaporation
flavoring volatile components are lost with the vapor. In order to recover these flavoring components,
saturated vapor coming from the evaporator is sent to a rectification column where essence is
withdrawn at the top as liquid. The most important flavor component in the vapor coming from grape
juice concentrating evaporator is methyl anthranilate, which is known to occur at 2*10-7 mole fraction
in the vapor. 90 percent of this component is to be recovered in a plate rectification column as top
product with 99 mole percent purity. Assuming constant molar over-flow;
a) Calculate minimum steam generation in the reboiler as k-mol per k-mol of feed to the column.
b) If the steam generation in the reboiler is 40 % greater than the minimum steam generation, what is
the number of the equilibrium plates needed for the specified recovery?
Due to the low concentration of the other volatile flavor components, feed to the column may be
treated as binary system consisting only of methyl antranilate and water vapor, and relative volatility
of methyl antranilate to water at high dilution is 3.5. [Ans.: a) G / F = 12 ]
5.20 An ethanol- propanol solution is to be separated in a plate rectification column at atmospheric
pressure. The feed is 40 mole percent vapor and contains 45 mole percent ethanol. 95 % of the ethanol
should be recovered in the top product, which should be 92 % pure by mole. The column is provided
with a partial condenser and a kettle-type reboiler, both of which have Murphree vapor phase
efficiencies of 100 %. If the feed rate is 250 k-mol/h, the overall column efficiency is 60 % and the
reflux ratio is set at 1.4 times its minimum value, calculate:
a) The composition of the bottom product,
b) The number of the real plates required in the column, assuming that feed plate is located optimally,
c) The duty of the condenser in kW.
The system may be assumed to have a constant relative volatility of 2.1 at the operating pressure.
Latent heat of vaporization of the solutions may be assumed constant at 47 000 kJ/k-mol.
5.21 It is required to design a rectification column to separate methanol from water at atmospheric
pressure. The following table gives the design requirements for the feeds and products;
Stream Quality Flow rate, k-mol/h Methanol mol fraction

Feed-1 Saturated vapor 400 0.50
Feed-2 Saturated liquid 200 0.30
Top product Saturated liquid 150 0.96
Bottom product Saturated liquid 0.04
Side product Saturated liquid 0.70
The column has a total condenser and a reboiler. Assuming constant molar over-flow;
a) Calculate the minimum reflux ratio,
b) For a reflux rate of 400 k-mol/h to the top plate, find the total number of the equilibrium plates
needed, the number of the plates to which each feed should be introduced and that from which the side
stream should be withdrawn and vapor flow rate to the column.
5.22 In the continuous rectification of methanol/n-propanol solution in a plate column operating 760
mmHg, the mole fractions of methanol in the liquid samples taken from the exit of the 1st, 2nd and 3rd
plates are measured as 0.88, 0.70 and 0.45 respectively under the total reflux conditions.
Calculate the Murphree liquid efficiencies of the three plates. The mole fraction of methanol in the
vapor going to the condenser is 0.95.
5.23 A batch of 10 000 kg sulfur dichloride(SCl2)- carbon tetra chloride(CCl4) solution at 25 oC and
containing 40 mass percent SCl2, will be rectified in a batch column at 760 mmHg, to produce a top
product of 90 mole percent SCl2. The operation will be carried out keeping the top product
composition constant and increasing the reflux ratio steadily until the mole fraction of SCl2 in the
batch-still drops to 0.15. The reflux ratio at the last moment of the distillation will be 20 % greater
than the minimum reflux ratio corresponding to the 0.15 mole fraction of SCl2 in the batch-still.
Calculate:
a) The number of the equilibrium plates needed.
b) The reflux ratio at the start of the distillation.
c) The total heat energy requirement.
d) The time of duration of one batch operation, for the conditions : heat transfer area in the batch-still
is 5 m2, over-all heat transfer coefficients for the heating and vaporization periods are 300 W/m2K and
750 W/m2K, and the heating is affected by the condensation of saturated steam at 1 atm absolute
pressure in the coils.
Specific heat and latent heat of vaporization of the solution may be taken constant at 125 kJ/k-moloC
and 30 000 kJ/k-mol over the operating temperature range.
5.24 A packed rectification column is to be designed to separate an equimolar solution of benzene and
toluene to obtain products of 95 percent purity at 760 mmHg. The feed is to be introduced as saturated
liquid. For the conditions stated HG= 0.5 m and HL=1.0 m. For a reflux ratio 25 % greater than the
minimum and assuming constant molar over-flow calculate;
a) NL, NG and NOG,
b) The heights of packing required for each section of the column.
5.25 A Plate lay-out for the internal design of a sieve-plate gas absorption column for gas and liquid
flow rates of 4.2 kg/sec and 6.1 kg/sec respectively, is assumed as follows: P.S. = 0.45 m, dh = 6 mm,
□ PT = 3 dh , hw = 50 mm, Lw/Dc= 0.705.
a) Calculate the diameter of the column for this lay-out, assuming a percent of flooding of 70.
b) Find out whether weeping will occur or not. If yes, what would you change in the assumed plate
lay-out?
c) Calculate the total pressure drop in the gas per plate.
Densities of liquid and gas and surface tension of the liquid are: 850 kg/m3, 2.2 kg/m3 and 0.40 N/m
respectively.
5.26 Design the enriching section of the column given in Problem.5.16) with the values at the top
plate. The thickness of the plates will be 5 mm. At the temperature of the top plate the densities and
surface tensions of the ethyl acetate and acetic acid are 825 kg/m3, 984 kg/m3, 0.017 N/m and 0.022
N/m respectively.
Chapter-6
LIQUID-LIQUID EXTRACTION
6.1 Introduction: Liquid-liquid extraction or solvent extraction, which is a mass

transfer operation, is used to separate liquid solutions. In this operation, the solute A,
which is dissolved in solvent C, is transferred into a new solvent B, which is either
insoluble or partially soluble in solvent C. Solvent C is named as raffinate solvent and
solvent B as extract solvent or simply the solvent. The limited solubilities of solvents
constitute the basis of this operation. Thus formed two liquid layers, each containing
all the components to different extend, in the case of partial solubility, separate from
each other due to the density difference. The layer, which contains extract solvent
more than raffinate solvent is called as extract phase and the other layer, which
contains the raffinate solvent more than extract solvent, is called as raffinate phase.
Raffinate or extract phase may be denser depending upon the conditions. The best
condition is attained when the extract and raffinate solvents are completely insoluble,
but this is a rather rare case. In most of the cases, the two solvents are partially soluble
within each other and hence all the components exist in each phase. If the contact time
of the two phases is long and/or the intensity of mixing is high, the two phases reach in
equilibrium. At equilibrium, the ratio of A to C in the extract phase is greater than that
of in the raffinate phase and as a result of this the separation of solute A from raffinate
solvent C occurs at certain degree. Repeating the contact with solvent B, separation
can be further increased. As it is seen, the liquid-liquid extraction is not a final
separation operation since the solute A must be separated from the new solvent B,
which is mostly done by rectification. It may be then asked: “why the solution of
A+C is not separated by direct application of rectification”. The answer to this
question is: “because of either physical impossibilities or economic
considerations”. Physical impossibilities occur, when the solution of A+C has
azeotropic point. In this case, by changing the solvent of the solution, azeotropism is
removed. Another example for physical impossibilities is the solution of heat sensitive
components. For example, if solute A is a heat sensitive material and the boiling point
of solvent C is high and the solution is dilute in A, the boiling point of the solution will
be inevitably high, which causes the decomposition of solute A at direct rectification
of the solution. Instead of rectifying the solution of A+C, rectifying the solution of
A+B, after replacing solvent C by new solvent B, which has relatively low boiling
point, prevents the decomposition of solute A during rectification. At some cases, the
solvent extraction followed by rectification may be more economic than the direct
rectification of the solution. This occurs, when the solution A+C is dilute in
component A, component C is the MVC and the latent heat of vaporization of which is
relatively high. In this case solvent C is first replaced with a new solvent B by solvent
extraction, which is more volatile than A and has a very low latent heat of vaporization
and then solute A is separated from solvent B by rectification. Although another
separation operation is added, the cost of recovery of unit amount of solute A is lower
than that of direct rectification due to the reduced energy requirement.
Liquid-liquid equilibria are required to understand and to design any solvent extraction
operation as the mass transfer in this operation is between two insoluble liquid phases.
6.2 Liquid-Liquid Equilibria: Certain quantities of liquids A, B and C are mixed
thoroughly until the equilibrium is attained and then the samples are taken from the
two layers, which form after stopping the mixing. By analysing the samples; x, xB and
xC ,which are the mass fractions of components A, B and C respectively in the
raffinate phase and y, yB and yC which are the mass fractions of the same components
in the extract phase are determined. By repeating the experiments at different
proportions of components A, B and C in the same way, a table is formed as shown
below. (Notice that the mass fractions having no subscript are the mass fractions of
solute A). As the solubilities change with temperature, the temperature is kept constant
R a f f i n a t e phase E x t r a c t p h a s e
x xB xC y yB yC
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
during the experiments and this temperature is reported with the experimental results.
The graphical representation of the results can be done on xy-type diagrams, when the
two solvents are completely insoluble within each other (in this case all the xB and yC
values are zero). This type of
representation is obtained by carrying
Weight ratio in extract phase, Y'=y /1-y
t = cons. X′ = x / x values against Y' = y/yB values

c
on a millimetric paper as shown in Fig.6.1.
Notice that X′ and Y′ are weight ratios. If
all the three components exist in both
phases, xy-type diagrams cannot be used
for the representation of equilibrium.
Ternary diagrams may be used. The right
angle triangular diagrams are preferred to
the equilateral triangular diagrams, as for
0.0 which special millimetric papers are
0.0 Weight ratio in raffinate phase, X'=x /1-x
required and enlargement of part of it is
Fig.6.1 Liquid-liquid equilibrium when B rather difficult. As shown in Fig.6.2, the
and C are insoluble within each other apexes of the triangle represent pure
components, the sides the binary liquid
mixtures of the components represented by
the two apexes and the points in the triangle, the ternary liquid mixtures. As
xC = 1-(x+xB) and yC = 1-(y+yB), there is no need for the representation of the mass
fractions of component C on the diagram. On these diagrams, graphical additions and
subtractions can be done. For example, if a ternary liquid solution represented by point
L is added to another ternary liquid solution given by point G, the resultant solution,
which is represented by point M is always on the straight line joining L and G. Point
M can be located by applying inverse lever-arm rule to the LG line, which is written as
A
Mass fraction of A in extract phase,y

1.0 1.0
Mass fractions of A in raffinate
and extract phases, x,y
0.5 G 0.5
M G1
L1
L
∆
0.0 B 0.0
C 0.0 0.5 1.0 0.0 0.5 1.0
Mass fractions of B in raffinate and Mass fraction of A in raffinate phase, x
extract phases, xB,yB
Fig.6.2 (a) Right angle triangular diagram, (b) distribution diagram
L * LM = G * GM , where L and G shows the quantities of liquids as kg. Similarly, if

from a ternary liquid solution represented by point L1, a ternary liquid solution
represented by point G1 is subtracted, the remaining liquid solution, which is
represented by point ∆ is always on the extension and beyond the point L1 of the
straight line joining L1 and G1. Inverse lever-arm rule written for line G1∆, point ∆
being the support point, locates the ∆ point.
The solubility diagram of the system is obtained by carrying x values against xB and
y values against yB from the table. Next to this diagram, the distribution diagram of
the system, which is plotted by carrying the values of x against the values of y, and
required to find the extract and raffinate phases at equilibrium is also plotted. By
plotting the experimentally found values of various ternary systems, two types of
solubility and distribution diagrams shown in Fig.6.3 and 6.4 were obtained. In the
ternary system shown in Fig.6.3, only one pair (pair of B-C) has partial solubility. The
other two pairs (pairs of A-B and A-C) dissolve within each other at any proportions.
Any point under the solubility curve such as point M shows heterogeneous ternary
mixtures and any point outside the curve shows homogeneous ternary solutions.
Accordingly, point J represents a binary heterogeneous mixture, which separates in
two binary homogeneous solutions represented by points R and T, whose compositions
can be directly read from the solubility diagram and their quantities are calculated by
applying inverse lever-arm rule to the line RJT. Point R gives the maximum solubility
of B in C, and point T the maximum solubility of C in B. The heterogeneous ternary
mixture represented by point M gives two homogeneous ternary solutions represented
by points G and L upon settling. Since they will be in equilibrium, they are located by
drawing the tie line passing through point M by trial and error with the help of
distribution diagram. Since the solution represented by point L is richer in the raffinate
solvent, it is called raffinate phase and the other phase, which is richer in the extract
solvent, is called extract phase. While the compositions of extract and raffinate phases
obtained are directly read from the solubility diagram, their amounts are found by
y
A
1.0x,y 1.0
Distribution curve x=y
xP=yP
P
yP
G P
y y
M G,L
Raffinate Extract phase curve
phase curve
L Tie line
x x
xB
0.0
B 0.0 x
C 0.0
R
yB J T 1.0 0.0 x xp 1.0
xB,yB
(b)
(a)
Fig.6.3 (a) Solubility, (b) Distribution diagram for one pair partially soluble system
applying inverse lever-arm rule to the line LMG. The part of the solubility curve
bounded by RLP represents raffinate phases; the remaining part represents extract
phases. Point P, at which the compositions of both phases are the same, is known as
plait point. The tie line reduces to a point at plait point. As it is seen from Fig.6.3b,
y/x ratio which is given by K and known as distribution coefficient is greater than 1.
This means that solute A prefers solvent B rather than solvent C.
In the ternary system shown in Fig.6.4, two pairs (pairs of A-B and B-C) are partially
y
A
1.0 1.0
x,y
U
x=y
Raffinate phase curve
L x
x
M V
Extract phase curve
Tie line Distribution curve
G y
y
0.0 G,L
B 0.0 x
C 0.0
R xB J T yB 1.0 0.0 x 1.0
xB,yB
(b)
(a)
Fig.6.4 (a) Solubility, (b) Distribution diagram of two pairs partially soluble system
soluble and the other pair (pair of A-C) is soluble at any proportions. Points U and V
show the maximum solubilities of A and B within each other. Any point between two
curves represents heterogeneous mixtures and any point outside the curves gives
homogeneous solutions. The tie line passing through point M locates the equilibrium
extract and raffinate phases, which will be obtained upon the settling of ternary
heterogeneous mixture represented by point M. RLU curve represents raffinate phases
and the TGV curve the extract phases. In this case, distribution coefficient K is smaller
than 1, which means preference of solute A is at raffinate solvent side.
The liquid-liquid equilibria are also represented on so-called solvent-free coordinated
diagrams, which involves first expressing of compositions of extract and raffinate
phases on solvent-free bases and then plotting them on xy-type diagram. This type of
diagrams is especially useful for two pairs partially soluble systems, as their extract
phase curves, which are rather short in right angle triangular diagrams, can be
extended to any value on these coordinates. For this, first the compositions of
components A, B and C are expressed by excluding solvent B in the denominators as
x'= x/(x+xC), x ′B = xB/(x+xC) and x ′C = xC/(x+xC) in the raffinate phase and as
y'= y/(y+yC), y′B = yB/(y+yC) and y′C = yC/(y+yC) in the extract phase and then by
carrying x ′B values against x' values and y′B values against y' values, raffinate and
extract phase curves are plotted as shown in Fig.6.5. Below this diagram, by plotting x'
values against y' values another diagram is also drawn, which is used to draw the tie
lines on the diagram above. Any point
t =cons.
between extract and raffinate curves,
y′B − y′ Extract phase curve such as point M represents
T
G y ′
B heterogeneous ternary mixture, which
y′B V upon settling gives equilibrium
Tie line extract and raffinate phases, which
x ′B
M
are located on the diagram by
R
drawing the tie line passing through
x ′B point M by trial and error with the
L U help of diagram below. While their
x ′B − x ′ Raffinate phase compositions are directly read from
curve the diagram, their amounts are
0 x′ y ′ 1.0 calculated by applying inverse lever-
x ′, y′ arm rule to the line LMG.
6.3 Selection of Solvent: In many
1.0
cases, there is more than one solvent
y′ that can be used for a specific
extraction operation. The following
L,G y =x properties of the solvents are looked
y′ at to select the best one among the
potential solvents: 1o) Selectivity of
solvent (β): It is defined as the ratio of
y/yC to x/xC at equilibrium, and is the
0 separation power of solvent B of
0 x′ 1.0
solute A from raffinate solvent C.
x′
Whatever is the α in rectification is
Fig.6.5 Liquid-liquid equilibrium on
solvent-free coordinates
the β in extraction. If β =1, this solvent has no selectivity for solute A and hence it
cannot be used for the extraction. Higher the value of β easier is the separation of
solute A from solvent C.
y/yC
β= (6-1)
x/x C
2o) Distribution coefficient (K): It is defined as K= y/x and it should be as great as
possible to accomplish the given extraction with small amount of solvent usage,
although it is not necessary that it should be greater than 1. 3o) Insolubility of solvent:
the selected solvent should have no or low solubility in raffinate solvent to minimize
the solvent losses, otherwise another rectification column is to be used to recover the
solvent dissolved in raffinate solvent. 4o) Separation of solvent from solute: as it is
stated before, the solution after extraction is separated by rectification. Hence, selected
solvent should not form azeotropic solution with solute A and when it is possible, the
relative volatility of this solution should be high. 5o) Density of solvent: for the
separation of extract and raffinate phases, density difference should exist between the
phases. Hence, the density of selected solvent should be different than the density of
raffinate solvent. 6o) Interfacial tension: in the extraction operation, one of the phases
is dispersed first in the other phase as small droplets by intensive mixing and then by
allowing the settling, the coalescence occurs. Interfacial tension between the liquids
plays an important role in dispersion and coalescence. Low interfacial tension means
easy dispersion but difficult coalescence. As short coalescence time is preferred,
selected solvent should have high interfacial tension with the raffinate solvent. 7o)
Chemical stability: as the solvent is recovered by rectification and re-used many times
and during which it is heated and cooled repeatedly, it should be chemically stable so
that no decomposition should occur. 8o) Other properties: whenever possible selected
solvent should have low viscosity and vapor pressure, should be non-toxic, should not
catch fire easily and should have low unit cost.
6.4 Extraction Operations: Extraction operations are carried out either as stage-wise
contact type of operation or continuous contact type of operation in practice.
6.4.1 Stage-Wise Operations: In the stage-wise contact type of operations, the two
phases come in contact for a certain time, during which mass transfer takes place
between the phases and then the two
Feed
phases separate out. The mixer-
Solvent,S,ys
F, xF settler unit shown in Fig.6.6 is a
typical stage-wise contact type of
equipment used in extraction
operations. The equipment, which
consists of two main sections, one
Extract
Mixer
phase,G,y
being mixing and the other settling
section, can be constructed as single
piece of equipment as shown in the
Raffinate Figure or, as two separate units. In
phase,L,x
Settler the mixing section, the two phases
are mixed thoroughly with the help
of a stirrer to disperse one of the
phases as small droplets in the other
Fig.6.6 Mixer-settler unit
Exit of light phase Exit of light phase
Heavy Heavy
Exit of heavy
Main phase phase
phase
interface
Dispersed
Perforated
light phase
plate
Coalesed
Perforated heavy phase
plate Down-comer Up-comer
Dispersed
Coalesed heavy phase
light phase
Light
Main
phase
interface
Light
phase Exit of
heavy
phase
(a) (b)
Fig.6.7 Perforated plate extraction column : a) light phase dispersed,

(b) heavy phase dispersed
phase during which main part of mass transfer occurs between the phases. If the
mixing time is enough, the two phases reach in equilibrium and the unit is then known
as equilibrium unit or equilibrium stage. The heterogeneous mixture then flows into
settling section of the unit, where coalescence of the drops occurs and the two phases
separate out and leave the unit through different channels. Operation is carried out in
continuous way, at which the feed and solvent are continuously pumped to the mixing
section and the extract and raffinate phases are withdrawn from the settling section
continuously.
Mixer-settler units are the only extraction equipment for single stage or cross-current
multi-stage operations. In the multi-stage counter-current operations perforated-plate
columns can also be used next to the mixer-settler units. These columns are similar to
the sieve-plate columns used in gas absorption and rectification operations but they
don’t have weirs. The light or heavy phase may be dispersed depending upon the
conditions. In Fig.6.7, two perforated plate extraction columns are shown in which
light and heavy phases are dispersed.
6.4.1.1 Single Stage Extraction: The amounts of raffinate and extract products and
their compositions can be calculated by simultaneous solution of the equilibrium
relationship and the total and components balance equations which can be written
along the equilibrium mixer-settler unit shown in Fig.6.8 as;
Total material balance: F+S = M1 = L1+G1 (6-2)
Solute A balance: FxF + Sys = M1xM1 = L1x1 +G1y1 (6-3)
Solvent B: FxFB+ SysB = M1xM1B = L1x1B + G1y1B (6-4)
where F and S are the amounts of feed and solvent as kg, if the operation is carried out
batch-wise, and the flow rates of the feed and
Extract solvent as kg/s, if the operation is conducted
product, G1,y1 continuously. When the solvent does not
Solvent, S,ys
contain solute A then ys=0. Points F and S can
1 easily be located on the diagram as their
compositions are known. It follows from
Feed, F,xF Fig.6.9 that the feed is a binary solution of A
Raffinate
product, L1,x1 and C and the solvent contains small amount
of solute A. Then either by applying inverse
Fig.6.8 An Equilibrium Stage
lever-arm rule to the line FS or by solving the
left hand side of equation (6-3) point M1 is
located. By drawing the tie line passing through point M1 by trial and error, points L1
and G1 and hence raffinate and extract products are located. While the compositions of
y
A
1.0 1.0
x,y
x=y
Gm
P
P
y1 G1 y1
xF F G1,L1
xM1 D
M1
x1 L1 x1
E
yS Lm S
0.0 B 0.0 x
0.0 x1B xM1B y1B ySB 1.0 0.0 x1 1.0
C xB,yB
(b)
(a)
Fig.6.9 Solution of single stage extraction
these products are directly read from the diagram, their amounts are calculated either
by applying inverse-lever-arm-rule to the line L1M1G1 or by simultaneous solution of
the right hand sides of equations (6-2) and (6-3). As it is seen, in the calculations the
stage is assumed as equilibrium stage.
For extraction operation, point M1 must lie always in the heterogeneous region. By
taking this fact into consideration, minimum and maximum values of solvent for a
given extraction can be calculated as follows: If the amount of solvent is reduced,
point M1 shifts toward point F. Hence point M1, coming to point D corresponds to the
minimum solvent quantity for the given extraction at which infinitely small amount of
extract phase shown by Gm is obtained. On the contrary, point M1 approaches to point
S with the increase in solvent amount. Hence point M1, coming to point E corresponds
to maximum solvent quantity for the given extraction at which infinitely small
amount of raffinate phase shown by point Lm is produced.
The percentage recovery of solute A into extract phase is given by;
Fx − L1x1
P.R. = F .100 (6-5)
Fx F
The percentage recovery of solute A into extract phase, in many cases, is rather small
in a single stage extraction. To increase this, more than one stage is connected in series
to form multi-stage cascades. As the connections of stages are done in two different
ways, two different types of operation are possible.
6.4.1.2 Cross-Current Multi-Stage Extraction: In this type of operation, the solvent
is divided in parts and each part is mixed in a stage with the raffinate phase coming
from the previous stage to recover the solute, which is not recovered in the previous
stage. The flow diagrams in real and schematic showing are given in Fig.6.10 for
three-stage operation. As it is seen, the stages are numbered from left to right and the
phases and their compositions leaving any stage are shown by writing the number of
the stage as subscript. The analysis of cross-current multi-stage extraction is easily
done by repeating the equations written for single stage operation, for each stage.
Hence, total material and solute A balances for any stage (stage n) in the cascade;
S,ys
F,xF S1 L1,x1 S2 L2,x2 S3 Solvent S,ys
Feed S1 S2 S3 Solvent
Feed
3 1 2 3 L3,x3
1 2
F,xF L1,x1 L2,x2
Raffinate
G1 G2 G3 product
G1 G2 G3
y1 y2 y3 L3,x3 y1 y2 y3
G, y Raffinate G, y
product Extract
Extract G3
product product
y3
(a) (b)
Fig.6.10 Flow diagram of cross-current multi-stage extraction
Total material balance: Ln-1 + Sn = Mn = Ln + Gn (6-6)

Solute A balance: Ln-1xn-1 + Snys = MnxMn = Lnxn + Gnyn (6-7)
By substituting Lo = F and xo = xF, these equations for the first stage (n=1) becomes,
F + S 1 = M1 = L 1 + G 1
FxF + S1ys = M1xM1 = L1x1 +G1y1
Points F and S1 can be located on the diagram as their compositions are known. Then,
as explained above, points M1, L1 and G1 are located and the amounts of L1 and G1 are
calculated. By taking n=2, equations (6-6) and (6-7) can be written for stage two as;
L1 + S2 = M2 = L2 + G2
L1x1 + S2ys = M2xM2 = L2x2 + G2y2
From which it is seen that points L1, M2 and S2 should be on the same straight line.
Hence, after joining point L1 with point S2, point M2 is located on this line as
explained above. From the right hand sides of the equations above, it is understood
that points L2, M2 and G2 should be on the same straight line and in addition, points L2
and G2 must be on the solubility curve. Hence, by drawing the tie line passing through
point M2, points L2 and G2 are located and the amounts of L2 and G2 are calculated.
The solution is continued in this way until reaching the last stage as shown in Fig.6.11.
y
A
1.0 1.0
x,y
x=y
P
y1 G1
y1 P
xF F
M1 1
x1 L1 x1
y2 G2 y2
2
y3 M2 y3
G3
x2 3
x2
L2
x3 M3 x3
yS L3
S
0.0 0.0
0.0
B 0.0
x
1.0
C xB,yB
x3 x2 x1 1.0
(b)
(a)
Fig.6.11 Solution of three-stage cross-current extraction on right angle triangular diagram
The percentage recovery of solute A is calculated from,

Fx F − L N x N
P.R. = .100 (6-8)
Fx F
If the solution is done on solvent-free coordinated diagram; for any stage n;
Total material balance: L′n −1 + S′n = M′n = L′n + G ′n (6-9)
Solute A balance: L′n−1x ′n−1 + S′n y′s = M′n x ′Mn = L′n x ′n + G ′n y′n (6-10)
Solvent B balance: L′n−1x′(n−1)B + S′n y′sB = M′n x ′MnB = L′n x′nB + G′n y′nB (6-11)
' ' ' ' '
where L , G , S , M and F are the mass flow rates of the streams on solvent-free basis.
These equations for the first stage (n=1) by taking L′o = F′ and x ′o = x ′F can be
written as;
F′ + S1′ = M1′ = L1′ + G1′
F′x ′F + S1′ y′s = M1′ x ′M1 = L1′ x1′ + G1′ y1′
F′x ′FB + S1′ y′sB = M1′ x ′M1B = L1′ x1B ′ + G1′ y1B′
Points F and S are first located on the diagram with the help of their known
compositions as shown in Fig.6.12. Then point M1 is located on the line joining these
two points in the known way. By drawing the tie line passing through point M1, points
L1 and G1 are located. The compositions of these phases are read from the diagram and
the amounts of L1′ and G1′ are calculated in the known way. Equations (6-9), (6-10)
and (6-11) are then written for the second and third stages and the amounts of phases
leaving the stages and their compositions are obtained in the same way as explained
above. The percentage recovery of solute A is calculated from;
S t =cons.
F′x ′F − L′N x ′N
y'SB P.R.= .100 (6-12)
F′x ′F
y'B-y'
G3
y′B G2 G1 y'1B If the raffinate and extract
x ′B
solvents are completely insoluble,
M3 the solution is much simplified, as
2
3 the flow rates of raffinat and
1
M2 extract solvents, C and B, do not
x'3B M1 x'B-x'
L3 change from stage to stage. A
L2 component A balance around
L1
stage n is written as;
F
x'F y'2 y'1 C X ′n −1 + B n Ys′ = C X ′n + B n Yn′ (6-13)
'
0 x'3 y'S x2' y 3 x'1 1.0
x',y'
1.0 From which,
y' C Ys′ − Yn′
y'2 − = (6-14)
y' Bn X′n−1 − X′n
y =x
y'3 is obtained. This equation

represents a straight line on X'Y'-
diagram passing through points
0
( X′n−1 ; Ys′) and (X′n ; Yn′ ) with a
' ' '
F x3 x2 x1 1.0 slope of (-C/Bn), which is known
x' as operating line for stage n.
Fig.6.12 Solution of cross-current three-stage Remember that the equilibrium
extraction on solvent-free coordinated diagram relationship in this case is also
given on X'Y'-diagram. Hence,
solution is done as follows: first, equilibrium relationship is drawn on X'Y'-diagram,
then equation (6-14) is written for the first stage by taking X′o = X′F as;
C Ys′ − Y1′
− =
B1 X′F − X1′
with the known values, point (X′F ; Ys′) is located on the diagram and the line with
slope of (–C/B1) passing through this point is drawn. The coordinates of intersection
point of this line with equilibrium curve give X1′ and Y1′ . Then by writing equation (6-
14) for the second and subsequent equilibrium stages, the solution is continued in the
same way. In Fig.6.13, solution for a cascade containing three equilibrium stages is
shown.
The percentage recovery of solute A is computed from the equation below;
CX′F − CX′N X′ − X′N
P.R. = .100 = F .100 (6-15)
C X′F X′F
Y'
Y'1
Equilibrium curve
Y'2
slope= -C/B1
1
Y'3 slope = -C/B3
2
slope = -C/B2
3
Y'S
0.0
X'2 X'1 X'F X'
0.0 X'3
Fig.6.13 Determination of equilibrium stages at cross-current

multi-stage extraction when the solvents are insoluble
6.4.1.3 Counter-Current Multi-Stage Extraction: The stages may also be connected

in another way such that the two phases flow in counter directions as shown in
Fig.6.14. The counter-current operation has advantages over the cross-current
operation. For a fixed percentage recovery; number of the equilibrium stages required
is smaller at the same solvent rate or at a constant number of equilibrium stages
required solvent rate is less. n shows any stage, N shows the last stage of the cascade.
Extract product Solvent

G1, y1 G2, y2 G3, y3 Gn, yn Gn+1, yn+1 GN, yN S, yS
1 2 n N
F, xF L1, x1 L2, x2 Ln-1, x n-1 Ln, x n LN-1, xN-1 LN, xN
Feed
Raffinate product
∆ (+)
Fig.6.14 Flow diagram of counter-current multi-stage extraction
Total material and solute A balances along the cascade are written as;
Total material balance: F + S = M = LN + G1 (6-16)
Solute A balance: FxF+Sys= MxM = LNxN+ G1y1 (6-17)
These equations indicate that point M lies on the FS and LNG1 lines, hence at the
intersection point of these two lines. Equation (6-16) can also be written as;
F - G1 = LN - S = ∆s (6-18)
where, ∆s is the total net flow which remains constant along the cascade, hence
equation (6-18) can be generalized to;
F - G1 = Ln - Gn+1 = LN - S = ∆s (6-19)
If F > G1 or LN > S, the total net flow is from left to right as shown in Fig.6.14,
otherwise it is from right to left. It is seen from equation (6-19) that point ∆s will be the
intersection point of the lines FG1 and LNS.
y
A
1.0 1.0
x,y
P
y1
G1 y2
xF F 1 x=y
G2
2 x1
L1 M y3
G3
x2
L2
3 G4
y4
L3 4 x3
∆S x4
0.0 LN=L4 S
B 0.0 x
C 0.0
xB,yB
1.0 0.0 x4 x3 x2 x1
Fig.6.15 Solution of four-stage counter-current extraction on right angle triangular diagram
With the help of equations given above the number of the equilibrium stages required
for a given extraction can be calculated on the equilibrium diagram of the system as
follows: Points F, S and LN are first located on the solubility diagram in Fig.6.15 as
their compositions are known . Notice that point LN should be on the solubility curve.
By joining points F and S, point M is located on this line in the known way. Then
point LN is joined with point M and is extended until cutting the solubility curve,
which gives point G1. Point G1 is joined with point F and extended; point S is joined
with point LN and extended. The intersection point is ∆s. Now drawing of equilibrium
stages can be started. By drawing the tie line passing through point G1, point L1 is
located; this tie line shows the first equilibrium stage in the cascade. According to
equation (6-19) points ∆s, L1 and G2 must be on the same straight line; in addition
point G2 must lie on the solubility curve, hence by joining points ∆s and L1 and
extending the line, point G2 is found. The raffinate phase L2, which is in equilibrium
with extract phase represented by point G2 can be found by drawing the tie line
passing through point G2. Then returning back to the point ∆s and joining it with point
L2 and extending the line, point G3 is located. The drawing is continued in this way
until reaching the point LN; once drawing the tie line once drawing the operating line
(the lines drawn from point ∆s are known as operating lines). The number of the tie
lines drawn gives the required number of the equilibrium stages for the given
extraction.
After computing the amount of extract product G1 by applying inverse lever-arm rule
to the line LNMG1, the percentage recovery of solute A is calculated from;
Fx F − LN x N
P.R. = .100 (6-20)
Fx F
For the solution of the problem on the solvent-free coordinated diagram; total
material balance on solvent-free basis and the solute A balance along the cascade can
be written as;
F' + S' = M' = G1′ + L′N (6-21)
F′x ′F + S′y′s = M′x ′M = G1′ y1′ + L′N x ′N (6-22)
Equation (6-21) can also be written as,
F′ − G1′ = L′n − G ′n +1 = L′N − S′ = ∆′s (6-23)
This means that total net flow on solvent-free basis remains constant along the
cascade.
If the feed does not contain any solvent then F' = F and if the solvent is pure, S' = 0,
S' y′s = 0, F' = M', X′F = X′M .
The solution on solvent-free
y'SB S
coordinated diagram of the system
is done as follows: first, points F, S
y′B
G3
G2
and LN are located on the diagram
G1 y'1B with the help of known
x ′B compositions (in Fig.6.16). Points
3
y'B-y' F and S are joined and point M is
2
located on this line in the known
M 1
way. By joining points LN and M
and extending this line, point G1 is
L3 LN L2
L1 located. According to equation (6-
x'N
'
x B-x ' 23), point ∆s is obtained by
drawing FG1 and SLN lines. Then,
' '
0 y'S ' y'
3 F
y 2 y 1 1.0 drawing of equilibrium stages is
x3
'
xF x',y' started. By drawing the tie line
1.0 passing through point G1, point L1
is obtained. Equation (6-23)
x'∆SB
∆S
indicates that points ∆s, L1 and G2
y' y' y =x should be on the same straight line;
hence by joining ∆s with L1 and
2
extending the line, point G2 is

'
y3 found. The tie line passing through
point G2 gives point L2. The
solution is continued by drawing
0
0 x3
'
x2'
x1'
1.0 once an operating line (the lines
x'
drawn from point ∆s are known as
Fig.6.16 Solution of counter-current extraction on operating lines) once a tie line until
solvent-free coordinated diagram
reaching the point LN. The number of the tie lines drawn gives the number of the
equilibrium stages required for the given extraction.
The percentage recovery of solute A is calculated from;
F′x′F − LN′ x′N
P.R. = .100 (6-24)
F′ x′F
If raffinate and extract solvents are completely insoluble, the solution is simplified as
the amounts of raffinate and extract solvent do not change from stage to stage. C and B
showing the mass flow rates of the solvents, the solute A balance between any stage n
and the last stage, N can be written as;
C X′N + B Yn′+1 = C X′n + B Ys′ (6.25)
If this equation is solved for Yn′ +1 ,
C C X′N
Yn′+1 = X′n + Ys′ −
B B (6-26)
' '
is obtained. This equation represents a straight line on X Y -diagram passing through
points ( X′N ; Ys′) and (X′F ; Y1′) with a slope of (C/B). The number of the equilibrium
stages is then found as follows: first, equilibrium relationship of the system is plotted
on a X'Y'-diagram, then the operating line given by equation (6-26) is drawn on the
same diagram as the values of C, B, Ys′ , X ′N and X ′F are all known at the start of the
design. The number of the right angle triangles located between equilibrium curve and
operating line, starting at one end and stopping at the other end of the cascade, gives
the number of the equilibrium stages required for the given extraction as shown in
Fig.6.17 (McCabe-Thiele method).
The percentage recovery of solute A into the
Y'
extract phase is given by;
Y' X′F − X N′
Equilibrium curve P.R. = .100 (6-27)
1
X′F
2 Minimum solvent rate: In counter-current

multi-stage extraction if the solvent rate S is
Operating line
slope= C/B reduced, point M shifts toward F and point ∆s
3 comes closer to the diagram as seen from
Fig.6.15. The closer ∆s means more
4 equilibrium stages for the same extraction.
Y's
Hence, for the same extraction, less number of
X'N X'F X'
equilibrium stages is required, if the solvent
rate is increased; and more number of
Fig.6.17 Determination of number of the equilibrium stages is needed, if the solvent
equilibrium stages in counter-current rate is decreased. If one of the operating lines
extraction, when solvents are insoluble coincides with a tie line during the
calculation, the required number of the
equilibrium stages then becomes infinite. The solvent rate corresponding to this
condition is known as minimum solvent rate. Of course, the solvent rate that is to be
selected for the operation is to be greater than the minimum solvent rate. Hence, the
minimum solvent rate for a given extraction is found as follows: arbitrary tie lines
between points F and LN are drawn and they are extended until cutting the extension of
SLN line. The tie line, which when extended cuts the SLN line at the farthest point from
the diagram, gives ∆sm, which is the ∆s point at minimum solvent rate. Usually this is
the tie line whose extension, passes through point F as shown in Fig.6.18. Then point
∆sm is joined with point F and extended until cutting the solubility curve, which is
shown by point (G1)m. Intersection point of lines (G1)mLN and FS locates point Mm. By
y
A
1.0 1.0
x,y
P
(G1)m (y1)m
x=y
F
Mm
∆S ∆Sm 0.0 LN S
B 0.0 x
C 0.0 1.0 0.0
xB,yB
Fig.6.18 Determination of minimum solvent rate
applying inverse lever-arm rule to line FMmS, minimum solvent rate Sm is calculated.
Operating solvent rate S is always selected as S=β (Sm), β being always greater than 1.
Its exact value is obtained by making an economic analysis around the combined
system of extraction and rectification units. Notice that point ∆s, which corresponds to
operating solvent rate, is always behind the point ∆sm.
6.4.1.4 Counter-Current Multi-Stage Extraction under Reflux: It is obvious that,

the extract product leaving a multi-stage cascade operating counter-currently may be
enriched up to a level that it is in equilibrium with the feed. No more enrichment is
possible in counter-current contact. For further enrichment of extract product, reflux
must be used at the extract product end. There is no need for reflux at the raffinate
product end. Flow diagram of a multi-stage cascade using reflux is shown in Fig.6.19.
Enriching section Stri pping section
Se,ye solvent
G1,y1 G2,y2 G3,y3 Gn,yn Gf,yf Gm,ym Gm+1,ym+1 GN,yN S,yS

Gn+1,yn+1 Gf+1,yf+1
solvent
separat 1 2 n f m N
G,y Lo L1,x1 L2,x2 Ln-1,xn-1 Ln,xn Lf-1,xf-1 Lf,xf Lm-1,xm-1 Lm,xm LN-1,xN-1 LN,xN
xo reflux
Raffinate
product
Extract Feed
D, xD product F, xF
Fig.6.19 Flow diagram of multi-stage extraction under reflux
As it is seen, the feed is introduced at somewhere between the first and last stages of
the cascade. In the enriching section, the solute A content of the extract phase is
increased by contacting this phase with a raffinate phase which is rich in solute A. The
raffinate phase, rich in solute A, is obtained by refluxing the part of the extract
product, which is produced by separating the solvent of the extract phase leaving the
first stage of cascade in a solvent separator, which is usually a distillation column. In
the stripping section, solute A is stripped off the raffinate phase by the extract phase
flowing in counter direction. Calculation of number of the equilibrium stages needed
for a given extraction is done on solvent-free coordinated diagram. In the enriching
section, total material balance between any stage n and the first stage is written as;
G ′n +1 = L′n + D′ (6-28)
This equation can also be written as,
G ′n +1 − L′n = D′ = ∆ ′e (6-29)
It follows from this equation that in the enriching section of the cascade there is a
constant total net flow, which is from right to left and equals the amount of extract
product on solvent-free basis. Similarly solute A balance in this section yields to:
G ′n +1 y′n +1 = L′n x ′n + D′x ′D (6-30)
which can also be written as;
G ′n +1 y′n +1 − L′n x ′n = D′x ′D = ∆ ′e y′∆e (6-31)
It follows from this equation that in the enriching section of the cascade there is a
constant solute A flow, which is from right to left and equals the amount of solute A
removed by the extract product.
From the solvent B balance in this section,
G ′n +1 y′(n +1)B − L′n x ′nB = D′x ′DB = ∆′e y′∆eB (6-32)
can also be written.
In the stripping section, total material balance on solvent-free basis between any stage
m and the last stage N gives;
L′m + S′ = G ′m+1 + L′N (6-33)
which can be written also as,
L′m − G ′m+1 = L′N − S′ = ∆′s (6-34)
This equation indicates that there is a total net flow in the stripping section of the
cascade which is given by ∆ ′s .
Solute A balance in this section becomes;
L′m x ′m + S′y′s = G ′m+1 y′m+1 + L′N x ′N (6-35)
which can also be written as,
L′m x ′m − G ′m+1 y′m+1 = L′N x ′N − S′y′s = ∆′s x ′∆s (6-36)
This means that in the stripping section there is a net flow of solute A whose value
equals ∆′s x ′∆s .
From the solvent B balance in this section,
L′m x ′mB − G′m+1 y′(m+1)B = L′N x′NB − S′y′sB = ∆′s x ′∆sB (6-37)
can also be written.
Total material balance for the whole cascade;
F' + S' = D' + L′N (6-38)
With the help of equations (6-29) and (6-34) this equation can also be written as;
F′ = ∆′e + ∆′s (6-39)
Determination of number of the equilibrium stages is done as follows: point F and S
are first located, as their compositions are known. Then, with the help of
x′D ( = x′o = y′∆e ) and x′N , points,
D(Lo) and LN are located.
y′SB S ∆e
y′B − y′ y′∆eB Point LN must lie on the
raffinate phase curve but not
G5
y′B G4
G3 the point Lo. Points S and LN
G2 G1
x ′B y′1B are joined and extended
beyond LN. A vertical from
5 4 x ′D (= x ′o = y′∆e ) fixes the
2
3 1 point G1, from which y1B ′ is
L5
LN read. The values of y1B ′ , x ′oB
L4 L3 L2 and selected RD are
L1
substituted into equation
x ′B − x ′ Lo,D
(6-40) and y′∆eB is solved.
1.0
0 x′N y′S x′F F x ′D = y′∆e With the help of this, point ∆e
x ′, y′
is located.
1.0
y′ y′1 L′ y′ − y1B ′
R D = o = ∆eB (6-40)
y′2 D′ y1B ′ − x ′oB
y′3 By joining point ∆e with point
x′∆SB F and extending the line until
y′4 ∆S y =x
cutting the extension of SLN
line, point ∆s is found. Then
y′5 drawing of equilibrium stages
is started. By drawing the tie
0
line passing through point G1,
0 ′
x 5 x′ x′4 x ′3 x′2 x′1 1.0
∆S x′ point L1 is located. Equation
(6-29) indicates that points
Fig.6.20 Solution of multi-stage extraction under reflux G2, L1 and ∆e must be on the
on solvent-free coordinated diagram same straight line (operating
line), hence by joining the
points L1 and ∆e , point G2 is found. Solution is then continued by drawing the tie line
passing through point G2. On the left hand side of point F, point ∆s is used instead of
point ∆e to draw the operating lines. While total number of the tie lines drawn gives
the number of the equilibrium stages required for the given extraction, the number of
the tie line cutting ∆eF∆s line gives the feed stage.
The reflux ratio is selected by the designer. If the reflux ratio is decreased, points ∆e
and ∆s approach the diagram, which means more stages are required for the given
extraction. On the contrary, if the reflux ratio is increased, points ∆e and ∆s go away
from the diagram, which means less number of stages is enough for the given
extraction. If during the drawing, one of the operating lines coincides with a tie line,
then infinite number of the stages is required for the given extraction. The reflux ratio
corresponding to this case is known as minimum reflux ratio. For the determination
of minimum reflux ratio, arbitrary tie lines between point F and D are drawn and
extended until cutting the vertical drawn at x ′D (= x ′o = y′∆e ) . The tie line, which when
extended cuts the vertical at the farthest point from the diagram, gives point ∆em from
which value of y′∆emB is read and finally from,
y′ − y1B′
R Dm = ∆emB (6-41)
′ − x ′oB
y1B
RDm is calculated. Selected RD for the extraction should always be greater than RDm at
which, point ∆e lies always beyond point ∆em.
6.4.2 Design of Mixer-Settler Units: The mixing section of a mixer-settler unit is
generally made as a closed vessel equipped with turbine type impeller. Vessel does not
contain baffles when it is operated full, which is a general practice. The two phases
enter the vessel through separate channels and are mixed usually less than 60 seconds
at which equilibrium or near equilibrium condition is attained. Turbine impellers are
generally flat-blade type and the ratio of impeller diameter (di) to the vessel diameter
(Dv) is kept between 0.25 and 0.33. The required power for this type of vessels, which
are full and do not contain baffles, can be found from Fig.6.21, where n is the
revolution of impeller per second, P is required power as Watt, ρM (kg/m3) and µM
(kg/ms) are the density and the viscosity of the mixture, which are obtained from the
following equations,
ρ M = ρs φs + ρ d φ d
µ 6 µ oφo
µ M = w (1 + ) , φ w > 0.4 (6-42)
φw µw + µo
µ 1.5 µ w φ w
µ M = o (1 + ) , φ w < 0.4
φo µw + µo
In the equations above, the subscripts s and d show the continuous and disperse phases
and w and o water and organic phases respectively. φ shows the volume fraction of
the component in the mixture, indicated at its subscript.
The volume fraction of dispersed phase in the vessel φ d , is usually smaller than its
value in the feed ( φ dF ) which is giving as;
φ dF = q dF /(q dF + q sF ) (6-43)
The ratio of φ d to φ dF is given as,
⎛ P q dF µ s2 ⎞ ⎛ µ 3s ⎞ ⎛ ρ s ⎞0.430 ⎛ σ 3 ρ s ⎞ ⎛ µ d ⎞
0.247 0.427 0401 0.0987
φd
= 3.39 ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ (6-44)
φ dF ⎝ LV σ 3
⎠ ⎝ dF s ⎠
q ρ 2
σ ⎝ ∆ρ ⎠ ⎝ 9.81 µ s ⎠
4
⎝ µs ⎠
where, qdF and qsF are the volumetric flow rates of dispersed and continuous phases
at vessel entrance as (m3/s), VL is the volume of liquid in the vessel as (m3), which is
defined as [VL= 0.785 D 2v z ], σ is the interfacial tension between two liquid phases as
(N/m) and z is the height of liquid level in the vessel as (m).
100 1
0.1
10 10000 100000 Re 1000000
P
d n 3ρ M
5
i
0.1
1 10 100 1000 10000 100000
d nρ M
2
Re = i
µM
Fig.6.21 Power requirment in un-baffled vessels equipped with turbine type impeller
The average diameter of dispersed phase liquid drops in the vessel, dp (m) and average
specific surface (mass transfer area per unit volume of mixture), av (m2/m3) are
calculated from;
−0.204
⎛ ⎞ ⎛ P ⎞ ⎛σ⎞
0.0473 0.274
− 2.066 + 0.732 φd µ s
d p = 10 ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ (6-45)
⎝ ρs ⎠ ⎝ VL ρ M ⎠ ⎝ ρs ⎠
6 φd
av = (6-46)
dp
Individual mass transfer coefficient of continuous phase, kLs can be estimated from the
following equation, which was obtained for mass transfer from small solid particles,
k Ls d p ⎡ ⎛ P ⎞
1/3
⎛ ρ ⎞
2/3 ⎤0.62
⎛ d ⎞
0.17
Sh s = = 2 + 0.47 ⎢ d 4/3 ⎜ ⎟ ⎜ ⎟ ⎥ ⎜ ⎟ Sc s0.36

s i
(6-47)
⎝ VL ⎠ ⎝ µ s ⎠ ⎦ ⎝ D v ⎠
p
D As ⎣
where DAs is the molecular diffusivity of solute A in continuous phase as (m2/s), which
may be component B or C and Scs is Schmidt number for continuous phase, which is
given as Scs = µs/ρs DAs.
Individual mass transfer coefficient of dispersed phase kLd is calculated from equation;
d ⎡3 ∞ ⎛ λ 64 D θ ⎞⎤
k Ld = p ln ⎢ ∑ Tn2 exp⎜⎜ − n 2 Ad ⎟⎟⎥ (6-48)
6 θ ⎣⎢ 8 1 ⎝ d p ⎠⎦⎥
where θ (s) is the residence time in the vessel, which is calculated from
θ = VL/(qsF+qdF). DAd (m2/s) is the molecular diffusivity of solute A in the dispersed
component, which can be component B or C. The values of Tn and λn are given in
Table.6.1.
Hence over-all mass transfer coefficient based on dispersed phase is obtained as;
1 1 1
= + (6-49)
K Ld k Ld m sd k Ls
where, msd is distribution coefficient defined as the ratio of molar concentration of
solute A in the continuous phase cAs (k-molA/m3 continuous phase) to the molar
concentration of solute A in dispersed phase cAd (k-molA/m3 dispersed phase).
Murphree stage efficiency is then based on the number of transfer units. The number
of over-all transfer units for dispersed phase in molar concentration units assuming
dilute solution, can be written as;
c Ad1
⌠ dc Ad
N od = ⎮ (6-50)
⌡c Ad 2 c Ad − c Ad
∗
where it is assumed that molar concentration of solute A in dispersed phase changes

from cAd1 to cAd2 and c ∗Ad is the molar concentration of solute A in dispersed phase,
when it reaches in equilibrium with the continuous phase. By assuming constant exit
concentration for thoroughly mixed vessel, the equation above is written as;
1 c −c 2
∫
c Ad1
N od = dc Ad = Ad1 Ad (6-51)
c Ad2 − c Ad2 cAd 2
∗
c Ad 2 − c∗Ad 2
Table 6-1. The values of Tn and λn in equation (6-48)
kLsdp/DAs λ1 λ2 λ3 T1 T2 T3
3.20 0.262 0.424 1.49 0.107
5.33 0.386
8.00 0.534
10.7 0.680 4.92 1.49 0.300
16.0 0.860 5.26 1.48 0.382
21.3 0.982 5.63 1.47 0.428
26.7 1.082 5.90 15.7 1.49 0.495 0.205
53.3 1.324 7.04 17.5 1.43 0.603 0.298
107 1.484 7.88 19.5 1.39 0.603 0.384
213 1.560 8.50 20.8 1.31 0.588 0.396
320 1.600 8.62 21.3 1.31 0.583 0.391
∞ 1.656 9.08 22.2 1.29 0.596 0.386
On the other hand from definition equation,

z z
N od = = (6-52)
H od u d / K Ld a v
can be written. Where, Hod (m) is the height of one over-all dispersed phase transfer
unit, ud (m/s) is the velocity of dispersed phase in the vessel, which is calculated from
[ ud= qdF /0.785 D 2v ].
As the Murphree stage efficiency for the dispersed phase is,
c −c
E Md = Ad1 ∗Ad2 (6-53)
c Ad1 − c Ad2
Then,
c Ad1 − c Ad 2 (c Ad1 − c Ad 2 ) /(c Ad 2 − c ∗Ad 2 )
E Md = =
(c Ad1 − c Ad 2 ) + (c Ad 2 − c ∗Ad 2 ) (c Ad1 − c Ad 2 ) /(c Ad 2 − c ∗Ad 2 ) +1
and finally with the help of equation (6-51);

N od
E Md = (6-54)
N od + 1
is obtained. By substituting the Nod value, which is obtained from equation (6-51) into
equation (6-54) the efficiency of mixer-settler unit is computed.
The mixture then flows into settling section of the unit as emulsion, which means one
of the phases is dispersed finely into another phase. The behaviour of the emulsion is
very important for the separation into two phases in the settler. The stable emulsions,
at which the droplet diameters are between 1-1.5 µm, the density difference of the
phases and the interfacial tension between the phases is small, cannot be separated
easily. When the diameter of the drops exceeds 1 mm., the separation quickens. The
high viscosity of continuous phase and the dust particles, which usually accumulate at
the interface, hinder the coalescence. An unstable emulsion settles and coalesces
rapidly as soon as it flows into settler and a sharp interface forms quickly, which is
known as primary break. However, one of the phases, usually that in majority, remains
clouded by very fine fog of the dispersed phase. The cloud will eventually settle and
leave the clouded phase clear, which is known as secondary break. In continuous
multi-stage operations the wait for secondary break between the stages usually is not
economic and it is contended with the primary break, which is a matter of minutes.
The velocity of emulsion from mixer to settler must be sufficiently low so that it does
not disturb the already separated phases in the settler. In sizing the settler, the settling
times measured in laboratory are used. In the absence of experimental measurements,
diameter of settler Dd (m), which is normally taken as ¼ of the length, is estimated
from;
Dd = 8.4 (qs+ qd)0.5 (6-55)
The emulsions containing very fine droplets may be passed through a coalescer in
order to increase the size of the droplets and hence reduce their settling time, before
entering the settler. Cotton fibres, glass wool, fibres glass, steel wool, polypropylene
cloth etc. can be used for this purpose.
APPENDICES
276
Table.App. 2.1 Laplace Transforms
Transform
No ∞
Function f(θ)
. ₤(s) = ∫ e −sθ f (θ)dθ
0
1
1 1
s
1
2 θ
s2
θ n −1 1
3 n = 1, 2, 3,...
(n − 1)! sn
1 1
4
(πθ) s
θ 1
5 2
π s3 / 2
1
6 eaθ
s−a
k ⎛ k2 ⎞
exp⎜ − ⎟ e −k s
k >0
⎝ 4θ ⎠
7
3
2 (πθ )
⎛ k ⎞ 1 −k
8 erfc⎜ ⎟ e s
k ≥0
⎝2 θ⎠ s
1 ⎛ k2 ⎞ 1 −k
9 exp⎜⎜ − ⎟⎟ e s
k ≥0
(πθ) ⎝ 4θ ⎠ s
θ ⎡ ⎛ k 2 ⎞⎤ ⎛ k ⎞ − 3 −k s
10 2 ⎢exp⎜⎜ − ⎟⎟⎥ − k erfc⎜ ⎟ s 2e k ≥0
π ⎣⎢ ⎝ 4θ ⎠⎦⎥ ⎝2 θ⎠
⎛ k ⎞ ⎛ k ⎞ ae − k s
− exp(ak ) exp(a 2θ)erfc⎜ a θ + ⎟ + erfc⎜ ⎟ k ≥0
11
⎝ 2 θ⎠ ⎝2 θ⎠ s (a + s )
⎛ k ⎞ e −k s
12 exp(ak ) exp(a θ)erfc⎜ a θ +
2
⎟ k ≥0
⎝ 2 θ⎠ s (a + s )
⎛ θ ⎞ 1
13 erf ⎜ ⎟ exp(k 2 s 2 )erfc(ks) k > 0
s
⎝ 2k ⎠
277
Table. App. 2.2 Error Function
2 u d 2 − u du
erf u = ∫ e − z dz ; (erf u ) = −
2 2
e . ; erf(-u) =-erf u; erf(o)=o;

π o dz π dz
erf(∞)=1
u erf u u erf u
0.00 0.0 1.1 0.880205
0.05 0.056372 1.2 0.910314
0.10 0.112463 1.3 0.934008
0.15 0.167996 1.4 0.952285
0.20 0.222703 1.5 0.966105
0.25 0.276326 1.6 0.976348
0.30 0.328627 1.7 0.983790
0.35 0.379382 1.8 0.989091
0.40 0.428392 1.9 0.992790
0.45 0.475482 2.0 0.995322
0.50 0.520500 2.1 0.997020
0.55 0.563323 2.2 0.998137
0.60 0.603856 2.3 0.998857
0.65 0.642029 2.4 0.999311
0.70 0.677801 2.5 0.999573
0.75 0.711156 2.6 0.999764
0.80 0.742101 2.7 0.999866
0.85 0.770668 2.8 0.999925
0.90 0.796908 2.9 0.999959
0.95 0.820891 3.0 0.999978
1.00 0.842701
278
Table. App. 4.1 Solubility of ammonia in water
kg NH3 Partial pressure of ammonia, mmHg

-----------
100 kg H2O 0oC 10oC 20oC 30oC 40oC 50oC 60oC
100 947
90 785
80 636 987
70 500 780
60 380 600 945
50 275 439 686
40 190 301 470 719
30 119 190 298 454 692
25 89.5 144 227 352 534 825
20 64 103.5 166 260 395 596 834
15 42.7 70.1 114 179 273 405 583
10 25.1 41.8 69.6 110 167 247 361
7.5 17.7 29.9 50.0 79.7 120 179 261
5 11.2 19.1 31.7 51.0 76.5 115 165
4 16.1 24.9 40.1 60.8 91.1 129.2
3 11.3 18.2 29.6 45.0 67.1 94.3
2 12.0 19.3 30.0 44.5 61.0
1 15.4 22.2 30.2
Table. App. 4.2 Solubility of sulphur dioxide in water
kg SO2 Partial pressure of sulphur dioxide, mmHg

----------
100 kg H2O 0oC 7oC 10oC 15oC 20oC 30oC 40oC 50oC
20 646 657
15 474 637 726
10 308 417 474 567 698
7.5 228 307 349 419 517 688
5.0 148 198 226 270 336 452 665
2.5 69 92 105 127 161 216 322 458
1.5 38 51 59 71 92 125 186 266
1.0 23.3 31 37 44 59 79 121 172
0.7 15.2 20.6 23.6 28.0 39.0 52 87 116
0.5 9.9 13.5 15.6 19.3 26.0 36 57 82
0.3 5.1 6.9 7.9 10.0 14.1 19.7 - -
0.1 1.2 1.5 1.75 2.2 3.2 4.7 7.5 12
0.05 0.6 0.7 0.75 0.8 1.2 1.7 2.8 4.7
0.02 0.25 0.3 0.3 0.3 0.5 0.6 0.8 1.3
279
Table. App. 4.3 Solubility of carbondioxide in 15.3% Monoethanolamine solution
Partial pressure k-mol CO2/ k-mol amine

of CO2,mmHg
40oC 60oC 80oC 100oC 120oC 140oC
1 0.383 0.096
5 0.438 0.152
10 0.471 0.412 0.194
30 0.518 0.459 0.379 0.265
50 0.542 0.482 0.405 0.299
70 0.558 0.498 0.422 0.322 0.200
100 0.576 0.516 0.442 0.347 0.227 0.109
200 0.614 0.552 0.481 0.393 0.281 0.162
300 0.639 0.574 0.505 0.423 0.314 0.194
400 0.657 0.591 0.523 0.442 0.336 0.219
500 0.672 0.605 0.538 0.458 0.355 0.237
600 0.686 0.615 0.550 0.472 0.370 0.254
760 0.705 0.631 0.566 0.489 0.390 0.275
1000 0.727 0.650 0.584 0.509 0.413 0.300
2000 0.702 0.637 0.562 0.476 0.366
3000 0.669 0.596 0.513 0.408
5000 0.712 0.641 0.562 0.464
7000 0.742 0.672 0.597 0.500
Table. App. 4.4 Solubility of H2S in 15.3% Monoethanolamine solution
Partial pressure k-mol H2S / k-mol amine

of H2S, mmHg
40oC 60oC 80oC 100oC 120oC 140oC
1 0.128 0.029
3 0.212 0.137 0.050 0.025 0.016
5 0.271 0.171 0.065 0.036 0.025
10 0.374 0.240 0.141 0.091 0.056 0.040
30 0.579 0.386 0.243 0.160 0.101 0.072
50 0.683 0.472 0.314 0.203 0.139 0.091
70 0.750 0.534 0.364 0.238 0.153 0.106
100 0.802 0.600 0.422 0.279 0.182 0.124
200 0.890 0.722 0.545 0.374 0.256 0.167
300 0.931 0.790 0.617 0.439 0.312 0.200
400 0.949 0.836 0.666 0.490 0.357 0.226
500 0.959 0.871 0.706 0.536 0.393 -
600 0.970 0.900 0.738 0.575 0.426
700 0.980 0.921 - 0.607 0.453
800 - 0.942 - 0.636 -
280
Table.App.5.1 Vapor-liquid equilibrium of acetone-water system at 760 mmHg
t(oC) 100 74.8 68.5 64.8 63.1 61.7 60.5 59.4 58.4 57.5 56.7 56.2
x 0.0 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.0
y 0.0 0.64 0.73 0.78 0.80 0.82 0.84 0.86 0.88 0.90 0.94 1.0
Table.App.5.2 Vapor-liquid equilibrium of chloroform-toluene system at 760 mmHg
t (oC) 110.7 105.2 101.1 94.5 89.0 84.0 79.3 74.9 70.8 67.2 63.9 61.1
x 0 0.05 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y 0 0.187 0.317 0.500 0.632 0.735 0.816 0.878 0.925 0.959 0.983 1.0
Table.App.5.3 Vapor-liquid equilibrium of methanol-n-propanol system at 760 mmHg
t(oC) 97.2 94.4 91.8 86.9 82.7 78.9 75.6 72.7 70.2 68.0 66.1 65.3 64.5
x 0.0 0.05 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.95 1.0
y 0.0 0.148 0.272 0.467 0.61 0.716 0.795 0.856 0.902 0.939 0.970 0.984 1.0
Table.App.5.4 Vapor- liquid equilibrium for methanol-water system at 760 mmHg
t (oC) 100 93.7 89.2 83.2 79.1 76.1 73.6 71.5 69.6 67.8 66.1 64.5
x 0 0.05 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y 0 0.243 0.390 0.562 0.664 0.735 0.791 0.839 0.882 0.923 0.962 1.0
Table.App.5.5 Vapor-liquid equilibrium for ethyl acetate - acetic acid system at 760 mmHg
t(oC) 118 113,4 109,3 102,5 97,0 92,6 88,9 85,9 83,3 81,1 79,1 77,2
x 0,0 0,05 0,10 0,20 0,30 0,40 0,50 0,60 0,70 0,80 0,90 1,0
y 0,0 0,18 0,32 0,51 0,64 0,74 0,80 0,86 0,90 0,93 0,97 1,0
Table.App.5.6 Vapor-liquid equilibrium for benzene- heptane system at 760 mmHg
t(oC) 97.4 96.3 94.1 92.0 90.0 88.1 86.3 84.6 83.1 81.6 80.8
x 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 0.95
y 0.105 0.187 0.337 0.457 0.552 0.638 0.714 0.782 0.85 0.922 0.958
Table.App.5.7 Vapor-liquid equilibrium for benzene- methylisobutylketone system at 760 mmHg
t(oC) 116.1 110.3 105.2 100.8 96.8 93.3 90.2 87.3 84.8 82.4 80.1
x 0.0 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.0
y 0.0 0.267 0.455 0.598 0.69 0.778 0.838 0.89 0.933 0.968 1.0
281
Table.App.5.8 Vapor-liquid equilibrium for acetaldehyde-ethanol system at 760 mmHg
t(oC) 78.3 79.3 79.8 77.1 69.1 58.4 48.1 39.7.1 33.1 28.1 24.1 21.1
x 0 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.0
y 0 0.030 0.100 0.358 0.650 0.841 0.931 0.969 0.986 0.994 0.998 1.0
Table.App.5.9 Vapor-liquid equilibrium for water-ethylenglycole system at 760 mmHg
t(oC) 197.1 178.9 165.8 148.1 136.2 127.4 120.5 115.0 110.3 106.3 103.0 100
x 0.0 0.05 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y 0.0 0.464 0.675 0.852 0.921 0.954 0.973 0.983 0.990 0.995 0.998 1.0
Table.App.5.10 Vapor-liquid equilibrium for benzene-toluene system at 760 mmHg
t(oC) 110.68 107.96 105.59 101.52 98.0 94.85 91.95 89.26 86.75 84.4 82.19 80.12
x 0.0 0.05 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.0
y 0.0 0.12 0.22 0.38 0.51 0.62 0.71 0.79 0.85 0.91 0.96 1.0
Table.App.5.11 Vapor-liquid equilibrium for sulfur dichloride-carbon tetrachloride system at 760 mmHg
t(oC) 76.7 74.5 72.4 70.5 68.6 66.9 65.2 63.6 62.1 60.7 59.3
x 0.0 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.0
y 0.0 0.18 0.32 0.43 0.54 0.65 0.73 0.81 0.89 0.95 1.0
x and y values at the above-given tables are the mole fractions of the first written components
Table.App.5.12 Enthalpy-composition data for aqueous ammonia at 10 bar
x, mass fraction of Specific enthalpy of y, mass fraction of Specific enthalpy of

ammonia in liquid saturated liquid, h (kJ/kg) ammonia in vapor saturated vapor,H (kJ/kg)
0 790 0 2 810
0.0951 600 0.622 2 280
0.20 420 0.824 1 960
0.30 310 0.903 1 775
0.40 200 0.94 1 650
0.5 140 0.958 1 580
0.6 100 0.97 -
0.7 140 0.975 -
0.8 160 0.98 1 530
0.9 240 0.99 -
1.0 310 1.0 1 500
282
Table.App.5 Periodic Table
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Group
Ia IIa IIIb IVb Vb VIb VIIb VIIIb Ib IIb IIIa IVa Va VIa VIIa VIIIa
Period
1 2
1 H He
1.01 4.00
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.94 9.01 10.81 12.01 14.01 15.99 19.00 20.18
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar
22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.70 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 98.91 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.75 127.60 126.90 131.29
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.91 137.33 138.91 178.49 180.95 183.85 186.21 190.20 192.22 195.08 196.97 200.59 204.38 207.20 208.98 (209) (210) (222)
87 88 89 104 105 106 107 108 109 110 111 112
7 Fr Ra Ac ** Rf Ha Sg Ns Hs Mt Uun Uuu Uub 113 114 115 116 117 118
(223) 226.03 (227) (261) (262) (263) (262) (265) (266)
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanoide * Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.12 140.91 144.24 (145) 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Actinoide ** Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.04 231.04 238.03 237.05 (244) (243) (247) (247) (251) (254) (257) (258) (259) (260)
283
REFERENCES
1- Mass Transfer Operations. 3rd ed. R.E.Treybal, McGraw-Hill, 1980.

2- Mass Transport Phenomena. C.J.Geankoplis. Holt, Rinehart and Winston, 1972.
3- Chemical Engineering. Vol.1 (2nd ed.) and Vol.2 (3rd ed.) J.M. Coulson and J.F.
Richardson. Pergamon Press, 1970-1978.
4- Perry’s Chemical Engineers’ Handbook. 7th ed. D.W.Green (edit.), McGraw-Hill, 1998.
5- Transport Processes and Unit Operations. 3rd ed. C.J.Geankoplis, Prentice-Hall, 1993.
6- Distillation Engineering. R.Billet, Chemical Pub. Co., 1979.
7- Mass Transfer (Turkish). E.Alpay, Ege Univ. Eng. Fac. Pub. No.3, 1984.
8- Stoffaustausch einschliesslich chemischer Reaktionen. H.Brauer, Sauerlander AG, Aarau,
1971.
9- Mass Transfer. T.K.Sherwood, R.L.Pigford and C.R.Wilke, McGraw-Hill, 1975.
10-Diffusional Mass Transfer. A.H.P Skelland, John Wiley, 1974.
11-Fundamentals of Transport Phenomena. R.W.Fahien, McGraw-Hill, 1983.
12-Mass Transfer. A.L.Hines and R.N.Maddox, Prentice-Hall, 1985.
13-Vapor-Liquid Equilibria. M.Hirata, S.Ohe and K.Nagahama, Elsev. Sci. Pub., 1975.
14-Elements of Fractional Distillation. E.R.Gilliland and C.S.Robinson, McGraw-Hill, 1950.
15-Azeotropic Data. Vol.1-2. L.E.Horsley. Am.Chem.Soc., 1952-1962.
16-Process Heat Transfer. D.Q.Kern, McGraw-Hill, 1950.
17-Gas-Liquid Reactions. P.V.Danckwerts, McGraw-Hill, 1970.
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Mass Transfer and Mass Transfer Operations - Erden Alpay and Mustafa Demircioğu

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Erden ALPAY Mustafa DEMİRCİOĞLU

Ege University-Engineering Faculty-Chemical Engineering Department

Chapter-1 : MASS TRANSFER BY MOLECULAR DIFFUSION 7

1.2 Mass Transfer by Molecular Diffusion in the Gases 9

Integration of the General Flux Equation 9

Equimolar Counter Transfers of A and B 9

A Transfers through Non-Transferring B 10

The Relationship between NA and NB is Fixed by Reaction Stoichiometry 11

The Relationship between NA and NB is Given by the Latent Heats of Vaporization 12

Mass Transfer with Varying Cross-Sectional Area 12

Mass Transfer by Molecular Diffusion in Multi-Component Gas Mixtures 14

Determination of Binary Diffusivities of Gases 14

Prediction of Binary Gas Diffusivities 18

Estimation of Binary Gas Diffusivities 20

Effect of Temperature and Pressure on Gas Diffusivity 22

1.3 Mass Transfer by Molecular Diffusion in Liquids 22

Determination of Molecular Diffusivities in Liquids 23

Estimation of Liquid Diffusivities 25

Molecular Diffusivity in Concentrated Liquid Solutions 29

Effect of Temperature on Molecular Diffusivity in Liquids 30

Molecular Diffusivity in Multi-Component Liquid Solutions 30

1.4 Continuity Equation for a Binary Mixture 30

1.5 Mass Transfer by Molecular Diffusion in Solids 33

Diffusion that is Independent of the Nature of the Solid 33

Diffusion that is Dependent on the Nature of the Solid 37

Diffusion of Liquids in Solids 37

Diffusion of Gases in Solids 38

The Relationship between the Fluxes at the Diffusion of Gases in Solids 42

Molecular Diffusivity of Gases in Solids and the Permeability 42

Chapter-2 : MASS TRANSFER BY TURBULENT DIFFUSION and

2.2 A and B Transfer under Equimolar Counter Transfer Conditions 48

2.3 A Transfers through Non-Transferring B 49

2.4 Mass Transfer Coefficients in Laminar Flow 49

Mass Transfer from a Gas into a Liquid Film in Laminar Flow 51

2.5 Mass Transfer Correlations 56

2.6 Mass Transfer Theories 59

Chapter-3 : MASS TRANSFER BETWEEN TWO PHASES 68

3.2 Equilibrium between Phases 68

3.3 Mass Transfer between Two Phases 69

3.4 Mass Transfer Flux 70

3.5 Overall Mass Transfer Coefficients and Overall Driving Forces 72

3.6 The Relationships between Individual and Overall Mass Transfer 73

Chapter-4 : GAS ABSORPTION 78

4.2 Gas-Liquid Equilibrium 79

4.3 Selection of Solvent 83

4.4 Absorption Operations 85

Gas Absorption in Continuous Contact Type of Equipment 85

Gas Absorption in Packed Column 95

Calculation of Number of Transfer Units 100

Calculation of Individual Heights of Transfer Units 104

Stage-Wise Contact Type of Absorption 110

Gas Absorption in Plate Columns 110

4.5 Non isothermal Absorption 126

4.6 Gas Absorption with Chemical Reaction 130

Gas Absorption with Instantaneous Chemical Reaction 133

Calculation of Height of Packing when Chemical Reaction is Instantaneous 135

Calculation of Height of Packing when Chemical Reaction is Slow 138

Chapter-5 : DISTILLATION 150

5.1 Introduction 150

5.2 Liquid-Vapor Equilibria 150

Ideal Solutions 153

Deviation from Ideality: Real and Azeotropic Solutions 155

Partial Solubility and Insolubility of the Components in Liquid Phase 158