Mass Transfer Sample Chapters

Revised Study
Material
For
GATE PSU
Chemical Engineering
Mass Transfer
GATE Syllabus
Ficks laws, molecular diffusion in fluids, mass transfer

coefficients, film, penetration and surface renewal
theories; momentum, heat and mass transfer analogies;
stage-wise and continuous contacting and stage
efficiencies; HTU & NTU concepts design and operation
of equipment for distillation, absorption, leaching,
liquid-liquid
extraction,
drying,
humidification,
dehumidification and adsorption.
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TABLE OF CONTENTS
Chapter 1
DIFFUSION
1.1 Introduction
1.2 Ficks Law
1.3 Relation Among Molar Fluxes
1.4 Diffusivity
1.4.1 Diffusivity in Gases
1.4.2 Diffusivity in Liquids
1.4.3 Diffusivity in Solids
1.5 Steady State Diffusion
1.5.1 Diffusion Through A Stagnant Gas Film
1.5.2 Equi-Molar Counter Diffusion
1.5.3 Diffusion into An Infinite Standard Medium
1.5.4 Diffusion in Liquids
1.5.5 Diffusion in Solids
1.6 Transient Diffusion
2
2
3
4
5
5
6
7
7
7
13
16
22
25
26
Chapter 2
MASS TRANSFER COEFFICIENTS
28
28
28
29
31
31
33
34
35
36
38
39
41
44
45
47
49
50
51
DISTILLATION
56
56
56
56
57
2.1 Introduction
2.2 Convective Mass Transfer Coefficient
2.3 Significant Parameters in Convective Mass Transfer
2.4 Application of Dimensionless Analysis to Mass Transfer
2.4.1 Transfer into a Stream Flowing Under Forced Convection
2.4.2 Transfer into a Phase Whose Motion is Due to Natural Convection
2.5 Analysis Among Mass, Heat And Momentum Transfer
2.5.1 Reynolds Analogy
2.5.2 Chilton Colburn Analogy
2.6 Convective Mass Transfer Correlations
2.6.1 Flat Plate
2.6.2 Single Sphere
2.6.3 Single Cylinder
2.6.4 Flow Through Pipes
2.7 Mass Transfer Between Phases
2.8 Simultaneous Heat And Mass Transfer
2.8.1 Condensation of Vapor on Cold Surface
2.8.2 The Wet Bulb Thermometer
Chapter 3
3.1 Introduction
3.2 Vapor Liquid Equilibria
3.2.1 Pressure Temperature Composition Diagram
3.2.2 Temperature And Composition Diagram
i
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3.2.3 Equilibrium Diagram

3.3 Relative Volatility
3.4 Raoults Law
3.5 Constant Boiling Mixtures
3.5.1 Minimum Boiling Mixtures
3.5.2 Maximum Boiling Mixtures
3.6 Flash Vaporization
3.7 Differential Distillation
3.8 Fractionation
3.8.1 Rectifying Section
3.8.2 Stripping Section
3.9 Number of Plates Analysis
3.9.1 The Method of McCabe And Thiele
3.9.2 The Method of Ponchon And Savarit
3.9.3 Fenskys Method
3.10 Reboilers
3.10.1 Kettle Reboilers
3.10.2 Thermosyphon Reboilers
3.10.3 Fired Reboilers
3.10.4 Forced Circulation Reboilers
3.11 Reflux Ratio
3.11.1 Total Reflux Ratio
3.11.2 Minimum Reflux Ratio
3.11.3 Optimum Reflux Ratio
3.12 Calculation For Rm
3.12.1 For Saturated Vapor Feed
3.12.2 For Saturated Liquid Feed
3.13 Tray Efficiency
3.13.1 Overall Efficiency
3.13.2 Murphree Plate Efficiency
3.13.3 Murphree Point Efficiency
57
57
58
58
58
59
60
61
62
62
63
63
63
66
68
68
69
69
71
71
72
72
73
74
74
74
75
75
75
75
76
Chapter 4
GAS ABSORPTION
82
82
82
83
88
90
91
91
92
93
HUMIDIFICATION AND DEHUMIDIFICATION
98
98
4.1 Introduction
4.2 Selection of Solvent
4.3 Single Component Absorption
4.4 Rate of Absorption
4.5 Calculation of Tower Height
4.5.1 When Equilibrium Curve And Operating Line Are Straight And Parallel
4.5.2 When Equilibrium Curve And Operating Line Are Straight And Non Parallel
4.6 Calculation For Ideal Number of Plates By Absorption Factor Method
4.8 HETP
Chapter 5
5.1 Introduction
ii
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5.2 Vapor Liquid Equilibrium

5.3 Dry Bulb Temperature
5.4 Wet Bulb Temperature
5.5 Dew Point Temperature
5.6 Adiabatic Saturation Temperature
5.7 Molal Humidity
5.8 Absolute Humidity
5.9 Saturation Humidity
5.10 Relative Humidity
5.11 Percentage Humidity
5.12 Humid Heat
5.13 Humid Volume
98
99
99
100
100
100
100
100
101
101
101
102
Chapter 6
DRYING
103
103
103
103
103
104
104
104
104
105
106
107
108
108
LIQUID EXTRACTION
111
111
111
111
112
114
117
118
120
LEACHING
122
122
122
123
124
6.1 Introduction
6.2 Moisture Content
6.2.1 Free Moisture Content
6.2.2 Unbound Moisture Content
6.2.3 Bound Moisture Content
6.2.4 Equilibrium Moisture Content
6.2.5 Critical Moisture Content
6.3 Rate of Drying
6.4 Drying Kinetics
6.5 Time Required For Drying
6.6 Moisture Movements in Solids During Drying in The Falling Rate Period
6.6.1 Liquid Diffusion Theory
6.6.2 Capillary Movement in Porous Solids
Chapter 7
7.1 Introduction
7.2 Equilibrium Relations in Extraction
7.2.1 Phase Rule
7.2.2 Triangular Coordinates And Equilibrium Data
7.3 Single Stage Liquid Extraction
7.4 Counter Current Process And Overall Balances
7.5 Stage to stage Calculation For Counter Current Extraction
7.6 Minimum Solvent Rate
Chapter 8
8.1 Introduction
8.2 Rate of Leaching
8.3 Equilibrium Relationship in Leaching
8.4 Equilibrium Diagrams For Leaching
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8.5 Single Stage Leaching

8.6 Counter Current Multi Stage Leaching
8.7 Constant Underflow in Counter Current Multistage Leaching
8.8 Variable Underflow in Counter Current Multistage Leaching
8.9 Variable Underflow in Counter Current Multistage Leaching: McCabe Thiele Method
124
125
126
128
130
Chapter 9
9.1 Introduction
9.2 Adsorption Kinetics
9.2.1 Langmuir Isotherm
9.2.2 Activated Carbon
9.2.3 Freundlich Isotherm
ADSORPTION
131
131
131
132
132
133
LEVEL 1
LEVEL 2
135
155
UNSOLVED QUESTIONS
179
QUESTIONS (2004 TO 2015)
190
190
194
197
200
204
208
211
213
215
217
219
221
SOLUTIONS
224
Chapter 10
Chapter 11
Chapter 12
2004
2005
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015
Chapter 13
iv
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DIFFUSION
CHAPTER
1
1.1 INTRODUCTION
The mass transfer is also important subject for chemical engineer. It is like as heat and
momentum transfer. Here is also two type of mass transfer that is molecular like as
conduction in heat transfer and convective mass transfer. The driving force is required
for any transfer; In mass transfer concentration difference is driving force. In this chapter
we will discuss molecular mass transfer.
The flux is defined as anything is passing through per unit area per unit time.
Molar
flux of a given species is a vector quantity denoting the amount of the particular species,
in either mass or molar units, that passes per given increment of time through a unit
area normal to the vector. The flux of species defined with reference to fixed spatial
coordinates, NA is
N
C A
---------------------- (1.1)
This could be written in terms of diffusion velocity of A, (i.e.,
) and average
velocity of mixture, , as
) C
--------------- (1.2)
By definition
C i
Therefore, equation (1.2) becomes
C A
C i
C i
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) y
C i
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For binary systems containing two components A and B,
) y
A (C A
) y
A (N A
C A (
) y
C
B
B)
----------- (1.3)
The first term on the right hand side of this equation is diffusional molar flux of A, and
the second term is flux due to bulk motion.
1.2 FICKS LAW:

An empirical relation for the diffusional molar flux, first postulated by Fick and,
accordingly, often referred to as Ficks first law, defines the diffusion of component A in
an isothermal, isobaric system. For diffusion in only the Z direction, the Ficks rate
equation is
JA D A B
where D
AB
dC A
dZ
is diffusivity or diffusion coefficient for component A diffusing through
component B, and dCA / dZ is the concentration gradient in the Z-direction.

A more general flux relation which is not restricted to isothermal, isobasic system could
be written as
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J A C DA B
dy A
dZ
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----------------- (1.4)
using this expression, Equation (1.3) could be written as
dy A
y
dZ
C DA B
--------------- (1.5)
1.3 RELATION AMONG MOLAR FLUXES:

For a binary system containing A and B, from Equation (1.5),
or
----------------------- (1.6)
-------------------- (1.7)
Similarly,
Addition of Equation (1.6) & (1.7) gives,
(y
y B) N
---------- (1.8)
By definition N = N A + N B and y A + y B = 1.
Therefore equation (1.8) becomes,
JA+JB=0
JA =JB
CD
3
AB
dy A
CD
dz
BA
dyB
dZ
--------------- (1.9)
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From
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yA+yB=1
dy A = dy B
Therefore Equation (1.9) becomes,

D AB = D BA ----------------------------------- (1.10)
This leads to the conclusion that diffusivity of A in B is equal to diffusivity of B in A.
1.4 DIFFUSIVITY
Ficks law proportionality, DAB, is known as mass diffusivity (simply as diffusivity) or as
the diffusion coefficient. DAB has the dimension of L
/ t, identical to the fundamental
dimensions of the other transport properties: Kinematic viscosity, = ( / ) in

momentum transfer, and thermal diffusivity, (= k / C ) in heat transfer.
Diffusivity is normally reported in cm2 / sec; the SI unit being m2 / sec.
Diffusivity depends on pressure, temperature, and composition of the system.
In table, some values of DAB are given for a few gas, liquid, and solid systems.
Diffusivities of gases at low density are almost composition independent, increase with
the temperature and vary inversely with pressure. Liquid and solid diffusivities are
strongly concentration dependent and increase with temperature.
General
range
of
values
of
Gases :
5 X 10 6
-------------
1 X 10-5
Liquids :
10 6
-------------
10-9
m2 / sec.
Solids :
5 X 10 14
-------------
1 X 10-10
m2 / sec.
diffusivity:
m2 / sec.
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In the absence of experimental data, semi theoretical expressions have been developed
which give approximation, sometimes as valid as experimental values, due to the
difficulties encountered in experimental measurements.
1.4.1 DIFFUSIVITY IN GASES:

Pressure dependence of diffusivity is given by
D AB
1
P
----------------------------------- (1.11)
And temperature dependency is according to
D AB T
----------------------------------- (1.12)
Diffusivity of a component in a mixture of components can be calculated using the

diffusivities for the various binary pairs involved in the mixture. The relation given by
Wilke is
D 1mixture
Where D
1
----------------------------------- (1.13)
y 3
y 2
y n
...........
D12 D13
D1n
1-mixture
is the diffusivity for component 1 in the gas mixture; D
1-n
is the
diffusivity for the binary pair, component 1 diffusing through component n; and y n is
the mole fraction of component n in the gas mixture evaluated on a component 1
free basis, that is
y 2
y2
----------------------------------- (1.14)
y 2 y 3 ....... y n
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1.4.2 DIFFUSIVITY IN LIQUIDS:

Diffusivity in liquid are exemplified by the values given in table Most of these values
are nearer to 10-5 cm2 / sec, and about ten thousand times shower than those in dilute
gases. This characteristic of liquid diffusion often limits the overall rate of processes
accruing in liquids (such as reaction between two components in liquids).
In chemistry, diffusivity limits the rate of acid-base reactions; in the chemical industry,
diffusion is responsible for the rates of liquid-liquid extraction. Diffusion in liquids is
important because it is slow.
Certain molecules diffuse as molecules, while others which are designated as
electrolytes ionize in solutions and diffuse as ions. For example, sodium chloride (NaCl),
diffuses in water as ions Na
and Cl-. Though each ions has a different mobility, the
electrical neutrality of the solution indicates the ions must diffuse at the same rate;
accordingly it is possible to speak of a diffusion coefficient for molecular electrolytes
such as NaCl. However, if several ions are present, the diffusion rates of the individual
cat ions and anions must be considered, and molecular diffusion coefficients have no
meaning.
Diffusivity varies inversely with viscosity when the ratio of solute to solvent ratio exceeds
five. In extremely high viscosity materials, diffusion becomes independent of viscosity.
1.4.3 DIFFUSIVITY IN SOLIDS:

Typical values for diffusivity in solids are shown in table. One outstanding characteristic
of these values is their small size, usually thousands of time less than those in a liquid,
which are in turn 10,000 times less than those in a gas.
Diffusion plays a major role in catalysis and is important to the chemical engineer. For
metallurgists, diffusion of atoms within the solids is of more importance.
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1.5 STEADY STATE DIFFUSION

In this section, steady-state molecular mass transfer through simple systems in which
the concentration and molar flux are functions of a single space coordinate will be
considered.
In a binary system, containing A and B, this molar flux in the direction of z, as given by
Eqn (1.5) is
CD
AB
dy A
y
dz
(N
N B ) --- (1.15)
1.5.1 DIFFUSION THROUGH A STAGNANT GAS FILM

The diffusivity or diffusion coefficient for a gas can be measured, experimentally using
Arnold diffusion cell. This cell is illustrated schematically in figure
The narrow tube of uniform cross section which is partially filled with pure liquid A, is
maintained at a constant temperature and pressure. Gas B which flows across the open
end of the tub, has a negligible solubility in liquid A,
and is also chemically inert to A. (i.e. no reaction
between A & B).
Component A vaporizes and diffuses into the gas
phase; the rate of vaporization may be physically
measured and may also be mathematically expressed
in terms of the molar flux.
Consider the control volume S z, where S is the cross
sectional area of the tube. Mass balance on A over this
control volume for a steady state operation yields
[Moles of A leaving at z + z] [Moles of A entering at z] = 0.
(i.e.)
SN
A z z
SN
A z
0.
-------------- (1.16)
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Dividing through by the volume, SZ, and evaluating in the limit as Z approaches zero,
we obtain the differential equation
dN A
0
dz
------------------------- (1.17)
This relation stipulates a constant molar flux of A throughout the gas phase from Z 1 to
Z2.
A similar differential equation could also be written for component B as,
dN B
0, ----------------------------------- (1.18)
dZ
and accordingly, the molar flux of B is also constant over the entire diffusion path from
z1 and z 2.
Considering only at plane z1, and since the gas B is insoluble is liquid A, we realize that
NB, the net flux of B, is zero throughout the diffusion path; accordingly B is a stagnant
gas.
From equation (1.15)
NA CD
AB
dy A
y
dz
A (N A
NA CD
AB
dy A
y
dz
CD
AB
N B)
Since N B = 0,
Rearranging,
NA
1 y
dy A
dz
------------ (1.19)
This equation may be integrated between the two boundary conditions:
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at z = z1
YA = YA1
at z = z2
YA = yA2
And
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Assuming the diffusivity is to be independent of concentration, and realizing that N A is

constant along the diffusion path, by integrating equation (1.19) we obtain
Z2
y A2
Z1
y A1
d z C DAB
NA
1 y A 2
ln
1 y A1
C D AB
Z2 Z1
dy A
1 y A
--------------(1.20)
The log mean average concentration of component B is defined as
B , lm
B2
y
ln
y
B2
B1
y B1
----------------------------------- (1.21)
Since y B 1 y A ,
B , lm
(1 y
A2
) (1 y
y
ln
A1
A2
y A1
A1
y
ln
A2
A2
y A1
------- (1.22)
Substituting from Eqn (5) in Eqn (4),

N
C D AB ( y A1 y A 2 )
Z 2 z1
y B, lm
For an ideal gas C
-------------------- (1.23)
n
p
, and
V
RT
For mixture of ideal gases y A
pA
P
Therefore, for an ideal gas mixture equation. (1.23) becomes

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D AB
( p A1 p A 2 )
----------------------------------- (1.24)
RT ( z2 z1 )
p B, lm
This is the equation of molar flux for steady state diffusion of one gas through a second
stagnant gas.
Many mass-transfer operations involve the diffusion of one gas component through
another non-diffusing component; absorption and humidification are typical operations
defined by these equation.
Example 1.1 Oxygen is diffusing in a mixture of oxygen-nitrogen at 1 std atm, 25C.

Concentration of oxygen at planes 2 mm apart are 10 and 20 volume % respectively.
Nitrogen is non-diffusing.
(a) Derive the appropriate expression to calculate the flux oxygen. Define units of
each term clearly.
(b) Calculate the flux of oxygen. Diffusivity of oxygen in nitrogen = 1.89 * 10 5 m / s.
Let us denote oxygen as A and nitrogen as B. Flux of A (i.e.) N A is
Solution:
made up of two components, namely that resulting from the bulk motion of A (i.e.), Nx A
and that resulting from molecular diffusion J A:
N A Nx A J A ---------------------------------- (1)
From Ficks law of diffusion,
D AB
dCA
dz
----------------------------------------- (2)
Substituting this equation (1)
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N A Nx A D AB
dCA
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----------------------------- (3)
dz
Since N = N A + N B and x A = C A / C equation (3) becomes
NA NA NB
CCA
D AB
dCA
dz
Rearranging the terms and integrating between the planes between 1 and 2,
dC A
dz
C A2
cD
C A1 N C C N N
AB
A
A
A
B
-------------- (4)
Since B is non diffusing N B = 0. Also, the total concentration C remains constant.

Therefore, equation (4) becomes
dC A
z
C
C A2
A1 N C N C
CD AB
A
A A
C C A2
1
ln
NA
C C A1
Therefore,
NA
CD AB
z
ln
C C A2
C C A1
---------------------------- (5)
Replacing concentration in terms of pressures using Ideal gas law, equation (5) becomes
NA
D AB P t
RTz
ln
P t P A2
P t P A1
--------------------------- (6)
where
D AB = molecular diffusivity of A in B
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P T = total pressure of system

R = universal gas constant
T = temperature of system in absolute scale
z = distance between two planes across the direction of diffusion
P A1 = partial pressure of A at plane 1, and
P A2 = partial pressure of A at plane 2
Given:
D AB = 1.89 * 10 5 m2/sec
P t = 1 atm = 1.01325 * 10 5 N/m 2
T = 25C = 273 + 25 = 298 K
z = 2 mm = 0.002 m
P A1 = 0.2 * 1 = 0.2 atm (From Ideal gas law and additive pressure rule)
P A2 = 0.1 * 1 = 0.1 atm
Substituting these in equation (6)
1.89 * 10 1.01325 * 10 ln 1 0.1
NA
8314 298 0.002
1 0.2
N A 4.55 10 5 kmol / m 2 .s
1.5.2 EQUI-MOLAR COUNTER DIFFUSION:

A physical situation which is encountered in the distillation of two constituents whose
molar latent heats of vaporization are essentially equal, stipulates that the flux of one
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gaseous component is equal to but acting in the opposite direction from the other
gaseous component; that is, NA = - NB.
The molar flux NA, for a binary system at constant temperature and pressure is described
by
or
CD
AB
AB
dy A
y
dz
dC A
y
dz
(N
(N
N B)
N B)
------- (1.25)
with the substitution of NB = - NA, Equation (1.25) becomes,
AB
dC A
dz
----------------- (1.26)
For steady state diffusion Equation (1.26) may be integrated, using the boundary
conditions:
at
z = z1
CA = CA1
and
z = z2
CA = CA2
Giving,
Z2
NA d z D
C A2
AB
Z1
dC
C A1
from which
D
z
2z1
For ideal gases, C A
13
AB
(C
A1
A2 )
------------------- (1.27)
nA
p
A . Therefore Equation (1.27) becomes
V
RT
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D AB
(P
R T ( z 2 z 1)
A1
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A2 ) ---------- (1.28)
This is the equation of molar flux for steady-state equi-molar counter diffusion.
Concentration profile in this equi-molar counter diffusion may be obtained from,
d
(N A ) 0 (Since NA is constant over the diffusion path).
dz
And from equation. (1.27)
AB
d CA
.
dz
Therefore
or
d
dz
CA
0. ----------------------------------- (1.29)
dz
AB
d CA
0.
d z
This equation may be solved using the boundary conditions to give
C
C
A
A1
A1
A2
zz1
z1 z 2
-------------- (1.30)
Equation, (1.30) indicates a linear concentration profile for equi-molar counter diffusion.
Example 1.2 Methane diffuses at steady state through a tube containing helium. At
point 1 the partial pressure of methane is p A1 = 55 kPa and at point 2, 0.03 m apart P A2
= 15 KPa. The total pressure is 101.32 kPa, and the temperature is 298 K. At this
pressure and temperature, the value of diffusivity is 6.75 * 10 5 m 2/sec.
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(i).
Calculate the flux of CH 4 at steady state for equi-molar counter diffusion.
(ii).
Calculate the partial pressure at a point 0.02 m apart from point 1.
Solution:
For steady state equi-molar counter diffusion, molar flux is given by
NA
D AB
RT z
p A 1 p A 2 --------------------------- (1)
Therefore;
NA
6.75 *10 5
kmol
55 15 2
8.314 * 298 * 0.03
m .sec
N A 3.633 * 10 5
kmol
m 2 sec
And from (1), partial pressure at 0.02 m from point 1 is:
3.633 * 10 5
6.75 * 10 5
55 p A
8.314 * 298 * 0.02
p A = 28.33 kPa
Example 1.3 For Equimolar counter diffusion from a sphere to a surrounding stationary
infinite medium, the mass flux N Ai of the diffusing component A at the interface is given
by N Ai
DA
RT
Ai
C Ab where DA is the diffusivity, R the radius of sphere and CAi and CAb
the molar concentrations of A at the interface and at a point far away from the sphere.
Show that the Sherwood number, based on the diameter of the sphere is equal to 2.
Solution:
The mass flux N Ai is given by

N Ai
DA
R
Ai
C Ab
--------------------------- (1)
The mass flux N Ai of the diffusing component A at the interface is also given by
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N Ai kC C Ai C Ab
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--------------------------- (2)
From the equations (1) and (2), we get

kC
DA
R
kC R
1
DA
kC d
2
DA
NSh
since R ,d=diameter of sphere

2
kC d
2
DA
1.5.3 DIFFUSION INTO AN INFINITE STANDARD MEDIUM:

Here we will discuss problems involving diffusion from a spherical particle into an
infinite body of stagnant gas. The purpose in doing this is to demonstrate how to set up
differential equations that describe the diffusion in these processes. The solutions,
obtained are only of academic interest because a large body of gas in which there are
no convection currents is unlikely to be found in practice. However, the solutions
developed here for these problems actually represent a special case of the more
common situation involving both molecular diffusion and convective mass transfer.
EVAPORATION OF A SPHERICAL DROPLET:
As an example of such problems, we shall consider the evaporation of spherical droplet

such as a raindrop or sublimation of naphthalene ball. The
vapor formed at the surface of the droplet is assumed to
diffuse by molecular motions into the large body of
stagnant gas that surrounds the droplet.
Consider a raindrop, as shown in figure. At any moment,
when the radius of the drop is r0, the flux of water vapor at
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any distance r from the center is given by
N A C D AB
dy
dr
N A N B
Here N B = 0 (since air is assumed to be stagnant)

Therefore,
dy
N A C D AB
dr
NA
Rearranging,
C D AB d y
NA
The flux N
1 y A
__________ (1.31)
dr
is not constant, because of the spherical geometry; decreases as the
distance from the center of sphere increases. But the molar flow rate at r and r + r are
the same.
This could be written as,
AN A
AN A
__________ (1.32)
r r
where A = surface area of sphere at r or r + r.

Substituting for A = 4 r 2 in equation (1.32),
4 r
NA
r r
4 r
NA
or
r
lim
r 0
17
NA
r r
NA
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d
r
dr
ss
NA 0
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__________ (1.33)
Integrating,
N A constant
From equation (1.34), r
N A r 02 N A 0
__________ (1.34)
Substituting for N A from equation (1.31),
r 02 N A 0
dr
r
C D AB d y A
r 02 N A 0
1 y A
dr
C D AB
dy
1 y
__________ (1.35)
Boundary condition:
And
At r = r 0
y A = y AS
At r =
y A = y A
Therefore equation (1.35) becomes,
r 02
NA 0
yy
1
C D AB ln 1 y A

r
r0
A
AS
Simplifying,
NA 0
C D AB
r0
1 y A
ln
1 y A S
__________ (1.36)
Time required for complete evaporation of the droplet may be evaluated from making
mass balance.
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Moles of water diffusing

moles of water leaving the droplet
unit time
unit time
4 r 02 N A 0
d
dt
4

r3 L
0
3
M A
4 r0 2
d r0
MA dt
__________ (1.37)
Substituting for N A0 from equation (1.36) in equation (1.37),
C D AB
r0
1 y A
L d r0

ln
1 y AS
MA dt
__________ (1.38)
Initial condition :
When t = 0
r0 = r1
Integrating equation (1.38) with these initial condition,

t
d t
MA
MA
1
C D AB
1
2 C D AB
1
1 y A
ln
1 y
AS
2
r1
1 y A
ln
1 y
AS
d r0
r1
__________ 1.39
Equation (1.39) gives the total time t required for complete evaporation of spherical
droplet of initial radius r 1.
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Example 1.4 A sphere of naphthalene having a radius of 2mm is suspended in a large

volume of shell air at 318 K and 1 atm. The surface pressure of the naphthalene can be
assumed to be at 318 K is 0.555 mm Hg. The D AB of naphthalene in air at 318 K is 6.92 *
10 6 m 2/sec. Calculate the rate of evaporation of naphthalene from the surface.
Solution:
Steady state mass balance over a element of radius r and r + r leads to
SNA
SNA
rr
0 ---------------------------- (1)
where S is the surface are (= 4 r 2)

dividing (1) by Sr, and taking the limit as r approaches zero, gives:
d r 2N A
dr
Integrating r 2 N A = constant (or) 4 r 2 N A = constant

We can assume that there is a film of naphthalene vapor / air film around naphthalene
through which molecular diffusion occurs.
Diffusion of naphthalene vapor across this film could be written as,
N A CD AB
dy
dr
N A N B
N B = 0 (since air is assumed to be stagnant in the film)
N A CD AB
dy
dr
N A CD AB
N A CD AB
20
d
dr
NA
yA
1 y A
d ln 1 y
dr
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W A = Rate of evaporation = 4 r 2 N A R = constant.
WA
WA
dr
r
4 D AB C d ln 1 y
4 r
CD AB d ln 1 y
dr
Boundary condition:
At r = R
0.555
7.303 * 10 4
760
ln (1 y A) = - 7.3 * 10 4
At r =
yA = 0
Therefore W A
dr
r
4 D AB C
WA
ln (1-y A) = 0
d ln 1 y A
7.3 *10 4
1
r 4 D AB C ln 1 y
R
0 7.3 *10
W A 0 4 D AB C 0 7.3 * 10 4
R
W A = 4 R D AB C * 7.3 * 10 4
P
1.01325 * 10 5
Gas cons tan t * T

8314 * 318
= 0.0383 kmol/m 3
Initial rate of evaporation:

Therefore W A = 4 * 3.142 * 2 * 10 3 * 6.92 * 10 6 * 0.0383 * 7.3 * 10 4
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= 4.863 * 10 12 kmol / sec

W A = 1.751 * 10 5 mol/hr.
1.5.4 DIFFUSION IN LIQUIDS:

Equation derived for diffusion in gases equally applies to diffusion in liquids with some
modifications. Mole fraction in liquid phases is normally written as x (in gases as y). The
.
M av
concentration term C is replaced by average molar density,
a) For steady state diffusion of A through non diffusivity B:

N A = constant , N B = 0
NA
D AB
xA1 x A2 ----------------------------------- (1.40)
z x BM M av
where Z = Z 2 Z 1, the length of diffusion path; and

X BM
X B 2 X B1
X
ln B 2
X B 1
----------------------------------- (1.41)
b) For steady state equi-molar counter diffusion:

N A = - N B = const
NA
D AB
Z
A1
C A2
D AB
x A1 x A 2 ----------------------------------- (1.42)
Z M av
Example 1.5 Calculate the rate of diffusion of butanol at 20C under unidirectional
steady state conditions through a 0.1 cm thick film of water when the concentrations of
butanol at the opposite sides of the film are, respectively 10% and 4% butanol by
22
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weight. The diffusivity of butanol in water solution is 5.9 * 10 6 cm 2/sec. The densities
of 10% and 4% butanol solutions at 20C may be taken as 0.971 and 0.992 g/cc
respectively. Molecular weight of butanol (C 4 H 9 OH) is 74, and that of water 18.
Solution:
For steady state unidirectional diffusion,
NA
D AB
z
x A1 x A2
x B, lm
where C is the average molar density.

M avg
Conversion from weight fraction the Mole fraction:
x A1
x A2
0.1 74
0.1 74
0.9 18
0.04 74
0.04 74
0.026
0.96 18
0.010
Average molecular weight at 1 & 2:
M1
M2
1
19.47 kg Kmol
0.1 74 0.9 18
1
18.56 kg Kmol
0.04 74 0.96 18
1 M1 2 M2

2
M avg
0.971 19.47 0.992 18.56

2
= 0.0517 gmol / cm 3
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= 51.7 kmol/m 3
x B,lm
x B 2 x B1
ln x B 2 x B1
(i.e.) x B,lm
1 x A2 1 x A1
1 x A2
ln
1 x A1
1 0.01 1 0.026
1 0.01
ln
1 0.026
0.016
0.982
0.0163
For more details
24
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Revised Study

Ficks laws, molecular diffusion in fluids, mass transfer

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MASS TRANSFER COEFFICIENTS

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3.2.3 Equilibrium Diagram

HUMIDIFICATION AND DEHUMIDIFICATION

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5.2 Vapor Liquid Equilibrium

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8.5 Single Stage Leaching

QUESTIONS (2004 TO 2015)

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This could be written in terms of diffusion velocity of A, (i.e.,

Therefore, equation (1.2) becomes

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For binary systems containing two components A and B,

1.2 FICKS LAW:

is diffusivity or diffusion coefficient for component A diffusing through

component B, and dCA / dZ is the concentration gradient in the Z-direction.

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using this expression, Equation (1.3) could be written as

1.3 RELATION AMONG MOLAR FLUXES:

Addition of Equation (1.6) & (1.7) gives,

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Therefore Equation (1.9) becomes,

/ t, identical to the fundamental

dimensions of the other transport properties: Kinematic viscosity, = ( / ) in

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1.4.1 DIFFUSIVITY IN GASES:

And temperature dependency is according to

Diffusivity of a component in a mixture of components can be calculated using the

is the diffusivity for component 1 in the gas mixture; D

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1.4.2 DIFFUSIVITY IN LIQUIDS:

and Cl-. Though each ions has a different mobility, the

1.4.3 DIFFUSIVITY IN SOLIDS:

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1.5 STEADY STATE DIFFUSION

1.5.1 DIFFUSION THROUGH A STAGNANT GAS FILM

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This equation may be integrated between the two boundary conditions:

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Assuming the diffusivity is to be independent of concentration, and realizing that N A is

The log mean average concentration of component B is defined as

Substituting from Eqn (5) in Eqn (4),

For an ideal gas C

For mixture of ideal gases y A

Therefore, for an ideal gas mixture equation. (1.23) becomes

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Example 1.1 Oxygen is diffusing in a mixture of oxygen-nitrogen at 1 std atm, 25C.

Substituting this equation (1)

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Since N = N A + N B and x A = C A / C equation (3) becomes

Since B is non diffusing N B = 0. Also, the total concentration C remains constant.

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P T = total pressure of system

1.89 * 10 1.01325 * 10 ln 1 0.1

8314 298 0.002