MASS TRANSFER and MASS TRANSFER OPERATIONS
Erden ALPAY
Mustafa DEMİRCİOĞLU
Ege UniversityEngineering FacultyChemical Engineering Department BornovaİzmirTURKEY
September2006
TABLE OF CONTENTS
(You can click subject name in order to reach the related page)
Preface 
vii 
Introduction 
1 
Chapter1 : 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 NonTransferring 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 CrossSectional Area 
12 
Mass Transfer by Molecular Diffusion in MultiComponent 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 MultiComponent 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 
SteadyState Diffusion 
33 
UnsteadyState 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 
Chapter2 : MASS TRANSFER BY TURBULENT DIFFUSION and MASS TRANSFER COEFFIENTS 
_{4}_{6} 
2.1 Introduction 
46 
2.2 A and B Transfer under Equimolar Counter Transfer Conditions 
48 
2.3 A Transfers through NonTransferring 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 
Chapter3 : 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 

Chapter4 : GAS ABSORPTION 
78 

4.1 Introduction 
78 

4.2 GasLiquid 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 

WettedWall 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 
StageWise 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 
Chapter5 : DISTILLATION 
150 
5.1 Introduction 
150 
5.2 LiquidVapor 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 
KValues 
162 
Bubble Point Temperature 
164 
Dew Point Temperature 
164 
EnthalpyComposition 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 LiquidGas (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 

Chapter6 : LIQUIDLIQUID EXTRACTION 
254 

6.1 Introduction 
254 

6.2 LiquidLiquid Equilibria 
255 

6.3 Selection of Solvent 
258 

6.4 Extraction Operations 
259 

StageWise Operations 
259 

Single Stage Extraction 
260 

CrossCurrent MultiStage Extraction 
262 
CounterCurrent MultiStage Extraction 
265 

CounterCurrent MultiStage Extraction under Reflux 
269 

Design of MixerSettler Units 
272 

Appendices 
276 

References 
284 
Preface
This CDbook covers the subjectmatter 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 liquidliquid extraction. Operations are discussed in both plate and packed columns including their internals and sizing. This CDbook 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, 2006İZMİR
Mustafa Demircioğlu mustafa.demircioglu@ege.edu.tr
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 (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
KMO _{4}
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
No part of this CDbook 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 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 ^{1}^{6} ) 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,
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
_{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
solid plate
(a)
(b)
Fig.2 Mass transfer (a) in laminar, (b) in turbulent flow
other layers have different velocities, which increase in zdirection. This type of flow is known as streamline or laminar flow. In this type of flow, there is not velocity component in the zdirection (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 zdirection 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 zdirections. As the plate is coated with dissolving solid A, a concentration gradient for component A in zdirection 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 zdirection, mass transfer in z direction must take place. In the laminar flow, since only the movement of single molecules in zdirection is possible, molecules of solute A diffuse from one layer to the next layer in zdirection. 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: liquidliquid, liquidgas, liquidsolid and gassolid. Gasgas system is not possible, as gases mix with each other in any proportion. As an example, take liquidgas 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
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
_{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
z
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
_{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}
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 petrochemical, 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 3540 %), and the sideproducts 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 solidliquid 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, liquidliquid 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
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
_{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 solidgas 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.
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
_{6}
Chapter1
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 _{A}_{z} ,is written as:
J Az = D AB
^{d}^{c} A
dz
(11)
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: kmolA/m ^{2} s. dc _{A} /dz is the concentration gradient causing the mass transfer as kmolA/m ^{3} m. () sign emphasizes that diffusion always occurs in the direction of decreasing concentration. D _{A}_{B} 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 AB 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 :
^{d}^{c} B
z
dz
(kmolA/s)
can
be
related
(12)
to
the
(13)
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 _{A}_{z} (kg A/m ^{2} s) is written as:
j
Az =D AB
^{d}^{ρ} ^{A}
dz
(14)
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
No part of this CDbook 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 zdirection as u _{A}_{z} and u _{B}_{z} . Then, the total molar flux of each component relative to the fixed coordinates are N _{A}_{z} = c _{A} u _{A}_{z} and N _{B}_{z} = c _{B} u _{B}_{z} , where c _{A} and c _{B} are molar concentrations of A and B (kmol/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 
(15)
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 _{A}_{z} = c _{A} (u _{A}_{z} 
u&
z
) =
c
A u Az 
c
A
u&
z
(16)
can be written. After substitutions from the equations above finally,
N Az = J Az +
^{c} ^{A} ( N _{A}_{z} + N _{B}_{z} )
c
(17)
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 _{A}_{z} + N _{B}_{z} )
The relationship between total molar flux and total molar rate ( N can be written as:
N =
Az
Az
)
(18)
(kmol A/s)
(19)
Similarly, if instead of molar units, the mass units are used; total mass flux of component A, n _{A}_{z} (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
(110)
(111)
8
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
1.2
MASS TRANSFER BY MOLECULAR DIFFUSION IN THE GASES
1.2.1. Integration of the General Flux Equation: Equation (17) can be integrated under various conditions. Let us consider its integration at steadystate with D _{A}_{B} and S _{m} are constant. First, substitute J _{A}_{z} from equation (11) and then separate the variables. With the limits of the integrals: at z=z _{1} c _{A} = c _{A}_{1} and at z = z _{2} c _{A} =c _{A}_{2} ;
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
(112)
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 (112),
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
(113)
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 (112) 
is 
found as: 
N A
=
N
A
D
AB
P
N
A
+
N
B
.
RTz
ln
(114)
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 (112) is indeterminate. Then, we go back to the equation (17), with N _{B} =N _{A} this equation becomes:
9
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
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 (17) was integrated.
N
A
D AB
=
z
(
c
A1
−
c
A2
)
(115)
is obtained. This equation is the special solution of equation (112) for this case. Similarly, the special solutions of equations (113) and (114) for this case are:
and
N
A
N
A
=
=
D AB
RTz
D
AB
P
RTz
(
p
A1
−
p
(
y
A1
−
A2
)
y
A2
(116) 

) 
(117) 
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 zeronetflux”. 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 NonTransferring B: This occurs in gas absorption operations. In this special case, since component B is not absorbed, N _{B} =0 and then equations (112), (113) and (114) 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
(118)
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 _{A}_{1} – c _{A}_{2} = c _{B}_{2} – c _{B}_{1} , p _{A}_{1} – p _{A}_{2} = p _{B}_{2} – p _{B}_{1} and y _{A}_{1} – y _{A}_{2} = y _{B}_{2} – y _{B}_{1} , the right hand sides of the equations given in (118) 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
)
(119)
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
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
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 nontransferring. 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.
(a)
P
p
B2
p
A2
P
P
p
B2
p
p
B1
p A2
(b)
Fig.1.1 Concentration profiles (a) in equimolar counter transfer and (b) in A transfers through nontransferring 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 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 N _{A} =  m N _{B} can be written. Hence, substituting N _{B} =  (n/m) N _{A} into any one of the equations (112), (113) and (114) N _{A} is calculated.
Example1.1) 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
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 _{A}_{B} = 4.10 ^{}^{5} m ^{2} /s.
11
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
Equation(113) can be used.
N
A
N
A
1
=
=
N
A
+
N
B
N
A
−
0.5N
A
1
−
0.5
Solution :
^{A}


= 2 

B
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} kmol A/m ^{2} s
N _{B} =  (0.5) N _{A} =  1.29*10 ^{}^{4} kmol 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/kmol). In this case substituting N _{B} =  (λ _{A} /λ _{B} ) N _{A} into one of the equations (1 12), (113) and (114) 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 CrossSectional Area: If the mass transfer area S _{m} does not remain constant and changes with z, the fluxes in the equation (17) do not
remain constant even at steadystate. Since, in this case
and N _{B} in the equation (17) are first replaced with
expressed as function of z and then the integral is performed. By dividing soobtained
( N
Az
)
with the S _{m} value calculated at the specified z, N _{A} at this z is obtained.
Example1.2) Calculation of Molar Flux in Varying CrossSection
SO _{2} (A) is transferring at steadystate through nontransferring O _{2} (B) in a metal conduit, 2.0 meter long, at 10 bars and 598 K. The crosssection 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
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
Calculate the total molar flux of SO _{2} at midpoint 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.
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.(17) 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
[ 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
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
1.2.7 Mass Transfer by Molecular Diffusion in MultiComponent 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 (112, (113) and (114) by making two modifications in the
N i second,
an effective diffusivity defined by equation (120) is taken in the place of D _{A}_{B} .
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
(120)
With these changes, the equation (112) becomes:
N
A
=
N
A
cD Aef
i
n
∑
=
A
N
i
z
ln
(121)
As it is seen from equation (1 20), effective diffusivity D _{A}_{e}_{f} , 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 (120) simplifies to:
D
Aef
^{=}
1 − y
A
n
∑
i = B
y
i
D
Ai
(122)
1.2.8 Determinat
equations above that to use any one of these, binary diffusivity, D _{A}_{B} 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. TwoBulb Method: This method is used when both components are gas at the experime ntation conditions. The experimental setup as shown in Fig.1.2, consists of two chambers with V _{1} , V _{2} volumes, connected with a capillary tube whose length and crosssection are l and S. This setup 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 chamber1 is charged with pure A and the chamber2 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
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
1 
o 
2 
c 
o 

c 
A1 
S 
m 
V 2 
A2 

V 
1 





c 
A1 
z 
l 
c A2 
Fig.1.2 Experimental setup for two bulb method
c hamber2 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
(123)
l
can be written. The accumulation of component A in chamber2 is due to the mass
transfer of this component from chamber1. Thus,
dz
= −
V
2
dc 
A2 
= 
S 
J 
= 
S 
m 
D 
AB 
(c 
A1 
− 
c 
A2 
) 

d 
θ 
m 
A 
l 
(124)
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 chamber1
n
(125)
(126)
) in the where and
chamber2 at the equation (126) a
beginning and at the end
o
f
nd substituted into equation 1
(
the experiment. If c _{A}_{1} is solv ed from 24) ,
⌠ ^{c}
⎮
A
2
⌡
c
o
A
2
dc
A2
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 _{A}_{B} finally,
D
AB
=
(127)
A can be found from equation
is obtained. Since V _{1} , V _{2} , S _{m} , l
(125), by measuring the c _{A}_{2} after an experimentation time of θ, D is calculated from equation (127). 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 zdirection by molecular diffusion, as its concentration at the liquidgas
interface (point1) is higher than that at the tube mouth (point2). Mass transfer takes
are all known, and
c
AB
15
No part of this CDbook may be multiplied for commercial purposes. E.Alpay & M.Demircioğlu
place under the conditions of “A transfers through nontransferring B”, as component
B is not absorbed into liquid A. So, any one of the
equations (119) can be written.
N
_{A} =
D
AB
P
RTz (p
B
)
ln
the liqui
d
(p
( p
A1
−
p
A2
)
(119)
Here, p _{A}_{1} is the partial pressure of component A at the
liquidgas interface and hence equals the vapor
pressure of
temperature. The partial pressure of A at the tube mouth (p _{A}_{2} ) 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 zdirection, 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 crosssectional 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 (119): 
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 
(128)
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 _{A}_{B} can be calculated from this equation.
Example1.3) 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 (128),
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
Viel mehr als nur Dokumente.
Entdecken, was Scribd alles zu bieten hat, inklusive Bücher und Hörbücher von großen Verlagen.
Jederzeit kündbar.