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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 N A and N B is Fixed by Reaction Stoichiometry

11

The Relationship between N A and N B 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 Coefficients

73

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 erden.alpay@ege.edu.tr

September, 2006-İZMİR

Mustafa Demircioğlu mustafa.demircioglu@ege.edu.tr

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 (KMO 4 ) 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 KMO 4 molecules. We understand from this that dissolved KMO 4 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 KMO 4 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 (KMO 4 ) had taken place: the dissolved KMO 4 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

this type of mass transfer is known as mass transfer by KMO 4 Fig.1 Dissolution of

KMO 4

type of mass transfer is known as mass transfer by KMO 4 Fig.1 Dissolution of KMO
type of mass transfer is known as mass transfer by KMO 4 Fig.1 Dissolution of KMO

Fig.1 Dissolution of KMO 4 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

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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 KMO 4 experiment, we can say that KMO 4 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 KMO 4 ), 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 KMO 4 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 KMO 4 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 10 16 ) 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,

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2

liquid is water). If the average velocity of flow

slipping one on the other. The velocity of the first layer adjacent to solid is zero and

u

x is small, the liquid flows as layers

z

liquid B x
liquid B
x
and u x is small, the liquid flows as layers z liquid B x solid plate
and u x is small, the liquid flows as layers z liquid B x solid plate

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 (u z =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

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3

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

volume next to the interface is less than the number of the ammonia molecules in unit volume in the bulk gas. Under this concentration difference, ammonia transfers from bulk gas to the interface

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 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

Gas phase Liquid phase A+C S A Bulk gas Bulk liquid interface
Gas phase
Liquid phase
A+C
S
A
Bulk gas
Bulk liquid
interface

z

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4

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 + O 2

from toluen e by oxidation with air oxygen. Toluene + O 2 Benzoic acid Although the

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

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5

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.

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6

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 J Az ,is written as:

J Az = -D AB

dc A

dz

(1-1)

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/m 2 s. dc A /dz is the concentration gradient causing the mass transfer as k-molA/m 3 m. (-) sign emphasizes that diffusion always occurs in the direction of decreasing concentration. D AB is called as molecular diffusivity or diffusion coefficient of component A in component B (m 2 /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:

Rate

flux,

J

of

molecular

Az

by :

J Bz = -D BA diffusion, J A J Az J = Az S m
J Bz = -D BA
diffusion, J
A
J
Az
J
=
Az
S
m

dc B

z

dz

(k-molA/s)

can

be

related

(1-2)

to

the

(1-3)

diffusional

where, S m (m 2 ) 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, j Az (kg A/m 2 s) is written as:

j

Az =-D AB

dρ A

dz

(1-4)

where

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

ρ

A (kgA/m 3 ) is the mass concentration of component A.

7

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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 u Az and u Bz . Then, the total molar flux of each component relative to the fixed coordinates are N Az = c A u Az and N Bz = c B u Bz , where c A and c B are molar concentrations of A and B (k-mol/m 3 ) . On the other hand, since the total molar concentration of the mixture is c=c A +c B , the molar average velocity of the mixture, (m/s) is then:

u&

z

u&

z

=

c

A

u

Az

+

c

B

u

Bz

=

N

Az

+

N

Bz

 

c

c

(1-5)

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;

J Az = c A (u Az -

u&

z

) =

c

A u Az -

c

A

u&

z

(1-6)

can be written. After substitutions from the equations above finally,

N Az = J Az +

c A ( N Az + N Bz )

c

(1-7)

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:

N Bz = J Bz +

c B

c

( N Az + N Bz )

The relationship between total molar flux and total molar rate ( N can be written as:

N =

Az

N Az S m
N
Az
S
m

Az

)

(1-8)

(k-mol A/s)

(1-9)

Similarly, if instead of molar units, the mass units are used; total mass flux of component A, n Az (kgA/m 2 s) is written as:

where

u z

n

Az

=

j

Az

+

ρ

A

u

z

=

j

Az

+

ρ

A

ρ

(n

Az

+

n

Bz

)

is the mass average velocity of the mixture and given as:

u

z

=

(

ρ u

A

Az

+ρ u

B

Bz

)/

ρ

=(

n

Az

+ n

Bz

)/ ρ

(1-10)

(1-11)

8

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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 D AB and S m are constant. First, substitute J Az from equation (1-1) and then separate the variables. With the limits of the integrals: at z=z 1 c A = c A1 and at z = z 2 c A =c A2 ;

is obtained. For the sake of simplicity

1

z

2

dz =−

c

A 2

dc

A

cD

AB

z

1

c

A1

cN

A

c

A

( N

A

+

N

B

)

subscript z is omitted. Upon integration,

z

2

z

1

=

1 ln

c

N

A c

A2

(N

A

+

N

B

)

cD

AB

 

N

A

+ N

B

c

N

A c

A1

(N

A

+

N

B

)

is found. If both sides of this equation are

multiplied by N A and z = z 2 -z 1 is taken, finally;

N A =

N

A

c D

AB

N

A

+

N

B

.

z

ln

N A c A2 − N + N c A B c N A A1
N
A
c A2
N
+ N
c
A
B
c
N A A1
N
+ N
c
A
B

(1-12)

is obtained. This equation can also be written in different forms. From the ideal gas

can be written, where P and

law,

p A are the total and partial pressure of component A, respectively. Substituting these into equation (1-12),

n

V

n

A

V

P =

RT

=

cRT

and

p A =

RT

=

c

A

RT

N A

=

N

A

D

AB

P

N

A

+

N

B

.

RTz

ln

N A p A2 − N P A + N B N A p A1
N
A
p A2
N
P
A + N
B
N
A
p A1
N
+ N
P
A
B

(1-13)

is

obtained. From Dalton’s law y A = p A /P, where y A 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:

N A

=

N

A

D

AB

P

N

A

+

N

B

.

RTz

ln

N A − y A2 N + N A B N A − y A1
N
A
− y
A2
N
+
N
A
B
N
A
− y
A1
N
+ N
A
B

(1-14)

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 N A and N B 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 N A and N B . 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, N A =-N B = constant and equation (1-12) is indeterminate. Then, we go back to the equation (1-7), with N B =-N A this equation becomes:

9

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N

A

= −

D

AB

dc

A

c

A

+

dz

c

[

N

A

+ −

(

N

A

)

]

= −

D

AB

dc

A

dz

+

0

if this equation is integrated under the conditions at which equation (1-7) was integrated.

N

A

D AB

=

z

(

c

A1

c

A2

)

(1-15)

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:

and

N

A

N

A

=

=

D AB

RTz

D

AB

P

RTz

(

p

A1

p

(

y

A1

A2

)

y

A2

 

(1-16)

)

(1-17)

As it is seen, at this special case N A = J A . It follows from this that there can’t be bulk flow in the transfer direction, when equimolar counter transfer occurs. Since in this case N A +N B =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, N B =0 and then equations (1-12), (1-13) and (1-14) simplify to:

N

A =

c D

AB

ln

c

B2

N

=

D

AB

P

ln

p

B2

z

c

B1

,

A

RTz

 

p

B1

,

N

A

=

D

AB

P

y

B2

ln

RTz

y

B1

(1-18)

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, c A1 – c A2 = c B2 – c B1 , p A1 – p A2 = p B2 – p B1 and y A1 – y A2 = y B2 – y B1 , the right hand sides of the equations given in (1-18) are first multiplied with the appropriate equation below,

c

A1

c

A2 =

B1

1,

p

A1

p

A2 =

p

B1

1

 

y

A1

y

A2

y

B2

y

B1

y

B2

y

B1

 

=

 

ln

y

B2

 

y

B1

) N A =

D

AB

P

= 1

(

y

B

(

RTz y

B

)

ln

c

B2

c

p

B2

then by definitions of logarithmic means, which are given below,

c

c

)

B2

c

B1

ln

c B2

c B1

finally;

N A =

D

AB

z

(

c

B

ln

( c

A1

=

c

(

c

A2

B

)

) ln

,

, N A =

p

B2

p

B1

ln

p

B2

p

B1

D

AB

P

(

RTz p

B

)

ln

=

(

p

B

( p

A1

) ln

p

,

A2

) ln

( y

A1

y

A2

)

(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 (-dp B /dz ) is not zero, and under this concentration gradient component B

10

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pressures,p A ,p B ,P

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 A B p A1 p B1 z 1 distance,z z 2 pressures,p A ,p
P
A
B
p
A1
p
B1
z 1
distance,z
z
2
pressures,p A ,p B ,P

(a)

P

p

B2

p

A2

P

A
A

P

p

B2

p

p

B1

A1 z 1 distance,z z 2
A1
z 1
distance,z
z 2

p A2

(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 N A and N B 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 An 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 N A = - m N B can be written. Hence, substituting N B = - (n/m) N A into any one of the equations (1-12), (1-13) and (1-14) N A 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 o C according

to the stoichiometry given below:

2A

25 o C according to the stoichiometry given below: 2A B Across a gas film of

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 D AB = 4.10 -5 m 2 /s.

11

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Equation(1-13) can be used.

N

A

N

A

1

=

=

N

A

+

N

B

N

A

0.5N

A

1

0.5

Solution :

A

 
 

= 2

= 2

B

z 1 2
z
1
2

N

A

=

(2)

(4 *10

5

2

m / s)(2 bar)

3

(0.083bar m / k

mol K)(273

+

25 K)(2 *10

3

m)

ln

2

2

(0.1/ 2)

(0.4/ 2)

catalystt

N A = (3.23 * 10 -3 ) ln (1.083) = 2.58 *10 -4 k-mol A/m 2 s

N B = - (0.5) N A = - 1.29*10 -4 k-mol B/m 2 s

1.2.5 The Relationship between N A and N B 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 λ A N A = - λ B N B , where λ A and λ B are latent heats of vaporization of the corresponding components (kJ/k-mol). In this case substituting N B = - (λ A /λ B ) N A into one of the equations (1- 12), (1-13) and (1-14) the fluxes can easily be calculated. Note that if λ A = λ B , equimolar counter transfers of A and B occurs. 1.2.6 Mass Transfer with Varying Cross-Sectional Area: If the mass transfer area S m 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 and are constant, N A Az N Bz N N Az Bz and and
N
and
are constant, N A
Az
N Bz
N
N
Az
Bz
and
and
S m is
S
m S
m

and N B in the equation (1-7) are first replaced with

expressed as function of z and then the integral is performed. By dividing so-obtained

( N

Az

)

with the S m value calculated at the specified z, N A at this z is obtained.

Example-1.2) Calculation of Molar Flux in Varying Cross-Section

SO 2 (A) is transferring at steady-state through non-transferring O 2 (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 SO 2 is measured as 0.22 bar and 0.055 bar at two ends.

12

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Calculate the total molar flux of SO 2 at mid-point of the conduit. The molecular diffusivity of SO 2 in O 2 at 1 bar and 25 o C is 2.25*10 -5 m 2 /s.

Solution : b=300 mm a 2 =200 mm S m1 N A S m2 a
Solution :
b=300 mm
a 2 =200 mm
S m1
N A
S m2
a
(S
S
p A2
a 1 =400 mm
N B = 0
p A1
b=300 mm
l/2
z
l

S m = b * a = 0.3 * a

(m 2 )

a =

a

1

a

1

a

2

0.4

0.2

z

=

0.4

l

2

z

=

0.4

S m = 0.3(0.4 - 0.1 z) = 0.12 - 0.03 z (m 2 )

0.1z

(m)

From eqn.(1-7) for N B =0

and

J A =−

D

AB

dp

a

RT dz

N

(1

p

A

)

=−

D

AB

dp

A

 
     
 

A

 

P

RT

dz

 
 

N

A

dz =−

D

AB

P

 

dp

A

 

After substituting for S m and separating the variables,

     
 

S

m

 

RT

 

P

p

A

 

dz

 

D

P

dp

N

   

=−

 

A B

 

A 2

A

 

A

l

o

0.12

0.03 z

 

RT

p

p

 

P p

A

   

A1

N A
N
A

[

ln 0.12

0.03 z

]

2

0

=

D

AB

P

ln

[

P

p

A

]

0.055

0 22

.

0.03

 

RT

1.75

D

AB

=

2.25*10

5

1

10

⎞ ⎛ 598

⎠ ⎝

298

= 7.61*10

6

m

2

/ s

Then from equation above,

N A =

1.11*10

9

k

At

(N

z = l / 2

(S m ) l /2 = 0.12 – 0.03 (1.0) = 0.09 m 2

A

)

l

/ 2

=

 

N

A

 

=

1.11*10

9

(S

m

)

l

/ 2

0.09

=

1.23 *10

8

k

mol A / s

=

2

molA / m s

cons tan t

13

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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 i second,

an effective diffusivity defined by equation (1-20) is taken in the place of D AB .

n

equations. First, all the N A + N B terms in the equations are replaced with

i = A

D Aef

n

 

N

A

y

A

N

i

 

i = A

= n

1

 

( y N

i

A

y

A

N )

i

i = A

D Ai

(1-20)

With these changes, the equation (1-12) becomes:

N

A

=

N

A

cD Aef

i

n

=

A

N

i

z

ln

N A c A2 − n c ∑ N i i = A N A
N
A
c A2
n
c
N
i
i
= A
N
A c
A1
n
c
N
i
i
= A

(1-21)

As it is seen from equation (1 -20), effective diffusivity D Aef , which can be synthesized from its binar y 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 N A is zero. In this case equation (1-20) simplifies to:

D

Aef

=

1 y

A

n

i = B

y

i

D

Ai

(1-22)

1.2.8 Determinat

equations above that to use any one of these, binary diffusivity, D AB must be known at the operating conditions. It was shown that effect of concentration on the diffusivity is n egligible. 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 experime ntation conditions. The experimental set-up as shown in Fig.1.2, consists of two chambers with V 1 , V 2 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

ion of Binary

Diffusivities of Gases: It is obvious from

the

14

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1

o

 

2

c

o

 

c

A1

 

S

m

m

V

2

A2

 

V

1

 
  V 1    
 
 
   
   
 
 

c

A1

 

z

l

 

c

A2

Fig.1.2 Experimental set-up for two bulb method

c hamber-2 is thoroughly mixed and analysed for component A. By ignoring the v olume of the capillary tube and assuming uniform concentrations in both chambers at

a ny time of the

diffusion, equation

dc

A

D

AB

(c

A 2

c

A1

)

J

= −

A

D

AB

(1-23)

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,

dz

= −

V

2

dc

A2

=

S

J

=

S

m

D

AB

(c

A1

c

A2

)

d

θ

m

A

l

(1-24)

is written. On the other hand, the average concentration of component A

system

(c

is

found

from

any

one

of

the

equations

below,

A

c

o

A1

,

c

o

A2

,

c

A1

,

c

V

A2

(

1

+ V

are molar concentrations of com

2

)

c

A

= V c

1

o

A1

+ V

2

c

o

A2

(

V

1

+ V

2

)

c

A

= V c

1

A1

+ V

2

c

A2

pone t A in chamber-1

n

(1-25)

(1-26)

) in the where and

chamber-2 at the equation (1-26) a

beginning and at the end

o

f

nd substituted into equation 1-

(

the experiment. If c A1 is solv ed from 24) ,

c

A

2

c

o

A

2

dc

A2

1 is solv ed from 24) , ⌠ c ⎮ A 2 ⌡ c o A

p( c

A

c

A2

)

=

θ

o

d θ

is obtained. Where, p is defined as

p

=

D

AB

(

V

1

+ V

2

)

(l/S

m

)V V

1

2

After performing integral, substituting p and solving for D AB finally,

D

AB

=

o lV 1 c −c V 2 A A2 ln S (V + V )
o
lV 1
c
−c
V 2
A
A2
ln
S
(V
+
V
)
θ
c
c
m
1
2
A
A2

(1-27)

A can be found from equation

is obtained. Since V 1 , V 2 , S m , l

(1-25), by measuring the c A2 after an experimentation time of θ, D 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

are all known, and

c

AB

15

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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 2 p A2 ≈0 N A z p o p A1 = l
gas B
2
p A2 ≈0
N
A
z
p o
p A1 =
l 1
A
Liquid A
Fig.1.3 Winkelmann
experime
nt
ρ
A dV
A
N =−
, where
A
M
S
d θ
A
m

equations (1-19) can be written.

N

A =

D

AB

P

RTz (p

B

)

ln

the liqui

d

(p

( p

A1

p

A2

)

(1-19)

Here, p A1 is the partial pressure of component A at the

liquid-gas interface and hence equals the vapor

pressure of

temperature. The partial pressure of A at the tube mouth (p A2 ) can be taken zero, by making volumetric 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

of A, which is equal to the mass transfer flux of A in

the z-direction, can be written as:

V A , M A and ρ A are volume, molecular weight and

o A ) at the experimentation

density of the liquid respectiv e ly. On the other hand, S m being the cross-sectional area

of the tube,V A = S m (l -z) and d V A = -S

can be written. If all these are substituted

m dz

into equation (1-19):

 

ρ

A

dz

=

D

AB

P

p o

A

M

A

dt

RTz (p

B

)

ln

 

z θ

 

D

M

A

P p

o

θ

and

z dz

=

AB

A

d

θ

and finally,

 
 

z

0

ρ

A

RT (

p

B

)

ln

o

   

o

 

2

2

 

2D

AB

M

A

P p

A

θ

 

z

θ

z =

0

ρ

A R T(p

B

 

)

ln

(1-28)

is obt ained. By measuring the liquid levels at the beginning (z 0 ) and at the end (z θ ) of the experimentation time θ, D AB 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 o C. The tube filled with liquid carbon tetra chloride till 10 mm

d in the

o C, v apor pressure and the

b elow its mouth is subjected to air flow. After 55

t ube falls 73.8 mm. W

d ensity of carbon tetrachloride are 282 mmHg and 1 500 kg/m .

hours and 29 minutes the level of the liqui

hat is the value of molecular diffusivity? At 50

3

M A = 154.

Solution:

From the givens, z o =10 mm and

z t =10 +73.8 = 83.8 mm.

(p

B

)

ln

=

760

(760

282)

ln[760 /(760

282)]

= 608.1 mmHg

θ = (55)(3 600) + (29)(60) = 199 740 sec. Then, from equation (1-28),

is found.

D AB

=

[(83.8)

2

2

(10) ]*10

6

(1 500)(0.083)(273

+

50)(608.1)

2(154)(1.013)(282)(199 740)

= 9.63*10

6

m