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

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

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

8.6 Counter Current Multi Stage Leaching 125
8.7 Constant Underflow in Counter Current Multistage Leaching 126
8.8 Variable Underflow in Counter Current Multistage Leaching 128
8.9 Variable Underflow in Counter Current Multistage Leaching: McCabe Thiele Method 130
Chapter 9
ADSORPTION 131
9.2 Adsorption Kinetics 131
9.2.1 Langmuir Isotherm 132
9.2.2 Activated Carbon 132
9.2.3 Freundlich Isotherm 133
Chapter 10
LEVEL 1 135
LEVEL 2 155
Chapter 11
UNSOLVED QUESTIONS 179
Chapter 12
QUESTIONS (2004 TO 2015) 190
2004 190
2005 194
2006 197
2007 200
2008 204
2009 208
2010 211
2011 213
2012 215
2013 217
2014 219
2015 221
Chapter 13
SOLUTIONS 224
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CHAPTER
1
DIFFUSION
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 A C A A ---------------------- (1.1)
This could be written in terms of diffusion velocity of A, (i.e., A ) and average

velocity of mixture, , as
N A C A ( A ) C A --------------- (1.2)
By definition
C i i
* i
C
Therefore, equation (1.2) becomes
C A
N A C A ( A ) C i i
C i
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C A ( A ) y A C i i
i
For binary systems containing two components A and B,
N A C A ( A ) y A (C A A C B B)
C A ( A ) y A (N A N B )
N A C A ( A ) y A N ----------- (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
dC A
JA D A B
dZ
where D AB 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
dy A
J A C DA B ----------------- (1.4)
dZ
using this expression, Equation (1.3) could be written as
dy A
N A C DA B y A N --------------- (1.5)
dZ
1.3 RELATION AMONG MOLAR FLUXES:
For a binary system containing A and B, from Equation (1.5),
N A J A y A N
or J A N A y A N ----------------------- (1.6)
Similarly,
J B N B y B N -------------------- (1.7)
Addition of Equation (1.6) & (1.7) gives,
J A J B N A N B (y A 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
dy A dyB
CD AB CD BA --------------- (1.9)
dz dZ
From 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

2
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 diffusivity:
Gases : 5 X 10 6 ------------- 1 X 10-5 m2 / sec.
Liquids : 10 6 ------------- 10-9 m2 / sec.
Solids : 5 X 10 14 ------------- 1 X 10-10 m2 / sec.
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
1
D AB ----------------------------------- (1.11)
P
And temperature dependency is according to
3
D AB T 2
----------------------------------- (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
1
D 1mixture ----------------------------------- (1.13)
y 2 y 3 y n
...........
D12 D13 D1n
Where D 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
y2
y 2 ----------------------------------- (1.14)
y 2 y 3 ....... y n
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.
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
dy A
N A CD AB y A (N A N B ) --- (1.15)
dz
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)
Dividing through by the volume, SZ, and evaluating in the limit as Z approaches zero,
we obtain the differential equation
dN A
0 ------------------------- (1.17)
dz
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)
dy A
NA CD AB y A (N A N B)
dz
Since N B = 0,
dy A
NA CD AB y A N A
dz
Rearranging,
CD AB dy A
NA ------------ (1.19)
1 y A dz
This equation may be integrated between the two boundary conditions:
at z = z1 YA = YA1
And at z = z2 YA = yA2
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
dy A
N A d z C DAB 1 y A
Z1 y A1
C D AB 1 y A 2
NA ln --------------(1.20)
Z2 Z1 1 y A1
The log mean average concentration of component B is defined as
y y
y
B2 B1
----------------------------------- (1.21)
ln
B , lm
y
y B1
B2

Since y B 1 y A ,
(1 y ) (1 y ) y y
y
A2 A1

A1 A2
------- (1.22)
ln ln
B , lm
y y
y A1 y A1
A2 A2

Substituting from Eqn (5) in Eqn (4),
C D AB ( y A1 y A 2 )
N -------------------- (1.23)
Z 2 z1
A
y B, lm
n p
For an ideal gas C , and
V RT
pA
For mixture of ideal gases y A
P
Therefore, for an ideal gas mixture equation. (1.23) becomes
D AB ( p A1 p A 2 )
N ----------------------------------- (1.24)
RT ( z2 z1 )
A
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.
Solution: Let us denote oxygen as A and nitrogen as B. Flux of A (i.e.) N A is

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,
dCA
J A D AB ----------------------------------------- (2)
dz
Substituting this equation (1)
dCA
N A Nx A D AB ----------------------------- (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,
dz C A2 dC A
cD C A1 N C C N N -------------- (4)
AB A A A B
Since B is non diffusing N B = 0. Also, the total concentration C remains constant.
Therefore, equation (4) becomes
z C dC A
C A2
CD AB A1 N C N C
A A A
1 C C A2
ln
NA C C A1
Therefore,
CD AB C C A2
NA ln ---------------------------- (5)
z C C A1
Replacing concentration in terms of pressures using Ideal gas law, equation (5) becomes
D AB P t P t P A2
NA ln --------------------------- (6)
RTz P t P A1
where
D AB = molecular diffusivity of A in B
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
5 5
NA 1 0.2
8314 298 0.002
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
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
dy A
N A CD AB y A (N A N B)
dz
dC A
or N A D AB y A (N A N B) ------- (1.25)
dz
with the substitution of NB = - NA, Equation (1.25) becomes,
dC A
N A D AB ----------------- (1.26)
dz
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 C A2
NA d z D AB dC A
Z1 C A1
from which
D
N A AB (C A1 C A2 ) ------------------- (1.27)
z 2z1
nA p
For ideal gases, C A A . Therefore Equation (1.27) becomes
V RT
D AB
N A (P A1 P A2 ) ---------- (1.28)
R T ( z 2 z 1)
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)
d CA
N A D AB .
dz
Therefore
d d CA
D 0.
d z
AB
dz
2
d CA
or
2
0. ----------------------------------- (1.29)
dz
This equation may be solved using the boundary conditions to give
C C A1 zz1
A
-------------- (1.30)
C A1
C A2 z1 z 2
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.
(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;
6.75 *10 5 kmol

NA 55 15 2
8.314 * 298 * 0.03 m .sec
kmol
N A 3.633 * 10 5
m 2 sec
And from (1), partial pressure at 0.02 m from point 1 is:
6.75 * 10 5
3.633 * 10 5
8.314 * 298 * 0.02
55 p A
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
DA
by N Ai
RT
C 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
DA
N Ai
R
C Ai C Ab --------------------------- (1)
The mass flux N Ai of the diffusing component A at the interface is also given by

N Ai kC C Ai C Ab --------------------------- (2)
From the equations (1) and (2), we get
DA
kC
R
kC R
1
DA
kC d d
2 since R ,d=diameter of sphere
DA 2
kC d
NSh 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
any distance r from the center is given by
N A C D AB
dy
dr
A
y A N A N B
Here N B = 0 (since air is assumed to be stagnant)
Therefore,
dy A
N A C D AB y A NA
dr
Rearranging,
C D AB d y A
NA __________ (1.31)
1 y A dr
The flux N A 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 r
where A = surface area of sphere at r or r + r.
Substituting for A = 4 r 2 in equation (1.32),
4 r 2
NA 4 r 2
NA 0
r r r
or
2 2
r NA r NA
r r r
lim 0
r 0 r
ss
d
dr
r 2
NA 0 __________ (1.33)
Integrating,
2
r N A constant __________ (1.34)
From equation (1.34), r

2
N A r 02 N A 0
Substituting for N A from equation (1.31),
2
r C D AB d y A
r 02 N A 0
1 y A dr
dr dy A
r 02 N A 0 C D AB __________ (1.35)
r 2 1 y A
Boundary condition:
At r = r 0 y A = y AS
And At r = y A = y A
Therefore equation (1.35) becomes,

r 02 NA 0
1

C D AB ln 1 y A yy A
r r0 AS
Simplifying,
C D AB 1 y A
NA 0 ln __________ (1.36)
r0 1 y A S

Time required for complete evaporation of the droplet may be evaluated from making
mass balance.
Moles of water diffusing moles of water leaving the droplet

unit time unit time
d 4
4 r 02 N A 0 r3 L
dt 3 0
M A

d r0
4 r0 2 L
__________ (1.37)
MA dt
Substituting for N A0 from equation (1.36) in equation (1.37),
C D AB 1 y A L d r0
ln __________ (1.38)
r0 1 y AS MA dt

Initial condition :
When t = 0 r0 = r1
Integrating equation (1.38) with these initial condition,
t L 1 1
0
d t
0
MA C D AB 1 y A r
r1
0 d r0
ln
1 y
AS
1 r1 2
t L
__________ 1.39
MA 2 C D AB 1 y A
ln
1 y
AS
Equation (1.39) gives the total time t required for complete evaporation of spherical
droplet of initial radius r 1.
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 0 ---------------------------- (1)

r rr
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 0
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
A
y A N A N B
N B = 0 (since air is assumed to be stagnant in the film)
dy A
N A CD AB y A NA
dr
d yA
N A CD AB
dr 1 y A

N A CD AB

d ln 1 y A
dr
W A = Rate of evaporation = 4 r 2 N A R = constant.
WA
4 r 2

CD AB d ln 1 y A
dr
WA
dr
2
4 D AB C d ln 1 y A
r
Boundary condition:
0.555
At r = R y A 7.303 * 10 4
760
ln (1 y A) = - 7.3 * 10 4
At r = yA = 0 ln (1-y A) = 0

d ln 1 y A
0
dr
Therefore W A
2
4 D AB C
R r 7.3 *10 4

WA
1
r 4 D AB C ln 1 y A 0 7.3 *10 4
R

1
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
C
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
= 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

concentration term C is replaced by average molar density, .
M av
a) For steady state diffusion of A through non diffusivity B:
N A = constant , N B = 0
D AB
NA
z x BM M av
xA1 x A2 ----------------------------------- (1.40)
where Z = Z 2 Z 1, the length of diffusion path; and
X B 2 X B1
X BM ----------------------------------- (1.41)
X
ln B 2
X B 1
b) For steady state equi-molar counter diffusion:
N A = - N B = const
D AB D AB
NA
Z
C A1 C A2
Z M av
x A1 x A 2 ----------------------------------- (1.42)
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
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
C
x A1 x A2
z x B, lm
where C is the average molar density.

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

1 M1 2 M2

M avg 2
0.971 19.47 0.992 18.56

2
= 0.0517 gmol / cm 3
= 51.7 kmol/m 3
x B,lm
x B 2 x B1

1 x A2 1 x A1

ln x B 2 x B1 1 x A2
ln
1 x A1

(i.e.) x B,lm
1 0.01 1 0.026
1 0.01
ln
1 0.026
0.016
0.982
0.0163
For more details

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Revised Study

Ficks laws, molecular diffusion in fluids, mass transfer

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3.2.3 Equilibrium Diagram 57

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5.2 Vapor Liquid Equilibrium 98

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8.5 Single Stage Leaching 124

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

Therefore, equation (1.2) becomes

For binary systems containing two components A and B,

1.2 FICKS LAW:

where D AB is diffusivity or diffusion coefficient for component A diffusing through

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

1.3 RELATION AMONG MOLAR FLUXES:

For a binary system containing A and B, from Equation (1.5),

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

Therefore equation (1.8) becomes,

Therefore Equation (1.9) becomes,

This leads to the conclusion that diffusivity of A in B is equal to diffusivity of B in A.

Ficks law proportionality, DAB, is known as mass diffusivity (simply as diffusivity) or as

Diffusivity is normally reported in cm2 / sec; the SI unit being m2 / sec.

Diffusivity depends on pressure, temperature, and composition of the system.

General range of values of diffusivity:

Gases : 5 X 10 6 ------------- 1 X 10-5 m2 / sec.

Liquids : 10 6 ------------- 10-9 m2 / sec.

Solids : 5 X 10 14 ------------- 1 X 10-10 m2 / sec.

1.4.1 DIFFUSIVITY IN GASES:

Pressure dependence of diffusivity is given by

And temperature dependency is according to

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

1.4.2 DIFFUSIVITY IN LIQUIDS:

Certain molecules diffuse as molecules, while others which are designated as

1.4.3 DIFFUSIVITY IN SOLIDS:

1.5 STEADY STATE DIFFUSION

1.5.1 DIFFUSION THROUGH A STAGNANT GAS FILM

Component A vaporizes and diffuses into the gas

Consider the control volume S z, where S is the cross

[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)

A similar differential equation could also be written for component B as,

From equation (1.15)

This equation may be integrated between the two boundary conditions:

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),

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

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

(b) Calculate the flux of oxygen. Diffusivity of oxygen in nitrogen = 1.89 * 10 5 m / s.

Solution: Let us denote oxygen as A and nitrogen as B. Flux of A (i.e.) N A is

From Ficks law of diffusion,

Substituting this equation (1)

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

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

P t = 1 atm = 1.01325 * 10 5 N/m 2

T = 25C = 273 + 25 = 298 K

P A2 = 0.1 * 1 = 0.1 atm

Substituting these in equation (6)