ChE 351

Mass Transfer Processes

E.G. Ankudey, PhD

Dept of Chemical Engineering, KNUST
September 2011

1
What the course is about
 Mass Transfer Operations deal with “unit
operations” involving “mass transfer” (a
microscopic process on a macroscopic
scale)

 Mass transfer is defined as the transportation

of one (or more) component from one phase
to another

 Motivation: in many industrial processes we

use mass transfer to achieve separation
(enrichment or removal) of a substance from
a mixture

 Emphasis is placed on separation processes

that involve equilibrium between the phases

2
 Course Content
 Importance of mass transfer
 Molecular diffusion
 Diffusion in binary mixtures
 Mass transfer models
 Interphase mass transfer
 Mass transfer with laminar and
turbulent flow
 Absorption in packed towers
 Effect of temperature on absorption
 Distillation
 Batch distillation
 Rayleigh equation
 Fractionation
 Binary distillation
 McCabe-Thiele method
 Ponchon-Savarit method
 Liquid solid extraction.
3
Why is this course important?
 Mass transfer operations are largely the
responsibility of chemical engineers

 Chemical plants usually have from 50 to

90% of their capital invested in
separation equipment

 There is virtually no industrial process

that does not involve purification of raw
materials or final separation of products

4
 Course Objectives
The student is expected to:

 Recognize the various modes of mass transfer

 Estimate diffusion coefficients under different physical conditions

 Determine mass transfer rates using Fick’s Law for one-dimensional

molecular diffusion in gases and liquids

 Use the rate equation with mass transfer coefficients to determine

mass transfer rates

 Calculate film mass transfer coefficients using literature correlations

or material balance findings

 Calculate overall mass transfer coefficients from film mass transfer

5
coefficients or material balance findings
 Course Objectives –cont’d
 Use analogies between heat transfer and mass transfer to
solve problems
 Determine liquid and gas flow rates required for
absorption and stripping columns

 Calculate the packing height for gas absorption towers.

 Obtain practical information including physical properties

from the literature relevant to contactor design

 Use McCabe and Thiele method to analyze binary

distillation problems

 Determine the number of stages and feed plate location in

simple binary distillations

 Understand the concept of tray and overall efficiency and

be able to determine the height of distillation column.
6
 References

Principles and Modern Applications of Mass

Transfer Operations 2nd Edition, © 2009

Jaime Benitez

Mass Transfer: Fundamentals and

Applications © 1985

Anthony L. Hines and Robert N. Maddox

Unit Operations Of Chemical Engineering

©2004

Julian C. Smith, Peter Harriott, Warren McCabe

7
 References

Transport Phenomena © 2006

Edwin N. Lightfoot, R. Byron Bird, Warren E. Stewart

Separation Process Principles © 2005

E.J. Henley, Ernest J. Henley, J. D. Seader

Mass Transfer Operations 3rd Edition © 1980

Robert Ewald Treybal

8
 Course Organisation

 4 hours regular lectures per week

 2 hours tutorial session per week or as needed
 8-12 Homework Assignments (10-20%)
 Two mid-semester exams (10-30%)
 Final Examination (50-70%)
 Office hours: Open door (feel free to walk in)

TA: Mr. Derrick Amoabeng

9
 Prerequisites

What do we need?

 Differential Equations (MATH 251/252)

 Material/Energy Balances (ChE 251/252)
 Thermodynamics (ChE 253/254)
 Fluid Transport (ChE 255)
 Heat Transfer (ChE 256)
 Kinetics and Rate of reactions (??)

10
Introduction to Mass Transfer
 Transfer of material from one homogeneous phase
to another

 Driving force is concentration difference or

difference in thermodynamic activity
 Results from differences in solubility, vapour pressure
or diffusivity.
 Independent of density and particle size

 Examples are distillation, gas absorption, extraction,

adsorption, dehumidification

 A limit to mass transfer occurs when the

concentration in the two phases is the same. i.e. the
two phases come to equilibrium

11
 Mass transfer operations
 The transfer of mass within a fluid mixture or across a phase boundary is
a process that plays a major role in many industrial processes. Examples
of such processes are:

 Dispersion of gases from stacks

 Removal of pollutants from plant discharge streams by absorption

 Stripping of gases from waste water

 Neutron diffusion within nuclear reactors

 Air conditioning

12
 Mass transfer operations
 Many of our day-by-day experiences also involve
mass transfer, for example:

 A lump of sugar added to a cup of coffee eventually

dissolves and then eventually diffuses to make the
concentration uniform.

 Water evaporates from ponds to increase the

humidity of passing-air-stream

 Perfumes presents a pleasant fragrance which is

imparted throughout the surrounding atmosphere.

 The mechanism of mass transfer involves both

molecular diffusion and convection.
13
 Properties of Mixtures
 Mass transfer always involves mixtures.
Consequently, we must account for the variation of
physical properties which normally exist in a given
system.

 When a system contains three or more

components, as many industrial fluid streams do,
the problem becomes complicated very quickly.

 The conventional engineering approach to

problems of multi-component system is to attempt
to reduce them to representative binary (i.e., two
component) systems.

 Explanation of definitions and relations which are

often used to explain the role of components within
14
a mixture.
 Concentration of Species
 Concentration of species in multi-component mixture can be
expressed in many ways. For species A, mass
concentration denoted by A is defined as the mass of A, mA
per unit volume of the mixture.

mA
ρA 
V ….……. (1)
 The total mass concentration density  is the sum of the
total mass of the mixture in unit volume:

ρ ρ
i
i

 where i is the concentration of species i in the mixture.

15
 Concentration of species
Molar concentration of, A, CA is defined as the number of
moles of A present per unit volume of the mixture.

By definition,
mass of A
Number of moles 
molecular weight of A
m
n A  A
………….. (2)
M A

Therefore from (1) & (2)

nA A ……... (3)
CA  
V MA
16
 Concentration of Species
For ideal gas mixtures,
pA V
n A  …….…. (4)
RT

[ from Ideal gas law PV = nRT]

nA pA
CA  
V RT
where pA is the partial pressure of species A in the mixture. V is the
volume of gas, T is the absolute temperature, and R is the universal gas
constant.
The total molar concentration or molar density of the mixture is given by

C  Ci ………. (5)

i 17
 Velocities
 In a multi-component system the various species
move at different velocities

 Evaluation of velocity of mixture requires the

averaging of the velocities of each species present.

 If  I is the velocity of species i with respect to

stationary fixed coordinates, then mass-average
velocity for a multi-component mixture defined in terms
of mass concentration is:

ρ ν i i ρ ν i i
ν i
 i …………. (6)
ρ i
i ρ

18
 Velocities
Similarly, molar-average velocity of the mixture  * is

C i V i
 *  i …………. (7)
C
For most engineering problems, there will be little
difference in  * and  and so the mass average velocity,
, will be used in most discussions.

The velocity of a particular species relative to the mass-

average or molar average velocity is termed as diffusion
velocity
(i.e.) Diffusion velocity =  i - 
19
 Mole and mass fractions
The mole fraction for liquid and solid mixture, x A ,and for gaseous
mixtures, y A, are the molar concentration of species A divided by the
molar density of the mixtures.
CA
x A  For solids and liquids
C ………. (8)
CA
y A  For gases
C
The mole fraction for liquid and solid mixture, x A ,and for gaseous
mixtures, y A, are the molar concentration of species A divided by the
molar density of the mixtures.

y i  1 x i  1 …….…. (9)
i i
Similarly, the mass fraction of component A in the mixture is;
A
wA  ……….. (10)
 20
 Example

The molar composition of a gas mixture at 273 K

and 1.5 x 10 5 Pa is:
O2 7%
CO 10%
CO 2 15%
N2 68%
Determine
•the composition in weight percent
•average molecular weight of the gas mixture
•density of gas mixture
•partial pressure of O 2.

21
 Solution
Consider 1 mole of gas mixture (basis). Then
O2 = 0.07 mol
CO = 0.10 mol
CO 2 = 0.15 mol
N2 = 0.68 mol

Molecular weight of the constituents are:

O2 = 2 * 16 = 32 g/mol
CO = 12 + 16 = 28 g/mol
CO 2 = 12 + 2 * 16 = 44 g/mol
N2 = 2 * 14 = 28 g/mol

Weight of the constituents are: (1 mol of gas mixture)

O2 = 0.07 * 32 = 2.24 g
CO = 0.10 * 28 = 2.80 g
CO 2 = 0.15 * 44 = 6.60 g
N2 = 0.68 * 28 = 19.04 g
Total weight of gas mixture = 2.24 + 2.80 + 6.60 + 19.04
= 30.68 g 22
Composition in weight percent:

2.24
O2  * 100  7.30%
30.68
2.80
CO  * 100  9.13%
30.68
6.60
CO 2  * 100  21.51%
30.68

19.04
N2  * 100  62.06%
30.68

23
Average molecular weight of the gas mixture
Weight of gas mixture
M 
Number of moles

30.68
M   30.68 g mol
1
Assuming that the gas obeys ideal gas law,
PV = nRT
n P

V RT
n
 molar density   m
V
Therefore, density (or mass density) =  mM
Where M is the molecular weight of the gas.

PM 1.5 * 10 5 * 30.68
Density   m M   kg m 3
RT 8314 * 273
24
= 2.03 kg/m 3
Partial pressure of O 2 = [mole fraction of O 2] * total pressure


7
100

* 1.5 * 10 5 
= 0.07 * 1.5 * 10 5
= 0.105 * 10 5 Pa

25
 Modes of mass transfer
 Two mechanisms of mass transfer
 Molecular diffusion and convective transfer

The total mass (or molar) flux of a given species in a direction

perpendicular to a stationary plane is a vector quantity and is given by
the product of the volumetric average velocity and the mass (or molar)
concentration

N A C A A …………. (11)

The total flux consists of the diffusive flux and the

convective flux
26
 Diffusivities

Diffusivities are defined with respect to a

plane moving at the volume average
velocity v*. By definition,

C i ν i
ν ν *  i …..…. (12)
C

27
 Diffusion flux
The total flux of A could be written in terms of diffusion velocity of A,
(i.e.,  A - ) and average velocity of mixture, , as

NA  CA ( A  )  CA ………. (13)

C  i i
By definition   *  i
C

Therefore, equation (13) becomes

CA
NA  CA ( A  )  Ci i
C i
 C A ( A  )  y A  C i  i …….. (14)
i
28
 Diffusion flux
For 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 ) ………… (15)

N A  C A ( A  )  y A N ..………. (16)

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.
29
 Flux notations
Mass flux of species i with respect to fixed coordinates

Total mass flux

ni  i v i

n  v
Molar flux of species i with respect to fixed coordinates

Ni  c i v i
Total molar flux

N  cv *

30
 Flux notations
Mass diffusion flux of species i with respect to the
mass-average velocity
j i  i (v i  v )

Molar diffusion flux of species i with respect to molar-

average velocity
Ji  ci (v i  v *)

The mass flux ni is related to the molar diffusion flux by

ni  j i  i v  j i  i n
The molar flux is related to the molar diffusions flux by

Ni  Ji  ci v *  Ji  y i N
 Fick’s law
An empirical relation for the diffusional molar flux, first postulated by
Fick and, accordingly, often referred to as Fick’s first law, defines the
diffusion of component A in an isothermal, isobaric system. For diffusion
in only the Z direction, the Fick’s rate equation is
dC A ………. (17)
JA   D AB
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,

isobaric system could be written as
dy A
J A   C DA B ………. (18)
dZ
using this expression, Equation (16) could be written as
dy A ………. (19)
N A   C DA B  y AN
dZ 32
Relation among molar fluxes

For a binary system containing A

and B,
N A J A y AN ………. (20)

J A  N A  y AN .……... (21)

J B  N B y BN ………. (22)

Addition of Equation (21) & (22) gives,

J A J B  N A  N B  (y A  y B) N
…… (23)

33
 Relation among molar fluxes
By definition N = N A + N B and y A + y B = 1.

Therefore equation (23) becomes,

JA+JB=0 ………..…. (24)

J A = -J B
dy A dyB
CD AB   C D BA …............... (25)
dz dZ

From y A + y B- = 1

dy A = - dy B ………………….. (26)
Therefore Equation (25) becomes,
D AB = D BA ……………... (27)

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

equal to diffusivity of B in A. 34
 Diffusivity
 Fick’s law proportionality, D AB, is known as mass diffusivity
(simply as diffusivity) or as the diffusion coefficient.

 D AB has the dimension of L 2 / t, identical to the fundamental

dimensions of the other transport properties:

 Kinematic viscosity,  = ( / ) in momentum transfer

 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 literature, some values of DAB are given for a few gas, liquid,
and solid systems. 35
 Table 1a: Mass Diffusivities in Gases
2 2
System T, K D AB P,m -Pa/s System T, K D AB P, m -Pa/s
Air Carbon dioxide
Ammonia 273 2.006 Ethanol 273 0.702
Aniline 298 0.735 Ethyl ether 273 0.548
Benzene 298 0.974 Hydrogen 273 5.572
Bromine 293 0.923 Methane 273 1.550
Carbon dioxide 273 1.378 Methanol 298.6 1.064
Carbon disulfide 273 0.894 Nitrogen 298 1.672
Chlorine 273 1.256 Nitrous oxide 298 1.185
Diphenyl 491 1.621 Propane 298 0.874
Ethyl acetate 273 0.718 Water 298 1.661
Ethanol 298 1.337 Hydrogen
Ethyl ether 293 0.908 Ammonia 293 8.600
Iodine 298 0.845 Argon 293 7.800
Methanol 298 1.641 Benzene 273 3.211
Mercury 614 4.791 Ethane 273 4.447
Naphthalene 303 0.870 Methane 273 6.331
Nitrobenzene 298 0.879 Oxygen 273 7.061
n-Octane 298 0.610 Pyridine 318 4.427
Oxygen 273 1.773 Nitrogen
Propyl acetate 315 0.932 Ammonia 293 2.441
Sulfur dioxide 273 1.236 Ethylene 298 1.651
Toluene 298 0.855 Hydrogen 288 7.527
Water 298 2.634 Iodine 273 0.709
Ammonia Oxygen 273 1.834
Ethylene 293 1.793 Oxygen
Carbon dioxide Ammonia 293 2.563
Benzene 318 0.724 Benzene 296 0.951
Carbon disulfide 318 0.724 Ethylene 293 1.844
Ethyl acetate 319 0.675 Water 308.1 2.857

36
 Table 1b: Mass Diffusivities in Liquids at Infinite Dilution

5 2 5 2
System T,K DAB x10 , cm /s System T,K DAB x 10 , cm/s

Chloroform (solvent B) Ethyl acetate (solvent B)

Acetone 298 2.35 Acetic acid 293 2.18
Benzene 288 2.51 Acetone 293 3.18
Ethanol 288 2.20 Ethyl benzoate 293 1.85
Ethyl ether 298 2.13 MEK 303 2.93
Ethyl acetate 298 2.02 Nitrobenzene 293 2.25
MEK 298 2.13 Water 298 3.20
Benzene (solvent B) Water (solvent B)

Acetic acid 298 2.09 Methane 298 1.49

Aniline 298 1.96 Air 298 2.00
Benzole acid 298 1.38 Carbon dioxide 298 1.92
Bromobenzene 281 1.45 Chlorine 298 1.25
Ciclohexane 298 2.09 Argon 298 2.00
Ethanol 288 2.25 Benzene 298 1.02
Formic acid 298 2.28 Ethanol 288 1.00
n-Heptane 353 4.25 Ethane 298 1.20
MEK 303 2.09 Oxygen 298 2.10
Naphthalene 281 1.19 Pyridine 288 0.58
Toluene 298 1.85 Aniline 293 0.92
Vinyl chloride 281 1.77 Ammonia 298 1.64

Acetone (solvent B) Ethylene 298 1.87

Acetic acid 288 2.92 Allyl alcohol 288 0.90
Acetic acid 313 4.04 Acetic acid 293 1.19
Benzoic acid 298 2.62 Benzoic acid 298 1.00
Formic acid 298 3.77 Propionic acid 298 1.06
Water 298 4.56 Vinyl chloride 298 1.34
Ethanol (solvent B) Ethylbenzene 293 0.81
Benzene 298 1.81 Sulfuric acid 298 1.73
Water 298 1.24 Nitric acid 298 2.60
Sources: Reid, R. C., J. M. Prausnitz, and B. E. Poling,
The Properties of Gases and
Liquids,4th ed., McGraw -Hill, New York (1987); Cussler, E.Diffusion,
L., Mass Transfer
in Fluid Systems,2nd ed., Cambridge University Press, Cambridge, UK (1997).

37
 Table 1c: Mass Diffusivities in the Solid State
System T, K

Hydrogen in iron 283 1.66 x 10 -9

323 11.4 x 10-9
373 124 x 10-9
-9
Hydrogen in nickel 358 11.6 x 10
-8
438 10.5 x 10
Carbon monoxide in nickel 1223 4.00 x 10-8
-8
1323 14.0 x 10
-9
Aluminum in copper 1123 2.20 x 10
293 1.30 x l0- 30
Uranium in tungsten 2000 1.30 x 10 - 11
-11
Cerium in tungsten 2000 95.0 x 10
-11
Yttrium in tungsten 2000 1820 x 10
-10
Tin in lead 558 1.60 x 10
- 10
Gold in lead 558 4.60 x 10
Gold in silver 1033 3.60 x 10- 10
Antimony in silver 293 3.60 x 10- 10
-9
Zinc in aluminum 773 2.00 x 10-9
Silver in aluminum 323 1.20 x 10
Bismuth in lead 293 l.l0 x 10 -16
Cadmium in copper 293 2.70 x 10 -15
Carbon in iron 1073 1.50 x 10 -8
-8
1373 45.0 x 10
Helium in silica 293 4.00 x 10- 10
773 7.80 x 10 -8
Hydrogen in silica 473 6.50 x 10- 10
773 1.30 x 10 -8
Helium in Pyrex 293 4.50 x 10-11
773 2.00 x 10 -8

Sources: Barrer, R. M., Diffusion in and through Solids, Macmillan, New York
(1941); American Society for Metals, Diffusion, ASM (1973); Cussler, E. L.,
Diffusion, Mass Transfer in Fluid Systems, 2nd ed., Cambridge University Press,
Cambridge, UK (1997).

38
 Diffusivities
 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.

39
 Range of diffusivity values

Gases : 5 X 10 –6 ------ 1 X 10-5 m2 / s.

Liquids : 10 –6 ------ 10-9 m2 / s.
Solids : 5 X 10 –14 ------ 1 X 10-10 m2 / s.

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

40
 General expressions
Pressure dependence of diffusivity is given by

1
D AB  (for moderate ranges of
pressures, up to 25 atm).
…. (28)
p

And temperature dependency is according to

3
D AB T 2 ……………………. (29)

 In the absence of experimental data, semi-empirical

expressions have been developed to estimate the diffusion
coefficient.
41
 Binary ideal gas systems
 Based on the kinetic theory of gases at moderate
pressures
 Lennard-Jones potential to evaluate the influence of
intermolecular forces
 The diffusion coefficient of gas pairs of nonpolar, non-
reacting molecules is given by the Wilke-Lee equation

DAB 
3.03  0.98 / M 10 T
1/ 2
AB
3
3
2

PM 1AB2 D
2
AB

42
 1
 1 1 
M AB  2  
 M A MB 

DAB = diffusion coefficient, cm2/s

MA, MB = molecular weights of A and B
T = temperature, K
P = pressure, bar
σAB = collision diameter, a Lennard-Jones parameter, Å
ΩD = diffusion collision integral, dimensionless

The collision integral is a function of the temperature and the

intermolecular potential field for one molecule of A and one molecule of
B. It is tabulated as a function of T* = κT/εAB, where κ is the Boltzmann
constant and εAB is the energy of molecular interaction of the binary
system A and B

43
An approximation of ΩD is obtained from the
following equation
a c e g
D    
T 
* b 
exp dT *
 exp fT 
*

exp hT * 

where T* = κT/εAB

a = 1.06036 e = 1.03587
b = 0.15610 f = 1.52996
c = 0.19300 g = 1.76474
d = 0.47635 h = 3.89411
44
 For a binary system of nonpolar molecular pairs,
the Lennard-Jones parameters may be obtained
as follows
 A  B
 AB   AB   A B
2

 The interaction parameters for the pure

components are usually obtained from viscosity
data

45
 In the absence of experimental data, the values of the
parameters for pure components may be estimated from
the following empirical correlations

A  1.15Tb
  1.18V
13
b 
where Vb is the molar volume of the substance as a
liquid at its normal boiling point in cm3/gmol and Tb is the
normal boiling temperature

Vb  0.285Vc
1.048

where Vc is the critical volume

 Otherwise, the atomic volume of each element present
are added together
46
47
48
49
50
 Fuller method

1.00 x107T 1.75(1 / M A  1 / MB )0.5

DAB 

P  v A    v B 
1
3
1
3

2

ΣvA = sum of structural volume increments of

component A

P = absolute pressure in atm

51
52
Multi-component diffusivities
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 …. (30)
D 1 mixture 
y 2 y 3 y n
  ........... 
D1 2 D1 3 D1 n
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  …..…. (31)
y2  y 3  ....... y n 53
 Example

Determine the diffusivity of CO 2 (1), O 2 (2) and N 2

(3) in a gas mixture having the composition:
CO2 : 28.5 %, O2 : 15%, N 2 : 56.5%,

The gas mixture is at 273 K and 1.2 * 10 5 Pa. The

binary diffusivity values are given as: (at 273 K)
D 12 P = 1.874 m 2 Pa/s
D 13 P = 1.945 m 2 Pa/s
D 23 P = 1.834 m 2 Pa/s

54
 Diffusivity of CO 2 in mixture
1
D 1m 
y 2 y 3

where D 12 D 13
y2
y 2 
0.15
  0.21
y2 y3 0.15  0.565
y3
y 3 
0.565
  0.79
y 2 y3 0.15  0.565
Therefore D 1m P 
1
0.21 0.79

1.874 1.945
= 1.93 m 2.Pa/s

Since P = 1.2 * 10 5 Pa,

1.93 5
D1m  5
 1.61 * 10 m 2
s 55
1.2 * 10
 Diffusivity of O 2 in the mixture,
1
D 2m 
y 1 y 3


D 21 D 23
Where
y1
y 1 
0.285
  0.335
y1  y3 0.285  0.565

(mole fraction on-2 free basis).

 y3 0.565
y3    0.665
y1  y3 0.285  0.565

56
 D 21 P = D 12 P = 1.874 m 2.Pa/sec
Therefore
1
D 2m P 
0.335 0.665

1.874 1.834
= 1.847 m 2.Pa/sec

1.847
D 2m   1.539 * 10  5 m 2 sec
1.2 * 10 5

By similar calculations Diffusivity of N 2 in the mixture can be

calculated, and is found to be, D 3m = 1.588 * 10 –5 m 2/s.

57
 Diffusivity in liquids
 Diffusivities in liquids are nearer to 10-5 cm2 / s, and
about ten thousand times slower than those in dilute
gases.

 This characteristic of liquid diffusion often limits the

overall rate of processes occurring in liquids

 Diffusivity limits the rate of acid-base reactions;

 Diffusion is responsible for the rates of liquid-liquid

extraction.

58
 Diffusivity in liquids
 Certain compounds diffuse as molecules,

 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;

 It is not possible to speak of a diffusion coefficient for

molecular electrolytes such as NaCl.

59
 Diffusivity in liquids
 If several ions are present, the diffusion rates of the individual
cations 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.

60
 Diffusivity in solids:

An outstanding characteristic of these values is their

small size, usually thousands of times 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. The diffusion of atoms within a
solid is of prime importance to the metallurgist.

61
 Steady State Diffusion
Steady-state molecular mass transfer through simple
systems in which the concentration and molar flux are
functions of a single space coordinate.

In a binary system, containing A and B, the molar flux in

the direction of z, as given by Eqn (16) is

dy A
N A  C D AB  y A (N A  N B) ……. (32)
dz

62
Diffusion through a stagnant gas film
The diffusivity or diffusion coefficient for a gas can be measured
experimentally using a diffusion cell. This cell is illustrated
schematically in figure.
Gas B
z=z2

Δz

z=z1=0

Liquid A
 Liquid A maintained at constant temperature and pressure

 Gas B has negligible solubility in A

 No reaction between A and B

63
Diffusion through a stagnant gas film
 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

64
 Mass balances

[Moles of A leaving at z + z] – [Moles of A entering at z] = 0. (i.e.)

SN A z  z  SN A z  0. ……. (32)

Dividing through by the volume, SZ, and evaluating in the limit as Z

approaches zero, we obtain the differential equation
dN A ……….…………. (33)
 0
dz
This relation stipulates a constant molar flux of A throughout the gas
phase from Z1 to Z2.
A similar differential equation could also be written for component B as,
d N B ………….…. (34)
 0,
d Z
and accordingly, the molar flux of B is also constant over the entire
diffusion path 65
 Mass balances
Since the gas B is insoluble in liquid A, we realize that NB, the net
flux of B, is zero throughout the diffusion path; (alternatively, B is a
stagnant gas along the diffusion path).
From equation 19

dy A
NA   C D AB  y A (N A  N B ) ……. (35)
dz
Since N B = 0,

dy A
NA   C D AB  y AN A …….…. (36)
dz
Rearranging,

 C D AB d y A
NA  …………………. (37)
1 y A d z 66
 Mass balances
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 NA is constant along the
diffusion path, by integrating equation (37) we obtain
Z2 y A2
dy A
N A  d z  C DAB  1 y ……. (38)
Z1 y A1 A

CD AB  1  y A2 
NA  ln   ……. (39)
Z 2  Z1  1  y A1 
67
 The log mean average concentration of component B is
defined as
y B 2  y B1
y B, lm  ……. (40)
ln  y B 2 

,
 y B1 

Since y B 1  y A

(1  y )  (1  y ) y y ……. (41)
y B, lm  
A2 A1 A1 A2

ln  y B 2 
 ln  y B 2 

 y B1   y B1 

Substituting Eqn (41) in Eqn (39),

C D AB ( y A1  y A2 ) ……. (42)
N A 
Z 2  z1 y B, lm

68
 Diffusion flux of gases
For an ideal gas
n p
C   ……. (43)
V RT
and for mixture of ideal gases
p A ……. (44)
y A 
P
Therefore, for an ideal gas mixture equation. (6) becomes

D AB ( p A1  p A2 ) ……. (45)
N A 
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
69
 Applications
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.

The concentration profile (yA vs. z) for this type of diffusion is

shown in figure:

70
 Example
Oxygen is diffusing in a mixture of oxygen-nitrogen at 1 std
atm, 25C. Concentration of oxygen at planes 2 mm apart
are 10 and 20 volume % respectively. Nitrogen is non-
diffusing.

•Derive the appropriate expression to calculate the flux

oxygen. Define units of each term clearly.
•Calculate the flux of oxygen. Diffusivity of oxygen in
nitrogen = 1.89 * 10 –5 m 2/s.

71
 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 ……. (a)

72
 Solution
From Fick’s law of diffusion,

dCA
J A  D AB ……. (b)
dz

Substituting this equation (a)

dCA
N A  Nx A  D AB ……. (c)
dz

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


NA  NA  NB  CA
C
 D AB
dCA
dz
…….. (d)
73
 Rearranging the terms and integrating between the planes
between 1 and 2,

dz C A2 dC A
 cD AB   C A1 N AC  C A N A  N B  ……. (e)

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

constant. Therefore, equation (4) becomes

z C A2 dC A
  ……. (f)
CD AB C A1 N C  N C
A A A

1 C  C A2
 ln ……. (g)
NA C  C A1
Therefore,
CD AB C  C A2 ……. (h)
NA  ln
z C  C A1
74
Replacing concentration in terms of pressures using Ideal gas law,
equation (h) becomes

D AB P t P t  P A2
NA  ln ……. (i)
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 = 25C = 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)
75
Substituting these in equation (i)

NA 

1.89 * 10  5 1.01325 * 10 5   1  0.1 
ln  
83142980.002  1  0.2 

= 4.55 * 10 –5 kmol/m 2.s

76
 Equimolar counter diffusion
 A physical situation which is encountered in the distillation
of two constituents whose molar latent heats of
vaporization are essentially equal

 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   C D AB  y A (N A  N B ) ……. (48)
dz
dC A ……. (49)
or N A   D AB  y A (N A  N B )
dz
 with the substitution of NB = - NA, Equation (49) becomes,

dC A
N A D AB ………………. (50)
dz
For steady state diffusion Equation. (50) 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 ) ……. (51)
z 2z1
For ideal gases, nA pA
C A  
V RT
. Therefore Equation. (51) becomes
D AB
N A  (P A1 P A2 ) ……. (52)
R T (z 2  z 1)
.
This is the equation of molar flux for steady-state equimolar counter
diffusion.

Concentration profile in these equimolar counter diffusion may be

obtained from,
d
(N A)  0 ……. (53)
dz
(Since NA is constant over the diffusion path).
And from equation. (50)

d CA ……. (54)
N A  D AB
dz
Therefore
d  d CA 
  D AB   0
. dz  dz 
or
2
d CA
2
 0. ……. (55)
dz

This equation may be solved using the boundary conditions to give

C C A1 zz1
A
 ……….. (56)
C A1
C A2 z1 z 2

Equation, (56) indicates a linear concentration profile for equimolar

counter diffusion.
 Example

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
the diffusivity is 6.75 * 10 –5 m 2/s.
 Calculate the flux of CH 4 at steady state for equimolar counter
diffusion.
 Calculate the partial pressure at a point 0.02 m apart from point 1.

Solution
For steady state equimolar counter diffusion, molar flux is given by

NA 
D AB
RT z
p A 1  p A 2 
Therefore;

6.75 * 10  5
NA  55  15 kmol
8.314 * 298 * 0.03 m 2 . sec

5 kmol
 3.633 * 10 2
m 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

In a gas mixture of hydrogen and oxygen, steady state

equimolar counter diffusion is occurring at a total pressure
of 100 kPa and temperature of 20C.

If the partial pressures of oxygen at two planes 0.01 m

apart, and perpendicular to the direction of diffusion are 15
kPa and 5 kPa, respectively and the mass diffusion flux of
oxygen in the mixture is 1.6 * 10 –5 kmol/m 2.s, calculate the
molecular diffusivity for the system.
 Solution
For equimolar counter current diffusion:

NA 
D AB
RTz
p A1  p A2 

where
N A = molar flux of A (1.6 * 10 –5 kmol/m 2.s):
D AB = molecular diffusivity of A in B
R = Universal gas constant (8.314 kJ/kmol.k)
T = Temperature in absolute scale (273 + 20 = 293 K)
z = distance between two measurement planes 1 and 2 (0.01 m)
P A1 = partial pressure of A at plane 1 (15 kPa); and
P A2 = partial pressure of A at plane 2 (5 kPa)
 Substituting these in the equation

D AB
1.6 * 10 5
 15  5
8.3142930.01

Therefore, D AB = 3.898 * 10 –5 m 2/sec

 Example
A tube 1 cm in inside diameter that is 20 cm long is filled with
CO2 and H2 at a total pressure of 2 atm at 0C. The diffusion
coefficient of the CO2 – H2 system under these conditions is
0.275 cm2/sec. If the partial pressure of CO2 is 1.5 atm at one
end of the tube and 0.5 atm at the other end, find the rate of
diffusion for:
 steady state equimolar counter diffusion (N A = - N B)
 steady state counter diffusion where N B = -0.75 N A, and
 steady state diffusion of CO2 through stagnant H2 (NB = 0)
 N A   C D AB
dy
dz
A
y A N A  N B 
Given N B = - N A
dyA dCA
N A   C D AB  D AB
dz dz

(For ideal gas mixture

pA
CA 
RT

where pA is the partial pressure of A; such that p A + p B = P)

Therefore
N A  D A B

d pA RT 
dz
For isothermal system, T is constant
Therefore  D AB d p A
NA 
RT dz
(i.e.) Z2 P A2
D AB
N A d z   d pA
Z1 RT P A1

NA 
D AB
RT z
p A1  p A2 

where Z = Z 2 – Z 1
Given: D AB = 0.275 cm 2/sec = 0.275 * 10 –4 m 2 /sec ; T = 0C = 273 K

NA 
0.275 * 10  4
8314 * 273 * 0.2

1.5 * 1.01325 * 10 5  0.5 * 1.01325 * 10 5 
6 k mol
 6.138 * 10 2
m sec
Rate of diffusion = N A S
Where S is surface area
Therefore rate of diffusion = 6.138 * 10-6 *  r 2
= 6.138 * 10 –6 *  (0.5 * 10 –2) 2
= 4.821 * 10 –10 k mol/sec
= 1.735 * 10 –3 mol/hr.
ii)
N A   C D AB
dy
dz
A
y A N A  NB 
given: N B = - 0.75 N A

Therefore

N A   C D AB
dy
dz
A
y A N A  0.75 N A 
dy A
 C D AB  0.25 y A NA
dz

dyA
N A  0.25 y A N A   C D AB
dz

dy A
N A d z   C D AB
1 0.25 y A

for constant N A and C

 Z2 y A2
dy A
N A  d z   CD AB  1  0.25 y
Z1 y A1 A

 
  a  b x  b ln a  b x  
dx 1
 


N A z   C D AB   1 
  
 ln 1  0.25 y A yy A2
 0.25  A1

4 CD AB  1  0.25 y A 2 
NA  ln  
z  1  0.25 y A 1 
 
Given:
p 2 * 1.01325 * 10 5
C   0.0893 K mol m 3
RT 8314 * 273
p A1 1.5
y A1    0.75
P 2
p A2 0.5
y A2    0.25
P 2
Substituting these in equation (2),

4 * 0.0893 * 0.275 * 10  4  1  0.25 * 0.25 

NA  ln 1  0.25 * 0.75 
0.2
kmol
 7.028 * 10  6
m 2 sec

Rate of diffusion = N A S = 7.028 * 10 –6 *  * (0.5 * 10 –2) 2

= 5.52 * 10 –10 kmol/sec
= 1.987 * 10 –3 mol/hr.
iii)
N A   CD AB
dyA
dz

 y A N A NB 
Given: N B = 0 dyA
N A   CD AB  yA NA
dz
Z2 y A2
dy A
N A  d z   CD AB  1 y
Z1 y A1 A

CD AB  1  y A2 
 ln  
Z  1  y A1 
 
0.0893 * 0.275 * 10  4   1  0.25  
 ln  1  0.75  
0.2   
5 kmol
 1.349 * 10
m 2 . sec
Rate of diffusion = 1.349 8 10 –5 *  * (0.5 * 10 –2) 2
= 1.059 Kmol / sec
= 3.814 mol/hr
 Practice Problem
 Water in the bottom of a narrow metal tube 0.5 cm in
diameter is held at a constant temperature of 293K.
The total pressure of air is 1 atm and the temperature
is 293K. Water evaporates and diffuses through the air
in the tube and the diffusion path (z2-z1) is 0.1524 m
long. Calculate the rate of evaporation at steady state
in kmol/s. The diffusivity of water at 293K and 1 atm is
0.250x10-4 m2/s. Assume that the system is
isothermal.

93
Diffusion into an infinite standard
medium
 Problems involving diffusion from a spherical particle into an
infinite body of stagnant gas.
 How to set up differential equations that describe the diffusion
in these processes.
 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
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.

At any moment, when the radius of the drop is r 0, 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  ……….. (57)

Here N B = 0 (since air is assumed to be stagnant)

 dy A
N A   C D AB y A NA
dr

Rearranging,

 C D AB d y A
N  ……….. (58)
A
1 y A dr

The flux N A is not constant, because of the spherical geometry; it

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
r r  r ……….. (59)
4 r 2 N A  4 r 2 N A 0
r  r r
where A = surface area of sphere at r or r + r.
Substituting for A = 4  r 2 in equation (59),
r 2NA  r 2NA
r  r r
lim 0
 r 0 r
d
dr
r  2
N A  0 ……….. (60)

Integrating, 2 ………... (61)

r N A  constant
From equation (61),

r 2 N A  r 02 N A 0

Substituting for N A from equation (58),

 2
r C D AB d y A
 r 02 N A 0
1 y A dr

dr dy A
r 02 NA 0    C D AB  ………... (62)
r 2 1 y A

Boundary condition :
At r = r 0 y A = y AS
and
At r =  y A = y A
Therefore equation (62) becomes,


r 02 NA 0
 1
  
 C D AB ln 1  y A   y A
 r r0 y AS

Simplifying,
C D AB  1 y A  
NA 0  ln   ………... (63)
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 L 
4 r 02 N A0    r 3  ………... (64)
dt 3 0
M A 

2  d r0
  4  r0 L
MA dt

Substituting for N A0 from equation (63) in equation (64),

C D AB 1  y A    L d r 0
ln    ………... (65)
r0  1  y AS  MA dt
 
 Initial condition :
When t = 0 r0 = r1

Integrating equation (65) with these initial condition,

t  L 1 1 0
d t  M r0 d r0
C D AB  1 y A   r 1
ln  
0 A
 1 y A S 
 

L 1 r 12
t  ………... (66)
MA 2 C D AB  1 y A  
ln  
 1 y A S 
 

Equation (66) gives the total time t required for complete evaporation of
spherical droplet of initial radius r 1.
 Combustion of a coal particle
The problem of combustion of spherical coal particle is similar to
evaporation of a drop with the exception that chemical reaction
(combustions) occurs at the surface of the particle. During combustion of
coal, the reaction C + O2  CO 2 occurs.

According to this reaction for every mole of oxygen that diffuses to the
surface of coal (maximum of carbon), react with 1 mole of carbon,
releases 1 mole of carbon dioxide, which must diffuse away from this
surface. This is a case of equimolar counter diffusion of CO 2 and O 2.
Normally air (a mixture of N 2 and O 2) is used for combustion, and in this
case N 2 does not take part in the reaction, and its flux is zero. N N  0  2

The molar flux of O 2 could be written as

N O 2   C D O 2  gas
d yO2
dr

 y O 2 N O 2  N CO 2  N N 2  …... (67)

Where D O 2  gas is the diffusivity of O 2 in the gas mixture.

Since NN2  0
and from stoichiometry N O 2   N CO 2

d yO2
equation (67) becomes N O 2   C D O 2  gas ………... (68)
dr

For steady state conditions,

d
dr
r  2

NO2  0
Integrating,
r 2
N O 2  constant  r 02 N O 2 s ………... (69)

Where r 0 is the radius of coal particle at any instant,

and N O 2 s is the flux of O 2 at the surface of the particle.
Substituting for N O ,
2

d yO2
2
 r C D O 2  gas  r 02 N O 2 s ………... (70)
dr
 Boundary condition s:
At r  r0 y O2  y O2 s
r  yO2  yO2
With these boundary condition, equation (70) becomes

y O2
 dr
r 02 N A 0  2
  C D O 2  gas  d yO2
r0 r y O2s

y 
which yields
C D O 2  gas
NO2 s  O2s yO2 ………... (71)
r0
For fast reaction of O 2 with coal, the mole fraction of O 2 at the surface of
O2 s 0
particle is zero. (i.e.,) y
 And also at some distance away from the surface of the particle

y O 2  y O 2   0.21

(because air is a mixture of 21 mole % O 2 and 79 mole % N 2)

With these conditions, equation (6) becomes,

0.21 C D O 2  gas
NO2s  ………... (72)
r0
 Example

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 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
r rr

where S is the surface are (= 4  r 2)

dividing (1) by Sr, 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
dyA
dr

 y A N A NB 
N B = 0 (since air is assumed to be stagnant in the film)

dyA
N A   CD AB  yA 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:
At r = R
0.555
yA   7.303 * 10  4
760
ln (1 – y A) = - 7.3 * 10 –4
At r =  y A = 0 ln (1-y A) = 0
Therefore


 d ln 1  y A  
dr 0
WA  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 
R *T 8314 * 318

= 0.0383 kmol/m 3

Therefore W A = 4 * 3.142 * 2 * 10 –3 * 6.92 * 10 –6 * 0.0383 *

7.3 * 10 –4
= 4.863 * 10 –12 kmol/s
= 1.751 * 10 –5 mol/h.
 Diffusion in Liquids
The equations derived for diffusion in gases equally apply 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
 For steady – state diffusion of A through non diffusivity B:
N A = constant , N B = 0


NA
D AB
  x A1  x A2  …….. (73)
z x BM  M  av

where Z = Z 2 – Z 1, the length of diffusion path; and

X B 2  X B1
X BM  …………. (74)
X B2 
ln  
 X B 1
 For steady – state equimolar counter diffusion :
N A = - N B = const

D AB   
NA
D AB
Z
C A1  C A2    
Z  M  av

x A1  x A 2  … (75)
 Example

Calculate the rate of diffusion of butanol at 20C 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

20C may be taken as 0.971 and 0.992 g/cm3

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 M 2 
 
 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
Therefore   0.982
0.0163


D AB    x A1  x A2 
NA  
2  M  avg x B, lm


5.9 * 10  6 * 10  4 * 51.7
*
0.026  0.010
2 0.982
0.1 * 10

7 kmol
 4.97 * 10
m2 s
 gmol
 1.789
m 2 .hr .

g
 1.789 * 74
m 2 . hr .

g
 132.4
m 2 . hr .
 Mass diffusion with homogeneous
chemical reaction
 Absorption operations involve contact of a gas mixture with a
liquid and preferential dissolution of a component in the
contacting liquid.

 Depending on the chemical nature of the involved molecules,

the absorption may or may not involve chemical reaction.

 The following analysis illustrates the diffusion of a

component from the gas phase into the liquid phase
accompanied by a chemical reaction in the liquid phase.
Mass diffusion with homogeneous
chemical reaction
Consider a layer of absorbing medium (liquid) as shown in
diagram.

At the surface of the liquid, the composition of A is CA 0. The

thickness of the film,  is so defined, that beyond this film
the concentration of A is always zero ; that is C A = 0. If
there is very little fluid motion within the film,

118
 N A   D AB
dCA
dz

CA
C
N A  N B  ….. (76)

If the concentration of A in the film, C A is assumed small, equation (76)

becomes

dCA
N A   D AB …………... (77)
dz
The molar flux N A changes along the diffusion path. This change is due to
the reaction that takes place in the liquid film. This changes could be
written as d
dz
N A  r A  0 …………. (78)

where –rA is the rate of disappearance of A. For a first order

reaction,
k
A  B
……….. (79)
r A  kC A
 with the substitution from equation (79) and (77) in equation (78),

d  dCA
 D AB   kCA  0 ….. (80)
dz d z 
For constant Diffusivity,
2
d CA
 D AB  kCA  0 ….. (81)
dz2
which is a second order ordinary differential equation. The
general solution to this equation is

   
C A  C 1 cos h  k z   C 2 sin h  k z ….. (82)
 D AB   D AB 
The constants of this equation can be evaluated from the
boundary conditions:
at Z=0 C A = C A0
And at Z= C A = 0.
 The constant C 1 is equal to C A0 , and C 2 is equal to
 C A0  
 k   ….. (83)
tan h  D AB 
with this substitution equation (82) becomes,
 
C A 0 sinh  k z 
   D AB 
….. (84)
C A  C A 0 cos h  k z  
 D AB   
tan h  k
D
 
 A B 
This equation gives the variation of concentration of A
with z (i.e concentration profile of A in the liquid). The molar
flux at the liquid surface can be determined by differentiating
equation (84), and evaluating the derivative
dCA
at z  0
dz

Differentiating C A with respect to z,

  
C A0 k cos h  k z 
dCA   D AB  D AB 
 C A0 k sin h  k z   ….. (85)
dz D AB  D AB   
tan h  k  
 D AB 

Substituting z = 0 in equation (85) and from equation (77),

 
 k
D AB
 
D AB C A 0
NA    ….. (86)
Z0    k 
 tan h    
 D 
 AB

For absorption with no chemical reaction, the flux of A is obtained

from equation (77) as

D AB C A 0
N  …………………. (87)
A 
which is constant throughout the film of liquid. On comparison of equation
(86) and (87), it is apparent that the term
    
 kD   tan h  k   
 D AB
 AB    

shows the influence of the chemical reactions. This term is a dimensionless

quantity, is often called as Hatta Number.
 Diffusion in solids
In certain unit operations of chemical engineering such as in drying or
in absorption, mass transfer takes place between a solid and a fluid
phase. If the transferred species is distributed uniformly in the solid
phase and forms a homogeneous medium, the diffusion of the species
in the solid phase is said to be structure independent. In this case
diffusivity or diffusion coefficient is direction – independent.
At steady state, and for mass diffusion which is independent of
the solid matrix structure, the molar flux in the z direction is :

dCA
N A   D AB  constant ….. (88)
dz
as given by Fick’s law. Integrating the above equation,

NA 

D AB C A1  C A2 
….. (89)
z
which is similar to the expression obtained for diffusion in a stagnant
fluid with no bulk motion (i.e. N = 0).
 Diffusion in process solids
 In some chemical operations, such as heterogeneous
catalysis, an important factor, affecting the rate of reaction
is the diffusions of the gaseous component through a
porous solid.

 The effective diffusivity in the solid is reduced below what it

could be in a free fluid, for two reasons.

 tortuous nature of the path increases the distance,

which a molecule must travel to advance a given
distance in the solid.

 free cross – sectional area is restricted. For many

catalyst pellets, the effective diffusivity of a gaseous
component is of the order of one tenth of its value in a
free gas.
 Diffusion in process solids
 If the pressure is low enough and the pores are small
enough, the gas molecules will collide with the walls more
frequently than with each other.

 This is known as Knudsen flow or Knudsen diffusion.

 Upon hitting the wall, the molecules are momentarily

absorbed and then given off in random directions.

 The gas flux is reduced by the wall collisions.

 By use of the kinetic flux, the concentration gradient is

independent of pressure ; whereas the proportionality
constant for molecular diffusion in gases (i.e. Diffusivity) is
inversely proportional to pressure.

 Knudsen diffusion occurs when the size of the pore is of the

order of the mean free path of the diffusing molecule.
 Transient Diffusion

Transient processes, in which the concentration at a

given point varies with time, are referred to as unsteady
state processes or time – dependent processes. This
variation in concentration is associated with a variation
in the mass flux. These generally fall into two
categories:

 the process which is in an unsteady state only

during its initial startup
 the process which is in a batch operation throughout
its operation.
 Transient Diffusion
 In unsteady state processes there are three variables-
concentration, time, and position

 Therefore the diffusion process must be described by partial

rather than ordinary differential equations

 Many solutions are for one-directional mass transfer as

defined by Fick’s second law of diffusion

C A 2 C A
 D AB ……... (90)
t z2
 Transient Diffusion
 This partial differential equation describes a physical situation in
which there is no bulk–motion contribution, and there is no
chemical reaction.

 This situation is encountered when the diffusion takes place in

solids, in stationary liquids, or in system having equimolar counter
diffusion.

 Due to the extremely slow rate of diffusion within liquids, the bulk
motion contribution of flux equation (i.e., y A  N i) approaches the
value of zero for dilute solutions ; accordingly this system also
satisfies Fick’s second law of diffusion.

 Transient Diffusion
 The solution to Fick’s second law usually has one of the two
standard forms.

 It may appear in the form of a trigonometric series which

converges for large values of time, or it may involve series
of error functions or related integrals which are most
suitable for numerical evaluation at small values of time.

 These solutions are commonly obtained by using the

mathematical techniques of separation of variables or
Laplace transforms.
Convective Mass Transfer Coefficient
 Diffusive mass transfer results from a concentration
gradient within a system.

 In systems involving liquids or gases, however, it is

very difficult to eliminate convection from the overall
mass-transfer process.

 Mass transfer by convection involves the transport of

material between a boundary surface (such as solid or
liquid surface) and a moving fluid or between two
relatively immiscible, moving fluids.

131
Convective Mass Transfer Coefficient

There are two different cases of convective mass

transfer:

 Mass transfer takes place only in a single phase

either to or from a phase boundary, as in sublimation
of naphthalene (solid form) into the moving air.

 Mass transfer takes place in the two contacting

phases as in extraction and absorption.

132
 Convective Mass Transfer Coefficient
In the study of convective heat transfer, the heat flux is connected to
heat transfer coefficient as

Q A  q  h ts tm   ….. (91)

The analogous situation in mass transfer is handled by an

equation of the form

N A  k c C As  C A  ….. (92)
 The driving force is the difference between the concentration at the
phase boundary, CAS and the concentration at some arbitrarily
defined point in the fluid medium, C A .

 The convective mass transfer coefficient kC is a function of

geometry of the system and the velocity and properties of the fluid
similar to the heat transfer coefficient, h.
133
 Significant Parameters in Convective
Mass Transfer
 Dimensionless parameters are often used to correlate
convective transfer data.
 Reynolds number and friction factor (momentum transfer)
 Prandtl and Nusselt numbers (convective heat transfer)

 The molecular diffusivities of the three transport process

(momentum, heat and mass) have been defined as:


Momentum diffusivity  

k ….. (93)
Thermal diffusivity  
Cp

Mass diffusivity D AB 134

 Correlations
It can be shown that each of the diffusivities has the dimensions
of L2 / t, hence, a ratio of any of the two of these must be
dimensionless.

The ratio of the molecular diffusivity of momentum to the

molecular diffusivity of heat (thermal diffusivity) is designated as
the Prandtl Number

Momentum diffusivity  Cp 
 Pr   ….. (94)
Thermal diffusivity  K

The analogous number in mass transfer is Schmidt number given as

Momentum diffusivity   ….. (95)

 Sc  
Mass diffusivity D AB  D AB
135
 Correlations
The ratio of the molecular diffusivity of heat to the molecular diffusivity of
mass is designated the Lewis Number, and is given by

Thermal diffusivity  k ….. (96)

 Le  
Mass diffusivity D AB  C p D AB

Lewis number is encountered in processes involving simultaneous

convective transfer of mass and energy.

136
 Sherwood number
 Consider the mass transfer of solute A from a solid to a fluid
flowing past the surface of the solid.

 For such a case, the mass transfer between the solid surface
and the fluid may be written as


N A  k c C As  C A   ….. (97)

137
 Sherwood number
Since the mass transfer at the surface is by molecular diffusion,
the mass transfer may also be described by

dCA
N A   D AB ….. (98)
dy y 0

When the boundary concentration, CAs is constant, equation (98) may

be written as

N A   D AB

d C A  C As  ….. (99)
dy y 0

Equation (97) and (99) may be equated, since they define the same flux of
component A leaving the surface and entering the fluid

 
k c C A s  C A    D AB
d
dy

C A  C As  ….. (100)
y 0 138
 Sherwood number
This relation may be rearranged into the following form:

kc
 

d C A  C As d y 
D AB C A  C A   y 0
….. (101)

Multiplying both sides of equation(100) by a characteristic length, L we

obtain the following dimensionless expression:

kc L 
d C A  C As d y  y 0
 ….. (102)
D AB C A S  C A   L
The right hand side of equation (102) is the ratio of the concentration
gradient at the surface to an overall or reference concentration
gradient; accordingly, it may be considered as the ratio of molecular
mass-transport resistance to the convective mass-transport resistance
of the fluid. This ratio is generally known as the Sherwood number, Sh
and analogous to the Nusselt number Nu, in heat transfer. 139
 Application of Dimensionless
Analysis to Mass Transfer
 One of the methods of obtaining equations for predicting
mass-transfer coefficients is the use of dimensionless
analysis.

 Dimensional analysis predicts the various dimensionless

parameters which are helpful in correlating experimental
data.

 There are two important mass transfer processes, which we

shall consider, the transfer of mass into a stream flowing
under forced convection and the transfer of mass into a
phase which is moving as the result of natural convection
associated with density gradients.

140
Transfer into a stream flowing under
forced convection
Consider the transfer of mass from the walls of a circular conduit to a
fluid flowing through the conduit. The mass transfer is due to the
concentration driving force C As – C A .

The important variables, their symbols and their dimensions are listed in
the table
Variable Symbol Dimensions

tube diameter D L

fluid density ρ M/L3

fluid viscosity μ M/Lt

fluid velocity υ L/t

mass diffusivity DAB L2/t

mass-transfer coefficient kc L/t 141

 Dimensionless analysis
 These variables include terms descriptive of the system
geometry, the flow and fluid properties and the quantity of
importance, k c.

 By the Buckingham method of grouping the variables, the

number of dimensionless  groups is equal to the number of
variables minus the number of fundamental dimensions.

 Hence the number of dimensionless group for this problem

will be three.

 With D AB,  and D as the core variables, the three  groups to

be formed are

142
  1  DABa  b
Dc kc ….. (102)

 2  DABd  e D f v ….. (103)

and

 g
3  DAB  h
Di  ….. (104)

Substituting the dimensions for  ,

 1  DABa  b
Dc kc

a
L 2  M
b
L
1 
 t

  3 L  c   ….. (105)
  L  t 
143
 Equating the exponents of the fundamental dimensions on both
sides of the equation, we have
L : 0 = 2a – 3b + c + 1
t : 0=–a–1
M: 0=b
Solving these equations,
a = –1, b = 0 and c=1
Thus
kc D
1  ……….. (106)
D AB
which is the Sherwood number.
The other two  groups could be determined in the same manner,
yielding
D …………... (107)
and  2 
D AB

3   Sc ….. (108)
 D AB
which is termed as Schmidt Number
144
Dividing 2 by 3, we get
 2  D     D 
      Re ….. (109)
 3  D AB    D AB


 

which is the Reynolds Number

The result of the dimensional analysis of mass transfer by forced
convection in a circular conduit indicates that a correlating relation could
be of the form,

Sh   Re, Sc  ….. (110)

Which is analogous to the heat transfer correlation

Nu   Re, Pr  ….. (111)

145
 Mass Transfer with natural
convection
 Natural convection currents develop if there exists any
variation in density within the fluid phase.

 The density variation may be due to temperature differences

or to relatively large concentration differences.

 In the case of natural convection involving mass transfer from

a vertical plane wall to an adjacent fluid, the variables of
importance are listed in the table.

146
Mass Transfer with natural convection
According to Buckingham theorem, there will be three
dimensionless groups. Choosing D AB, L and  as the core
variables, the  groups to be formed are

 1  DABa L b  c k c ….. (112)

 2  DABd Le  f  ….. (113)

 3  DAB
g
L  gA
h i ….. (114)

147
 Table
Variable Symbol Dimensions

characteristic length L L

fluid density ρ M/L3

fluid viscosity μ M/Lt

buoyant force gΔρA M/L2t2

mass diffusivity DAB L2/t

mass-transfer coefficient kc L/t

148
 Solving for the dimensionless groups, we obtain

kc L ….. (115)
π1   Sh
D AB
ρ D AB 1
π   ….. (116)
2
μ Sc

and L3 g   A
  ….. (117)
3
 D AB
With the multiplication of 2 and 3, we obtain a dimensionless
parameter analogous to the Grashof number in heat transfer by natural
convection
  D AB  L 3 g   A 
 2 3     
   D AB 
    
L3  g   A
  Gr AB ….. (118)
 2 149
The result of the dimensional analysis of mass transfer by
natural convection indicates that a correlating relation could
be of the form,

Sh   Gr AB , Sc   ….. (119)

150
Analogies among Mass, Heat and
Momentum Transfer
 Analogies among mass, heat and momentum transfer have their
origin either in the mathematical description of the effects or in
the physical parameters used for quantitative description.

 To explore those analogies, it could be understood that the

diffusion of mass and conduction of heat obey very similar
equations. In particular, diffusion in one dimension is described
by the Fick’s Law as
dCA
J   D AB ….. (120)
A
dz
Similarly, heat conduction is described by Fourier’s law as

dT
q  k ….. (121)
dz
where k is the thermal conductivity. 151
 Mass, Heat and Momentum Transfer
The similar equation describing momentum transfer as given by
Newton’s law is
d
  ….. (122)
dz
where  is the momentum flux (or shear stress) and  is the viscosity of
fluid.

 It has become conventional to draw an analogy among mass, heat

and momentum transfer. Each process uses a simple law combined
with a mass or energy or momentum balance.

 The analogies are useful in understanding the transfer phenomena

and as a satisfactory means for predicting behaviour of systems for
which limited quantitative data are available.

152
Mass, Heat and Momentum Transfer

The similarity among the transfer phenomena and accordingly the

existence of the analogies require that the following five conditions exist
within the system

 The physical properties are constant

 There is no mass or energy produced within the system. This

implies that there is no chemical reaction within the system

 There is no emission or absorption of radiant energy.

 There is no viscous dissipation of energy.

 The velocity profile is not affected by the mass transfer. This

implies there should be a low rate of mass transfer.

153
Reynolds Analogy

The first recognition of the analogous behaviour of mass,

heat and momentum transfer was reported by Osborne
Reynolds in 1874. Although his analogy is limited in
application, it served as the base for seeking better
analogies.

Reynolds postulated that the mechanisms for transfer of

momentum, energy and mass are identical. Accordingly,

kc h f
  ….. (123)
    Cp 2
154
 Reynolds Analogy
Here h is heat transfer coefficient
f is friction factor
  is velocity of free stream

 The Reynolds analogy is interesting because it suggests

a very simple relation between different transport
phenomena.

 This relation is found to be accurate when Prandtl and

Schmidt numbers are equal to one.

 This is applicable for mass transfer by means of turbulent

eddies in gases. In this situation, we can estimate mass
transfer coefficients from heat transfer coefficients or
from friction factors.
155
 Chilton-Colburn analogies
Chilton and Colburn, using experimental data, sought
modifications to the Reynold’s analogy that would not have the
restrictions that Prandtl and Schmidt numbers must be equal to
one. They defined a j factor for mass transfer as
kc
jD  Sc  2 3 ….. (124)
 
The analogous j factor for heat transfer is
23
j H  St Pr ….. (125)

where St is Stanton number =

Nu

h ….. (126)
Re Pr  v  C p

Based on data collected in both laminar and turbulent flow

regimes, they found
f
jD  jH  ….. (127)
2 156
This analogy is valid for gases and liquids within the range of 0.6 < Sc
< 2500 and 0.6 < Pr < 100.

The Chilton-Colburn analogy has been observed to hold for many

different geometries for example, flow over flat plates, flow in pipes,
and flow around cylinders.

157
 Example
A stream of air at 100 kPa pressure and 300 K is flowing on the top
surface of a thin flat sheet of solid naphthalene of length 0.2 m with a
velocity of 20 m/sec. The other data are:

Mass diffusivity of naphthalene vapor in air = 6 * 10 –6 m 2/sec

Kinematic viscosity of air = 1.5 * 10 –5 m 2.sc
Concentration of naphthalene at the air-solid naphthalene
interface = 1 * 10 –5 kmol/m3

Calculate:
 the average mass transfer coefficient over the flat plate
 the rate of loss of naphthalene from the surface per unit width

Note: For heat transfer over a flat plate, convective heat transfer
coefficient for laminar flow can be calculated by the equation.

Nu  0.664 Re1L 2 Pr 1 3
You may use analogy between mass and heat transfer. 158
 Solution
Given: Correlation for heat transfer

Nu  0.664 Re1L 2 Pr 1 3
The analogous relation for mass transfer is

Sh  0.664 Re1L 2 Sc 1 3
where
Sh = Sherwood number = kL/D AB
Re L = Reynolds number = L/
Sc = Schmidt number =  / ( D AB)
k = overall mass transfer coefficient
L = length of sheet
D AB = diffusivity of A in B
 = velocity of air
 = viscosity of air
 = density of air, and
/ = kinematic viscosity of air. 159
 Substituting for the known quantities in equation (1)

13
k 0.2  0.220   1.5 * 10  5 
12
 0.664    
6 * 10  6 5
 1.5 * 10   6 * 10  6 
 

k = 0.014 m/s

Rate of loss of naphthalene = k (C Ai – C A)

= 0.014 (1 * 10 –5 – 0)
= 1.4024 * 10 –7 kmol/m 2 s

Rate of loss per meter width = (1.4024 * 10 –7) (0.2)

= 2.8048 * 10 –8 kmol/m.s
= 0.101 gmol/m.hr.
160
Convective Mass Transfer Correlations
 Extensive data have been obtained for the transfer of
mass between a moving fluid and certain shapes, such
as flat plates, spheres and cylinders.

 The techniques include sublimation of a solid,

vapourization of a liquid into a moving stream of air and
the dissolution of a solid into water.

 These data have been correlated in terms of

dimensionless parameters and the equations obtained
are used to estimate the mass transfer coefficients in
other moving fluids and geometrically similar surfaces.

161
 Flat Plate
From the experimental measurements of rate of evaporation from a liquid
surface or from the sublimation rate of a volatile solid surface into a
controlled air-stream, several correlations are available. These correlation
have been found to satisfy the equations obtained by theoretical analysis
on boundary layers,

Sh  0.664 ReL1 2Sc 1 3 laminar  Re L  3 * 10 5 ….. (128)

Sh  0.036 ReL0.8 Sc 1 3 turbulent Re L  3 * 10 5 ….. (129)

Using the definition of j factor for mass transfer in equation (128) and
(129) we obtain

j D  0.664 ReL 1 2 laminar  Re L  3 * 10 5 ….. (130)

J D  0.037 ReL 0.2 turbulent Re L  3 * 10 5 ….. (131)

These equations may be used if the Schmidt number is in the

162
range 0.6 < Sc < 2500.
 Single Sphere
Correlations for mass transfer from single spheres are
represented as addition of terms representing transfer by purely
molecular diffusion and transfer by forced convection, in the form
Sh  Sh o  C Re m Sc n ….. (132)

Where C, m and n are constants, the value of n is normally taken

as 1/3
For very low Reynold’s number, the Sherwood number should
approach a value of 2. Therefore the generalized equation
becomes

m 1 3 ….. (133)
Sh  2  C Re Sc

163
 Single Sphere
For mass transfer into liquid streams, the equation given by Brain and
Hales


Sh  4  1.21 2 3 12
Pe AB  ….. (134)

correlates the data that are obtained when the mass transfer
Peclet number, Pe AB is less than 10,000. This Peclet number is
equal to the product of Reynolds and Schmidt numbers (i.e.)

Pe AB  Re Sc ….. (135)

For Peclet numbers greater than 10,000, the relation given by

Levich is useful

Sh  1.01 Pe1AB3 ….. (136)

164
 Single Sphere
The relation given by Froessling

Sh  2  0.552 Re 1 2 Sc 1 3 ….. (137)

correlates the data for mass transfer into gases Reynold’s numbers
ranging from 2 to 800 and Schmidt number ranging 0.6 to 2.7.
For natural convection mass transfer the relation given by Schultz


Sh  2  0.59 Gr AB Sc 1 4 ….. (138)

is useful over the range

2 * 10 8 < Gr AB Sc < 1.5 * 10 10

165
 Example
The mass flux from a 5 cm diameter naphthalene ball placed
in stagnant air at 40C and atmospheric pressure, is 1.47 * 10
–3 mol/m 2. sec. Assume the vapor pressure of naphthalene

to be 0.15 atm at 40C and negligible bulk concentration of

naphthalene in air. If air starts blowing across the surface of
naphthalene ball at 3 m/s by what factor will the mass transfer
rate increase, all other conditions remaining the same?
For spheres :

Sh = 2.0 + 0.6 (Re) 0.5 (Sc)0.33

Where Sh is the Sherwood number and Sc is the Schmids

number. The viscosity and density of air are 1.8 * 10 –5
kg/m.s and 1.123 kg/m 3, respectively and the gas constant is
82.06 cm 3 . atm/mol.K. 166
 Flow Through Pipes
Mass transfer from the inner wall of a tube to a moving fluid has
been studied extensively. Gilliland and Sherwood, based on the
study of rate of vapourisation of nine different liquids into air given
the correlation

p B, l m 0.83 0.44 ….. (140)

Sh  0.023 Re Sc
P

Where p B, lm is the log mean composition of the carrier gas,

evaluated between the surface and bulk stream composition. P is
the total pressure. This expression has been found to be valid over
the range
2000 < Re < 35000
0.6 < Sc < 2.5 167
Linton and Sherwood modified the above relation making it suitable for
large ranges of Schmidt number. Their relation is given as
….. (141)
Sh  0.023 Re 0.83 Sc 1 3
and found to be valid for
2000 < Re < 70000
and 1000 < Sc < 2260

Example

A solid disc of benzoic acid 3 cm in diameter is spun at 20 rpm and

25C. Calculate the rate of dissolution in a large volume of water.
Diffusivity of benzoic acid in water is 1.0 * 10 –5 cm 2/sec, and
solubility is 0.003 g/cc. The following mass transfer correlation is
applicable:
Sh = 0.62 Re ½ Sc 1/3
Where D2  and  is the angular
Re 
 speed in radians/time 168
Solution

Dissolution rate = N A S ….. (*1)

Where N A = mass flux, and
S = surface area for mass transfer
N A = k c (C As – C A ) ….. (*2)
Where C As is the concentration of benzoic acid in water at the surface
of the dose.
C A is the concentration of benzoic acid in water for an infinite
distance from the surface of the disc.
Given:
Sh = 0.62 Re ½ Sc 1/3
(i.e.) 1 1
kc D D 2   2   3
 0.62     ….. (*3)
D AB      D AB 
   
20
 * 2  radian sec
60
1 rotation = 2  radian
169
Therefore 20 rotation per minute = 20 * 2  radian/min
 For water  = 1 g/cm 3  = 1 centipoise = 0.01 g/cm.sec.
From (*3),
1 1
    2   3

k c  0.62 D AB  
     D AB 
1 1
5  40  60 * 1 2  0.01  3
 0.62 * 1.0 * 10 *   5

 0.01   1 * 1.0 * 10 
= 8.973 * 10 –4 cm/sec.
From (*2),
N A = 8.973 * 10 –4 (0.003 – 0)
= 2.692 * 10 –6 g/cm 2.sec
From (*1),
N A S = N- A * (2r 2)
= 2.692 * 10 –6 * (2 * 1.5 2)
= 3.805 * 10 –5 g/sec
= 0.137 g/hr. 170