Mass Transfer Process Lecture Note PDF
Mass Transfer Process Lecture Note PDF
Mass Transfer Process Lecture Note PDF
Course Content
Distillation
Batch distillation
Rayleigh equation
Fractionation
Binary distillation
McCabe-Thiele method
Ponchon-Savarit method
Course Objectives
The student is expected to:
Recognize the various modes of mass transfer
Estimate diffusion coefficients under different physical conditions
References
Principles and Modern Applications of Mass
Transfer Operations 2nd Edition, 2009
Jaime Benitez
References
Transport Phenomena 2006
Edwin N. Lightfoot, R. Byron Bird, Warren E. Stewart
2005
Course Organisation
TA:
Prerequisites
What do we need?
10
11
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.
14
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
.. (1)
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,
Number of moles
mass of A
molecular weight of A
.. (2)
CA
nA A
V MA
... (3)
16
Concentration of Species
For ideal gas mixtures,
pA V
.. (4)
RT
CA
nA
pA
V
RT
C Ci
i
. (5)
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:
. (6)
18
Velocities
Similarly, molar-average velocity of the mixture * is
C i V
i
. (7)
CA
C
CA
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
i
x i 1
.. (9)
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
2.24
* 100 7.30%
30.68
2.80
CO
* 100 9.13%
30.68
CO 2
6.60
* 100 21.51%
30.68
N2
19.04
* 100 62.06%
30.68
23
30.68
30.68 g mol
1
n
P
V
RT
n
molar density m
V
Therefore, density (or mass density) = mM
Where M is the molecular weight of the gas.
Density m
PM
1.5 * 10 5 * 30.68
M
kg m 3
RT
8314 * 273
= 2.03 kg/m 3
24
7
* 1.5 * 10 5
100
= 0.07 * 1.5 * 10 5
= 0.105 * 10 5 Pa
25
N A C A
. (11)
Diffusivities
Diffusivities are defined with respect to a
plane moving at the volume average
velocity v*. By definition,
*
C
i
... (12)
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
By definition
. (13)
C
i
CA
NA CA ( A ) Ci i
C i
C A (
) y A C i
.. (14)
i
28
Diffusion flux
For systems containing two components A and B,
N A C A (
C A (
N
A
A
C A (
) y A (C A A C B B )
) y A (N A N B )
A
) y
(15)
... (16)
Flux notations
Mass flux of species i with respect to fixed coordinates
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 molaraverage 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
Ficks law
An empirical relation for the diffusional molar flux, first postulated by
Fick and, accordingly, often referred to as Ficks first law, defines the
diffusion of component A in an isothermal, isobaric system. For diffusion
in only the Z direction, the Ficks rate equation is
JA D
AB
dC A
dZ
. (17)
J A C DA B
dy A
dZ
. (18)
C DA B
dy A
y
dZ
AN
. (19)
32
y AN
. (20)
J A N A y AN
.... (21)
J B N B y BN
. (22)
N A N B (y
A y B) N
(23)
33
AB
dy A
dyB
C D BA
dz
dZ
... (24)
............... (25)
y A + y B- = 1
dy A = - dy B
Therefore Equation (25) becomes,
D AB = D BA
.. (26)
... (27)
34
Diffusivity
Ficks 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:
In literature, some values of DAB are given for a few gas, liquid,
and solid systems.
35
T, K D AB P,m -Pa/s
273
298
298
293
273
273
273
491
273
298
293
298
298
614
303
298
298
273
315
273
298
298
2.006
0.735
0.974
0.923
1.378
0.894
1.256
1.621
0.718
1.337
0.908
0.845
1.641
4.791
0.870
0.879
0.610
1.773
0.932
1.236
0.855
2.634
293
1.793
318
318
319
0.724
0.724
0.675
System
Carbon dioxide
Ethanol
Ethyl ether
Hydrogen
Methane
Methanol
Nitrogen
Nitrous oxide
Propane
Water
Hydrogen
Ammonia
Argon
Benzene
Ethane
Methane
Oxygen
Pyridine
Nitrogen
Ammonia
Ethylene
Hydrogen
Iodine
Oxygen
Oxygen
Ammonia
Benzene
Ethylene
Water
T, K
D AB P, m -Pa/s
273
273
273
273
298.6
298
298
298
298
0.702
0.548
5.572
1.550
1.064
1.672
1.185
0.874
1.661
293
293
273
273
273
273
318
8.600
7.800
3.211
4.447
6.331
7.061
4.427
293
298
288
273
273
2.441
1.651
7.527
0.709
1.834
293
296
293
308.1
2.563
0.951
1.844
2.857
36
System
T,K
Chloroform (solvent B)
Acetone
Benzene
Ethanol
Ethyl ether
Ethyl acetate
MEK
298
288
288
298
298
298
2.35
2.51
2.20
2.13
2.02
2.13
Acetic acid
Acetone
Ethyl benzoate
MEK
Nitrobenzene
Water
293
293
293
303
293
298
2.18
3.18
1.85
2.93
2.25
3.20
1.49
2.00
1.92
1.25
2.00
1.02
1.00
1.20
2.10
0.58
0.92
1.64
298
298
298
281
298
288
298
353
303
281
298
281
2.09
1.96
1.38
1.45
2.09
2.25
2.28
4.25
2.09
1.19
1.85
1.77
Methane
Air
Carbon dioxide
Chlorine
Argon
Benzene
Ethanol
Ethane
Oxygen
Pyridine
Aniline
Ammonia
298
298
298
298
298
298
288
298
298
288
293
298
1.87
2.92
4.04
2.62
3.77
4.56
Ethylene
Allyl alcohol
Acetic acid
Benzoic acid
Propionic acid
Vinyl chloride
298
288
313
298
298
298
288
293
298
298
298
0.90
1.19
1.00
1.06
1.34
298
298
1.81
1.24
Ethylbenzene
Sulfuric acid
Nitric acid
293
298
298
0.81
1.73
2.60
Ethanol (solvent B)
Benzene
Water
Water (solvent B)
Acetone (solvent B)
Acetic acid
Acetic acid
Benzoic acid
Formic acid
Water
Benzene (solvent B)
Acetic acid
Aniline
Benzole acid
Bromobenzene
Ciclohexane
Ethanol
Formic acid
n-Heptane
MEK
Naphthalene
Toluene
Vinyl chloride
DAB x10 , cm /s
37
Hydrogen in iron
Hydrogen in nickel
Carbon monoxide in nickel
Aluminum in copper
Uranium in tungsten
Cerium in tungsten
Yttrium in tungsten
Tin in lead
Gold in lead
Gold in silver
Antimony in silver
Zinc in aluminum
Silver in aluminum
Bismuth in lead
Cadmium in copper
Carbon in iron
Helium in silica
Hydrogen in silica
Helium in Pyrex
T, K
283
323
373
358
438
1223
1323
1123
293
2000
2000
2000
558
558
1033
293
773
323
293
293
1073
1373
293
773
473
773
293
773
1.66 x 10 -9
11.4 x 10-9
124 x 10-9
-9
11.6 x 10
-8
10.5 x 10
4.00 x 10-8
-8
14.0 x 10
-9
2.20 x 10
1.30 x l0- 30
1.30 x 10 - 11
-11
95.0 x 10
-11
1820 x 10
-10
1.60 x 10
- 10
4.60 x 10
3.60 x 10- 10
3.60 x 10- 10
-9
2.00 x 10-9
1.20 x 10
l.l0 x 10 -16
2.70 x 10 -15
1.50 x 10 -8
-8
45.0 x 10
4.00 x 10- 10
7.80 x 10 -8
6.50 x 10- 10
1.30 x 10 -8
4.50 x 10-11
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
39
5 X 10 6
10 6
5 X 10 14
----------------
1 X 10-5
10-9
1 X 10-10
m2 / s.
m2 / s.
m2 / s.
40
General expressions
Pressure dependence of diffusivity is given by
AB
. (28)
AB
. (29)
DAB
3.03 0.98 / M 10 T
1/ 2
AB
2
AB
PM 1AB2 D
42
M AB
DAB
MA, MB
T
P
AB
D
1
1
2
M A MB
* b
c
e
g
*
*
exp dT
exp fT
exp hT *
where T* = T/AB
a
b
c
d
=
=
=
=
1.06036
0.15610
0.19300
0.47635
e
f
g
h
=
=
=
=
1.03587
1.52996
1.76474
3.89411
44
AB
A B
2
AB A B
45
1.18V
13
b
1.15Tb
Vb 0.285Vc
1.048
47
48
49
50
Fuller method
DAB
P v A v B
1
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
D 1 mixture
1
y 3
y 2
y n
...........
D1 2
D1 3
D1 n
. (30)
y 2
y2
y2
y 3 ....... y n
... (31)
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%,
54
Diffusivity of CO 2 in mixture
D 1m
y 2
where
D 12
y2
y 2
y2 y3
y3
y 3
Therefore
y3
D 1m P
y 3
D 13
0.15
0.21
0.15 0.565
0.565
0.79
0.15 0.565
1
0.21
0.79
1.874
1.945
= 1.93 m 2.Pa/s
D1m
1.93
5
2
1.61
*
10
m
s
5
1.2 * 10
55
D 2m
y 1
D 21
Where
y 1
y1
y1 y3
D 23
0.285
0.335
0.285 0.565
y3
y3
y1 y3
0.565
0.665
0.285 0.565
56
D 21 P = D 12 P = 1.874 m 2.Pa/sec
Therefore
D 2m P
0.335
0.665
1.874
1.834
= 1.847 m 2.Pa/sec
D 2m
1.847
1.2 * 10 5
1.539 * 10 5 m 2 sec
Diffusivity in liquids
Diffusivities in liquids are nearer to 10-5 cm2 / s, and
about ten thousand times slower than those in dilute
gases.
58
Diffusivity in liquids
Certain compounds diffuse as molecules,
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
dy A
C D AB
y
dz
(N
N B)
. (32)
62
z=z2
z=z1=0
Liquid A
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)
dN A
0
dz
.. (33)
d N B
d Z
0,
.. (34)
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
NA
dy A
C D AB
y A (N A N B ) . (35)
dz
Since N B = 0,
NA
dy A
C D AB
y AN
dz
.. (36)
Rearranging,
NA
C D AB d y A
1 y A d z
. (37)
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
Z1
A1
d z C DAB
NA
CD
Z
AB
Z1
dy A
1 y
A
y
. (38)
1 y A2
ln
1 y A1
. (39)
67
ln y B 2
B1
y B 1 y A
Since
y B, lm
(1 y
) (1 y
ln y B 2
y
B1
A2
A1
A1
A2
ln y B 2
y
B1
. (41)
C D AB ( y A1 y A2 )
Z 2 z1
y B, lm
. (42)
68
V
RT
. (43)
p A
. (44)
D AB
( p A1 p A2 )
RT ( z2 z1)
p B, lm
. (45)
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.
70
Example
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 nondiffusing.
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
N A Nx A J A
. (a)
72
Solution
From Ficks law of diffusion,
D AB
dCA
. (b)
dz
N A Nx A D AB
dCA
. (c)
dz
NA NA NB
CA
C
D AB
dCA
dz
.. (d)
73
. (e)
C C A2
1
ln
NA
C C A1
Therefore,
NA
CD AB
z
ln
. (f)
. (g)
C C A2
C C A1
. (h)
74
NA
D AB P t
RTz
ln
P t P A2
P t P A1
. (i)
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)
75
83142980.002
1 0.2
76
N
or
C D AB
dy A
y
dz
D AB
dC A
y
dz
(N A N B )
(N A N B )
. (48)
. (49)
AB
dC A
dz
. (50)
NA d z D
C A2
dC
AB
Z1
C A1
from which
AB
z 2z1
(C
A1
A2 )
. (51)
nA
pA
V
RT
N
.
D AB
(P
R T (z 2 z 1)
A1
A2 )
. (52)
d
(N
dz
A)
. (53)
AB
d CA
dz
. (54)
Therefore
d
dz
or
d CA
D AB
0
dz
CA
dz
0.
. (55)
C
C
A
A1
A1
A2
zz1
z1 z 2
.. (56)
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;
NA
6.75 * 10 5
55 15 kmol
3.633 * 10
kmol
sec
3.633 * 10
6.75 * 10 5
55 p A
8.314 * 298 * 0.02
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 20C.
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)
1.6 * 10
D AB
8.3142930.01
15 5
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 0C. 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)
dy
N A C D AB
dz
N A N B
Given N B = - N A
N A C D AB
(For ideal gas mixture
CA
dyA
dz
D AB
dCA
dz
pA
RT
dz
(i.e.)
Z2
N A d z
Z1
NA
D AB
RT
P A2
d pA
P A1
p A1 p A2
RT z
D AB
where Z = Z 2 Z 1
Given: D AB = 0.275 cm 2/sec = 0.275 * 10 4 m 2 /sec ; T = 0C = 273 K
NA
0.275 * 10 4
k mol
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)
C D AB
dy
dz
N A
NB
given: N B = - 0.75 N A
Therefore
N A C D AB
C D AB
dy
dz
dy
dz
N A 0.75 N A
0.25 y
N A 0.25 y A N A C D AB
N A d z C D AB
for constant N A and C
dy
dyA
dz
1 0.25 y
NA
Z2
y A2
Z1
1 0.25 y
A
y A1
N A d z CD AB
dy
dx
1
a b x b ln a b x
N A z C D AB
NA
ln 1 0.25 y A
0.25
4 CD AB
z
yy
1 0.25 y A 2
ln
1 0.25 y A 1
A2
A1
Given:
p
2 * 1.01325 * 10 5
C
0.0893 K mol m 3
RT
8314 * 273
A1
A2
p A1
P
1.5
0.75
2
p A2
P
0.5
0.25
2
NA
4 * 0.0893 * 0.275 * 10 4
0.2
7.028 * 10 6
kmol
1 0.25 * 0.25
ln 1 0.25 * 0.75
m 2 sec
iii)
N A CD AB
Given: N B = 0
dyA
N A CD AB
dz
dyA
dz
Z2
N A d z CD AB
Z1
y A N A NB
yA NA
y A2
dy
1 y
A
y A1
1 y A2
ln
1 y A1
Z
0.0893 * 0.275 * 10 4
0.2
CD AB
1.349 * 10
Rate of diffusion
1 0.25
ln 1 0.75
kmol
m 2 . sec
= 1.349 8 10 5 * * (0.5 * 10 2) 2
= 1.059 Kmol / sec
= 3.814 mol/hr
Practice Problem
93
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
N A N B
.. (57)
N A C D AB
dy
dr
NA
Rearranging,
C D AB d y
1 y A
.. (58)
dr
AN A
4 r 2 N A
AN A
4 r 2 N A
r r
r r
r
.. (59)
r r
r 0
d
r
dr
Integrating,
r 2NA
N A constant
.. (60)
... (61)
r 2 N A r 02 N A 0
Substituting for N A from equation (58),
r 02
C D AB d y A
r 02 N A 0
1 y A
dr
NA 0
dr
r
C D AB
dy
1 y
... (62)
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
r r0
y A
y AS
Simplifying,
NA 0
C D AB
r0
1 y A
ln
1 y A S
... (63)
unit time
unit time
4
r 02
N A0
d
dt
4
L
3
r
0
3
M A
4 r0
... (64)
d r0
MA dt
C D AB
r0
1 y A L d r 0
ln
1 y AS
MA dt
... (65)
Initial condition :
When t = 0
r0 = r1
d t M
A
0
1
C D AB
L
MA
0
1
r0 d r0
1 y A r 1
ln
1 y A S
1
2 C D AB
r 12
1 y A
ln
1 y A S
... (66)
Equation (66) gives the total time t required for complete evaporation of
spherical droplet of initial radius r 1.
N O 2 C D O 2 gas
Where
D O 2 gas
d yO2
dr
y O 2 N O 2 N CO 2 N N 2
... (67)
NN2 0
Since
N O 2 N CO 2
N O 2 C D O 2 gas
d
r
dr
d yO2
dr
... (68)
NO2 0
Integrating,
N O 2 constant r 02 N O 2 s
... (69)
and
Substituting for N O ,
2
2
r C D O 2 gas
d yO2
dr
r 02 N O 2 s ... (70)
Boundary condition s:
At
r r0
y O2 y O2 s
yO2 yO2
r 02 N A 0
r0
which yields
NO2 s
dr
r
C D O 2 gas
C D O 2 gas
r0
O2s
y O2
d yO2
y O2s
yO2
... (71)
For fast reaction of O 2 with coal, the mole fraction of O 2 at the surface of
particle is zero. (i.e.,) y
O2 s 0
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,
NO2s
0.21 C D O 2 gas
r0
... (72)
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
rr
d r 2N A
dr
N A CD AB
dyA
dr
y A N A NB
N A CD AB
dyA
N A CD AB
N A CD AB
dr
d
dr
yA NA
yA
1 y A
d ln 1 y A
dr
WA
WA
4 r 2 CD AB d ln 1 y A
dr
dr
r
4 D AB C d ln 1 y
Boundary condition:
At r = R
yA
0.555
7.303 * 10 4
760
ln (1 y A) = - 7.3 * 10 4
y A = 0 ln (1-y A) = 0
At r =
Therefore
WA
dr
r
4 D AB C
d ln 1 y A
7.3 *10 4
WA
1
r 4 D AB C ln 1 y A
R
0 7.3 *10
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
NA
D AB
z x BM
x A1 x A2
M av
.. (73)
X BM
X B 2 X B1
X B2
ln
X
B 1
. (74)
NA
D AB
Z
C A1 C A2
D AB
x A1 x A 2
Z M av
(75)
Example
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.
Solution
For steady state unidirectional diffusion,
NA
D AB
x A1 x A2
C
z
x B, lm
where C is the average molar density.
M avg
Conversion from weight fraction the Mole fraction:
x A1
x A2
0.1 74
0.1 74
0.9 18
0.04 74
0.04 74
0.96 18
0.026
0.010
M1
M2
1
19.47 kg Kmol
0.1 74 0.9 18
18.56 kg Kmol
0.04 74 0.96 18
1 M1 2 M 2
2
M avg
x B,lm
x B 2 x B1
ln x B 2 x B1
1 x A2 1 x A1
1 x A2
ln
1 x A1
(i.e.)
x B,lm
Therefore
NA
1 0.01 1 0.026
1 0.01
ln
1 0.026
0.016
0.982
0.0163
D AB
2 M avg
x A1 x A2
x B, lm
5.9 * 10 6 * 10 4 * 51.7
0.1 * 10
4.97 * 10
0.026 0.010
kmol
m2 s
0.982
1.789
gmol
m 2 .hr .
1.789 * 74
132.4
g
m 2 . hr .
g
m 2 . hr .
N A D AB
dCA
dz
CA
C
N A N B
.. (76)
N A D AB
dCA
dz
... (77)
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
N A r A
dz
. (78)
A B
r A kC A
.. (79)
with the substitution from equation (79) and (77) in equation (78),
dCA
d
D AB
kCA 0
dz
d z
For constant Diffusivity,
D AB
CA
dz2
kCA 0
.. (80)
.. (81)
C A C 1 cos h
D AB
z C 2 sin h
D AB
z .. (82)
C A0
tan h
D AB
.. (83)
C A C A 0 cos h
D AB
C A 0 sinh k
z
D AB
tan h k
D
A
B
.. (84)
dCA
dz
at z 0
dCA
dz
C A0
D AB
sin h k
z
D AB
C A0
D AB
tan h
cos h k
z
D AB
k
D AB
.. (85)
NA
Z0
D AB C A 0
D AB
tan h
D
AB
.. (86)
D AB C A 0
. (87)
kD
AB
tan h
D AB
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 :
N A D AB
dCA
dz
constant
.. (88)
NA
D AB C A1 C A2
z
.. (89)
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 variablesconcentration, 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 Ficks second law of diffusion
C A
t
D AB
2 C A
z2
... (90)
Transient Diffusion
This partial differential equation describes a physical situation in
which there is no bulkmotion 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 Ficks second law of diffusion.
Transient Diffusion
The solution to Ficks 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.
131
132
Q A q h ts tm
.. (91)
N A k c C As C A
.. (92)
Thermal diffusivity
Mass diffusivity D AB
k
Cp
.. (93)
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
Cp
Momentum diffusivity
Pr
Thermal diffusivity
.. (94)
Momentum diffusivity
Sc
Mass diffusivity
D AB
D AB
.. (95)
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
Le
Mass diffusivity
D AB
C p D AB
.. (96)
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
N A D AB
dCA
dy
.. (98)
y 0
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
C A C As
dy
.. (100)
y 0
138
Sherwood number
This relation may be rearranged into the following form:
kc
D AB
d C A C As d y
C A C A
.. (101)
y 0
kc L
D AB
d C A C As d y
C A S C A L
y 0
.. (102)
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
Symbol
Dimensions
tube diameter
fluid density
M/L3
fluid viscosity
M/Lt
fluid velocity
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
Dc kc
.. (102)
2 DABd e D f v
.. (103)
.. (104)
and
g
3 DAB
Di
1 DABa
L
1
t
M
3
L
Dc kc
L c
L
t
.. (105)
143
kc D
.. (106)
D AB
D AB
D AB
... (107)
Sc
.. (108)
144
Dividing 2 by 3, we get
2 D
3 D AB
D AB
D
Re
.. (109)
Sh Re, Sc
.. (110)
Nu Re, Pr
.. (111)
145
146
1 DABa L b c k c
.. (112)
2 DABd Le f
.. (113)
g
3 DAB
.. (114)
L gA
h
147
Table
Variable
Symbol
Dimensions
characteristic length
fluid density
M/L3
fluid viscosity
M/Lt
buoyant force
gA
M/L2t2
mass diffusivity
DAB
L2/t
kc
L/t
mass-transfer coefficient
148
and
kc L
Sh
D AB
D AB
Sc
L3 g A
D AB
.. (115)
.. (116)
.. (117)
2 3
D AB
L 3 g A
D AB
L3 g A
Gr AB
.. (118)
149
Sh Gr AB , Sc
.. (119)
150
D AB
dCA
.. (120)
dz
dT
q k
dz
where k is the thermal conductivity.
.. (121)
151
d
dz
.. (122)
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
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.
kc
Cp
.. (123)
154
Reynolds Analogy
Here h is heat transfer coefficient
f is friction factor
is velocity of free stream
Chilton-Colburn analogies
Chilton and Colburn, using experimental data, sought
modifications to the Reynolds 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
jD
kc
Sc 2 3
.. (124)
j H St Pr
where St is Stanton number =
23
Nu
h
Re Pr v C p
.. (125)
.. (126)
jD jH
.. (127)
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 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
k 0.2
6 * 10 6
0.220
0.664
5
1.5 * 10
12
1.5 * 10 5
6 * 10 6
13
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
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,
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
.. (132)
Sh 2 C Re
Sc
1 3 .. (133)
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)
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 Reynolds 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)
165
Example
The mass flux from a 5 cm diameter naphthalene ball placed
in stagnant air at 40C and atmospheric pressure, is 1.47 * 10
3 mol/m 2. sec. Assume the vapor pressure of naphthalene
to be 0.15 atm at 40C 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
p B, l m
P
0.023 Re
0.83
Sc
0.44
.. (140)
Linton and Sherwood modified the above relation making it suitable for
large ranges of Schmidt number. Their relation is given as
Sh 0.023 Re 0.83 Sc 1 3
.. (141)
Example
A solid disc of benzoic acid 3 cm in diameter is spun at 20 rpm and
25C. 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 Sc 1/3
Where
D2
and is the angular
Re
speed in radians/time 168
Solution
.. (*1)
Dissolution rate = N A S
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 Sc 1/3
(i.e.)
kc D
D AB
D 2
0.62
1
2
1
3
D AB
.. (*3)
20
* 2 radian sec
60
1 rotation = 2 radian
Therefore 20 rotation per minute = 20 * 2 radian/min
169
k c 0.62 D AB
D AB
0.62 * 1.0 * 10
40 60 * 1
*
0.01
1
2
0.01
5
1 * 1.0 * 10
1
3
= 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 * (2r 2)
= 2.692 * 10 6 * (2 * 1.5 2)
= 3.805 * 10 5 g/sec
= 0.137 g/hr.
170