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Many of air day-by-day experiences also involve mass transfer, for example:
(i)
(ii)
(iii)
mA
V
------------------------------------
(1)
The total mass concentration density is the sum of the total mass of the mixture
in unit volume:
By definition,
Number of moles
m
M
mass of A
molecularweight of A
A
A
----------------------------- (2)
nA
V
M
A
A
pA V
RT
nA
p
A
V
RT
C C
i
3.2.2 Velocities
In a multicomponent system the various species will normally move at different
velocities; and 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
3
i
i
i
i
C i V
i
For most engineering problems, there will be title difference in * and and so
the mass average velocity, , will be used in all further 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 -
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
C
CA
C
(gases).
(i.e.)
x
i
y
i
wA
10. The molar composition of a gas mixture at 273 K and 1.5 * 10 5 Pa is:
O2
CO
CO 2
N2
7%
10%
15%
68%
Determine
a)
b)
c)
d)
Calculations:
Let the gas mixture constitutes 1 mole. Then
O2
CO
CO 2
N2
= 0.07 mol
= 0.10 mol
= 0.15 mol
= 0.68 mol
= 2 * 16 = 32 g/mol
= 12 + 16 = 28 g/mol
= 12 + 2 * 16 = 44 g/mol
= 2 * 14 = 28 g/mol
= 0.07 * 32 = 2.24 g
= 0.10 * 28 = 2.80 g
= 0.15 * 44 = 6.60 g
= 0.68 * 28 = 19.04 g
2.24
* 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
O2
M
Average molecular weight of the gas mixture
30.68
30.68 g mol
1
n
P
V
RT
n
molar density m
V
Density m M
PM
1.5 * 10 5 * 30.68
kg m 3
RT
8314 * 273
= 2.03 kg/m 3
7
* 1.5 * 10 5
100
= 0.07 * 1.5 * 10 5
= 0.105 * 10 5 Pa
6
A A
---------------------- (1)
) C
--------------- (2)
By definition
C i
CA
C i
C i
) y
C i
i
C
C
A
A
(
(
A
A
) y
) y
A (C A
A (N A
A C
N B )
B)
) y
----------- (3)
The first term on the right hand side of this equation is diffusional molar flux of A,
and the second term is flux due to bulk motion.
3.3.1 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
J A C DA B
dy A
dZ
----------------- (4)
C DA B
dy A
y
dZ
N
--------------- (5)
or
----------------------- (6)
Similarly,
-------------------- (7)
(y
B) N
---------- (8)
By definition N = N A + N B and y A + y B = 1.
Therefore equation (8) becomes,
JA+JB=0
J A = -J B
CD
From
AB
dy A
CD
dz
BA
dy B
dZ
--------------- (9)
yA+yB=1
dy A = - dy B
3.4 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: Kinematic viscosity,
= ( / ) in momentum transfer, and thermal diffusivity, (= k / C ) in heat
transfer.
Diffusivity is normally reported in cm2 / sec; the SI unit being m2 / sec.
Diffusivity depends on pressure, temperature, and composition of the system.
In table, some values of DAB are given for a few gas, liquid, and solid systems.
Diffusivities of gases at low density are almost composition independent, incease
with the temperature and vary inversely with pressure. Liquid and solid
diffusivities are strongly concentration dependent and increase with temperature.
General range of values of diffusivity:
5 X 10 6
10 6
5 X 10 14
Gases :
Liquids :
Solids :
-------------------------------------
1 X 10-5
10-9
1 X 10-10
m2 / sec.
m2 / sec.
m2 / sec.
AB
1
p
AB
D 1 mixture
1
y 3
y 2
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
10
y 2
y2
y2
y 3 ....... y n
9. 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/sec
D 13 P = 1.945 m 2 Pa/sec
D 23 P = 1.834 m 2 Pa/sec
Calculations:
Diffusivity of Co 2 in mixture
D 1m
y 2
D 12
y 2
where
y 3
y 3
D 13
y2
y2 y3
y3
y2 y3
D 1m P
Therefore
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/sec
Since P = 1.2 * 10 5 Pa,
D 1m
1.93
1.2 * 10 5
1.61 * 10 5 m 2 sec
D 2m
y 1
D 21
y 1
y 3
D 23
y1
y y
1
3
Where
(mole fraction on-2 free bans).
0.285
0.335
0.285 0.565
and
y 3
y3
y1 y3
0.565
0.665
0.285 0.565
and
D 21 P = D 12 P = 1.874 m 2.Pa/sec
Therefore
D 2m P
1
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
12
CD
AB
dy A
y
dz
13
(N
N B)
--- (1)
(i.e.)
SN
A z z
SN
A z
0.
-------------- (1)
dN A
0
dz
------------------------- (2)
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,
dN B
0,
dZ
14
and accordingly, the molar flux of B is also constant over the entire diffusion path
from z1 and z 2.
Considering only at plane z1, and since the gas B is insoluble is liquid A, we
realize that NB, the net flux of B, is zero throughout the diffusion path; accordingly
B is a stagnant gas.
From equation (1) (of section 3.5)
NA CD
AB
dy A
y
dz
A (N A
NA CD
AB
dy A
y
dz
AN A
CD
AB
N B)
Since N B = 0,
Rearranging,
NA
1 y
dy A
dz
------------ (3)
Z2
y A2
Z1
y A1
d z C DAB
NA
CD
Z
AB
15
dy A
1 y A
1 y A2
A1
ln
--------------(4)
Since
B, lm
B, lm
1 y
ln y
y
B2
B1
B1
A,
(1 y
B2
A2
ln
) (1 y
A2
A1 )
A1
A1
ln
y
A2
A2
A1
------- (5)
C
For an ideal gas
C D AB ( y A1 y A2 )
Z 2 z1
y B, lm
-------------------- (6)
n
p
V
R T , and
pA
P
D AB
RT ( z2 z1)
(p
A1
A2 )
B, lm
This is the equation of molar flux for steady state diffusion of one gas through a
second stagnant gas.
16
N A Nx A J A
---------------------------------- (1)
J A D AB
dCA
dz
----------------------------------------- (2)
N A Nx A D AB
dCA
dz
----------------------------- (3)
NA NA NB
CCA
D AB
dCA
dz
Rearranging the terms and integrating between the planes between 1 and 2,
17
dC A
dz
C A2
cD
C A1 N C C N N
AB
A
A
A
B
-------------- (4)
dC A
z
C
C A 2
A1 N C N C
CD AB
A
A A
C C A2
1
ln
NA
C C A1
Therefore,
NA
CD AB
z
ln
C C A2
C C A1
---------------------------- (5)
Replacing concentration in terms of pressures using Ideal gas law, equation (5)
becomes
NA
D AB P t
RTz
ln
P t P A2
P t P A1
--------------------------- (6)
where
D AB = molecular diffusivity of A in B
P T = total pressure of system
R = universal gas constant
T = temperature of system in absolute scale
z = distance between two planes across the direction of diffusion
P A1 = partial pressure of A at plane 1, and
P A2 = partial pressure of A at plane 2
Given:
D AB = 1.89 * 10 5 m2/sec
P t = 1 atm = 1.01325 * 10 5 N/m 2
T = 25C = 273 + 25 = 298 K
z = 2 mm = 0.002 m
P A1 = 0.2 * 1 = 0.2 atm (From Ideal gas law and additive pressure rule)
P A2 = 0.1 * 1 = 0.1 atm
Substituting these in equation (6)
18
NA
= 4.55 * 10
1 0.2
kmol/m .sec
CD
AB
(y
zy
A1
B, lm
A2 )
------------------ (1)
A,L d z
M A dt
-------------------------- (2)
A,L
M A is the molar density of A in the liquid phase
where
under Psuedo steady state conditions, equations (1) & (2) can be equated to give
19
CD
A,L d z
M A dt
AB
A1 y A2 )
(y
zy
B, lm
--------------- (3)
A,L y B, lm M
dt C D
t 0
to z = zt as:
Zt
A1 y
AB ( y
t0
z dz
A2 )
Zt 0
yielding
A,L y B, lm M
C D AB ( y A1 y A2 )
2
t
z
2
2
t0
-------- (4)
AB
A,L y B, lm
A1 y
M A C (y
A2 ) t
2
t
z
2
2
t0
D AB
A, L y Blm
MAC y
A1
A2
20
2
t
Z
2
2
t0
figure
y B, l m
y B 2 y B1
y B2
ln
y B1
where
y B2 = 1 y A2
A1
y B1 = 1 y A1
p A1
P
= 0.0754
y A2 = 0
y B, lm
Therefore
7.64
101.3
1 0.9246
0.9618
1
ln
0.9246
P
1.01325 * 10 5
C
RT
8314 * 273 39.4
= 0.039 k mol /m3
Therefore
D AB
0.08 2 0.02 2
850 * 0.9618
CD
AB
dy A
y
dz
21
(N
N B)
or
AB
dC A
y
dz
(N
N B)
------- (1)
dC A
dz
AB
----------------- (2)
For steady state diffusion Equation. (2) may be integrated, using the boundary
conditions:
at z = z1
CA = CA1
and z = z2
CA = CA2
Giving,
Z2
NA d z D
Z1
C A2
AB
dC
C A1
from which
C
For ideal gases,
2z1
AB
(C
A1
A2 )
------------------- (3)
nA
p
A
V
R T . Therefore Equation. (3) becomes
D AB
(P
R T ( z 2 z 1)
A1
A2 )
---------- (4)
This is the equation of molar flux for steady-state equimolar counter diffusion.
Concentration profile in these equimolar counter diffusion may be obtained from,
22
d
(N A ) 0
dz
(Since NA is constant over the diffusion path).
And from equation. (2)
AB
d CA
dz .
AB
d CA
d z
Therefore
d
dz
d
CA
dz
or
0
.
0.
C
C
A1
A1
A2
zz1
z1 z 2
-------------- (5)
Calculation:
For steady state equimolar counter diffusion, molar flux is given by
23
NA
Therefore;
NA
D AB
p A1 p A 2
RT z
--------------------------- (1)
6.75 * 10 5
55 15 kmol
3.633 * 10
6.75 * 10 5
55 p A
8.314 * 298 * 0.02
p A = 28.33 kPa
11. 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.sec, calculate the
molecular diffusivity for the system.
Solution:
For equimolar counter current diffusion:
NA
D AB
RTz
p A1 p A2
------------------------ (1)
where
N A = molar flux of A (1.6 * 10 5 kmol/m 2.sec):
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 equation (1)
24
D AB
1.6 * 10 5
15 5
N A C D AB
i)
Given
dy
dz
N A N B
NB = - NA
Therefore
dy
N A C D AB
dz
CA
N A D A B
D AB
dCA
dz
pA
R T where pA is the partial pressure of A; such
d p A RT
dz
Therefore
For isothermal system, T is constant
Therefore
NA
Z2
D AB d p A
RT
N A d z
(i.e.)
NA
Z1
D AB
RT z
dz
D AB
RT
p A1 p A2
P A2
d pA
P A1
---------------------------------- (1)
25
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
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
N A N B
given: N B = - 0.75 N A
Therefore
N A C D AB
C D AB
N A 0.25 y
dy
dz
dy
dz
0.25 y
A N A C D AB
N A d z C D AB
dy
N A 0.75 N A
A
NA
dy
dz
1 0.25 y
N A d z CD AB
Z1
y A2
dy
y A1 1 0.25 y A
26
4 CD AB
z
Given:
p
2 * 1.01325 * 10 5
0.0893 K mol m 3
RT
8314 * 273
p A 1 1. 5
y A1
0.75
P
2
p A2
0. 5
y A2
0.25
P
2
NA
4 * 0.0893 * 0.275 * 10 4
0. 2
kmol
7.028 * 10 6
m 2 sec
1 0.25 * 0.25
ln 1 0.25 * 0.75
iii)
N A CD AB
Given:
Therefore
Z2
dy
Z1
dz
dy
N A N B
NB = 0
N A CD AB
N A d z CD AB
1
y
ln 1 0.25 y A y A2
A1
0.25
1 0.25 y A 2
ln
1 0.25 y A 1
---------------------------------- (2)
N A z C D AB
NA
dx
a b x b ln a b x
y A2
dz
dy
y A1 1 y
27
NA
CD AB
Z
1 y
ln
1 y
A2
A1
ln 1 0.75
0. 2
kmol
1.349 * 10 5
m 2 . sec
Rate of diffusion = 1.349 8 10 5 * * (0.5 * 10 2) 2
= 1.059 Kmol / sec
= 3.814 mol/hr
3.5.4 Diffusion into an infinite standard medium :
Here we will discuss problems involving diffusion from a spherical particle
into an infinite body of stagnant gas. The purpose in doing this is to demonstrate
how to set up differential equations that describe the diffusion in these processes.
The solutions, obtained are only of academic interest because a large body of
gas in which there are no convection currents is unlikely to be found in practice.
However, the solutions developed here for these problems actually represent a
special case of the more common situation involving both molecular diffusion and
convective mass transfer.
a) Evaporation of a spherical Droplet:
As an example of such problems, we shall consider the evaporation of
spherical droplet such as a raindrop or sublimation of naphthalene ball. The
vapor formed at the surface of the droplet is assumed to diffuse by molecular
motions into the large body of stagnant gas that surrounds the droplet.
Consider a raindrop, as shown in figure. At any moment, when the radius
Figure
Evaporation of a raindrop
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
28
N A C D AB
Rearranging,
dy
dr
C D AB d y
NA
1 y A
NA
dr
__________ (1)
The flux N A is not constant, because of the spherical geometry; decreases
as the distance from the center of sphere increases. But the molar flow rate at r
and r + r are the same.
This could be written as,
AN A
AN A
r r
__________ (2)
where A = surface area of sphere at r or r + r.
Substituting for A = 4 r 2 in equation (2),
4 r
NA
r r
4 r
NA
or
lim
r 0
d
r
dr
ss
Integrating,
NA
r r
NA
NA 0
N A constant
__________ (3)
__________ (4)
N A r 02 N A 0
C D AB d y A
r 02 N A 0
1 y A
dr
r 02 N A 0
dr
r
C D AB
dy
1 y
Boundary condition :
At r = r 0
y A = y AS
And
At r =
y A = y A
Therefore equation (5) becomes,
29
A
A
__________ (5)
r 02
1
r
NA 0
C D AB ln 1 y A
r0
yy
A
AS
Simplifying,
NA 0
C D AB
r0
1 y A
ln
1 y
AS
__________ (6)
Time required for complete evaporation of the droplet may be evaluated from
making mass balance.
unit time
unit time
d 4
4 r 02 N A 0 r 03 L
dt 3
M A
d r0
4 r0 2 L
MA dt
__________ (7)
Substituting for N A0 from equation (6) in equation (7),
A
AS
MA
1 y
C D AB
ln
1 y
r0
d r0
dt
__________ (8)
Initial condition :
When t = 0 r 0 = r 1
Integrating equation (8) with these initial condition,
t
dt
1
C D AB
1
1 y
ln
MA
1
2 C D AB
r1
1 y
r0 d r0
A
AS
r 12
1 y
ln
1 y
AS
__________ (9)
Equation (9) gives the total time t required for complete evaporation of spherical
droplet of initial radius r 1.
b) 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)
30
occurs at the surface of the particle. During combustion of coal, the reaction
C + O2
CO 2
cccurs. 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 takes part in the
i.e. N
2
reaction, and its flux is zero.
.
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
__________ (1)
Where
D O 2 gas
Since
(1) becomes
NN2 0
N O 2 C D O 2 gas
N O 2 N CO 2
, equation
d yO2
dr
__________ (2)
d
r
dr
NO2 0
__________ (3)
Integrating,
N O 2 constant r 02 N O 2 s
__________ (4)
C D O 2 gas
Boundary condition :
At
And
NO2
d yO2
dr
NO2s
is the flux of O 2
r 02 N O 2 s
r r0
yO2 yO2s
yO
yO
2
2
At
With these boundary condition, equation (5) becomes
31
__________ (5)
r 02 N A 0
r0
dr
r
C D O 2 gas
which yields
C D O 2 gas
NO2s
r0
O2s
y O2
y O2s
yO2
d yO2
__________ (6)
For fast reaction of O 2 with coal, the mole fraction of O 2 at the surface of particle
yO
2
iz zero. (i.e.,)
.
And also at some distance away from the surface of the particle
y O 2 y O 2 0.21
% N 2)
With these conditions, equation (6) becomes,
NO2s
0.21 C D O 2 gas
r0
____________ (7)
Figure
Combustion of a particle of coal
5. A sphere of naphthalene having a radius of 2mm is suspended in a large
volume of shell air at 318 K and 1 atm. The surface pressure of the naphthalene
can be assumed to be at 318 K is 0.555 mm Hg. The D AB of naphthalene in air
at 318 K is 6.92 * 10 6 m 2/sec. Calculate the rate of evaporation of naphthalene
from the surface.
Calculation
Steady state mass balance over a element of radius r and r + r leads to
SNA
SNA
rr
---------------------------- (1)
dividing (1) by Sr, and taking the limit as r approaches zero, gives:
d r 2N A
dr
32
We can assume that there is a film of naphthalene vapor / air film around
naphthalene through which molecular diffusion occurs.
Diffusion of naphthalene vapor across this film could be written as,
N A CD AB
dy
dr
N A N B
N A CD AB
N A CD AB
N A CD AB
dy
dr
d
dr
1 y
d ln 1 y
WA
WA
= constant.
CD AB d ln 1 y
dr
dr
r
dr
W A = Rate of evaporation = 4 r 2 N A
4 r
NA
4 D AB C d ln 1 y
Boundary condition:
y
At r = R
dr
1
r
WA
WA
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
4 D AB C
d ln 1 y A
7.3 *10 4
4 D AB C ln 1 y
0 7.3 *10
W A 0 4 D AB C 0 7.3 * 10 4
R
33
W A = 4 R D AB C * 7.3 * 10 4
P
1.01325 * 10 5
C
av .
density,
a) For steady state diffusion of A through non diffusivity B:
N A = constant , N B = 0
NA
D AB
z x BM
av
x A1 x A2
X B 2 X B1
X BM
X B2
ln
X B 1
NA
D AB
Z
C A1 C A2
D AB
Z M
av
x A1 x A 2
NA
D AB
z
x A1 x A2
x B, lm
avg
x A1
0.1 74
0.026
0.1 74 0.9 18
0.04 74
0.04 74 0.96 18
x A2
0.010
1
19.47 kg Kmol
0.1 74 0.9 18
1
18.56 kg Kmol
0.04 74 0.96 18
M1
M2
1 M 1
2 M 2
avg
= 0.0517 gmol / cm 3
= 51.7 kmol/m 3
x B,lm
x B 2 x B1
ln x B 2 x B1
1 0.01
1 x A2 1 x A1
1 x A2
ln
1 x A1
1 0.026
1 0.01
ln
1 0.026
0.016
0.982
0.0163
x B,lm
(i.e.)
35
NA
Therefore
x A1 x A2
D AB
2 M
avg
x B, lm
5.9 * 10 6 * 10 4 * 51.7
0.1 * 10 2
kmol
4.97 * 10 7
m 2 sec
gmol
1.789
m 2 .hr .
g
1.789 * 74
m 2 . hr .
g
132.4
m 2 . hr .
0.026 0.010
0.982
N A D AB
dCA
dz
CA
C
N A N B
____________ (1)
If concentration of A in the film, C A is assumed small, equation (1) becomes
N A D AB
dCA
dz
____________ (2)
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
NA rA 0
dz
____________ (3)
where rA is the rate of disappearance of A. For a first order reaction,
36
A B
rA kC A
____________ (4)
with the substitution from equation (4) and (2) in equation (3),
dCA
d
D AB
kCA 0
d z
d z
For constant Diffusivity,
D AB
CA
kCA 0
dz2
____________ (5)
which is a second order ordinary differential equation. The general solution to this
equation is
C A C 1 cos h
D AB
z C 2 sin h
D AB
_______ (6)
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
tan h
D AB
C A 0 sin h k
z
D AB
k
z
D AB
tan h k
z
D AB
C A C A 0 cos h
_______ (7)
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 (7), and evaluating the derivative
dCA
dz
at z 0
dCA
dz
C A0
D AB
sin h
D AB
C A0
D AB
____________ (8)
37
tan h
cos h
D AB
D AB
NA
D AB C A 0
Z 0
D AB
k
tan h
D AB
____________ (9)
For absorption with no chemical reaction, the flux of A is obtained from equation
(2) as
D AB C A 0
____________ (10)
which is constant throughout the film of liquid. On comparison of equation (9) and
D AB
tan h
D AB
shows
dCA
N A D AB
dz
constant
NA
D AB C A1 C A2
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. First, the tortuous nature of
the path increases the distance, which a molecule must travel to advance a given
38
distance in the solid. Second, the 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.
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 is 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.
3.6 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:
i)
the process which is in an unsteady state only during its initial
startup, and
ii)
the process which is in a batch operation throughout its operation.
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.
Although the differential equations for unsteady state diffusion are easy to
establish, most solutions to these equations have been limited to situations
involving simple geometries and boundary conditions, and a constant diffusion
coefficient.
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
__________ (1)
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.
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
39
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.
40