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Note1 333
Note1 333
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:
mass of A
molecular weight of A
Number of moles =
m
M
----------------------------- (2)
nA
=
V
M
A
A
pA V
RT
nA
p
= A
V
RT
C = C
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
mass-average velocity for a multicomponent mixture defined in terms of mass
concentration is,
i
i
i
i
* =
C i V
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.)
=1
=1
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 =
30.68
= 30.68 g mol
1
n
P
=
V
RT
n
= molar density = m
V
Density = m
PM
1.5 * 10 5 * 30.68
=
M =
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
=C
A A
---------------------- (1)
= C
) + C
--------------- (2)
By definition
= * =
C i
CA
C i
C i
= C
) +
= C
) + y
C i
N
N
= C
= C
= C
A
A
A
(
(
(
A
A
A
) + y
) + y
) + y
A (C A
A (N A
A
+C
+N B )
A
B)
----------- (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
A more general flux relation which is not restricted to isothermal, isobasic system
could be written as
dy A
dZ
J A = C DA B
----------------- (4)
= C DA B
dy A
+ y
dZ
--------------- (5)
N A = J
J A = N
or
+y
+y
A
A
N
AN
----------------------- (6)
Similarly,
= N
+y
-------------------- (7)
+J
= N
+N
(y
+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
dyB
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
y n is the mole fraction of component n in the gas mixture evaluated on a
component 1 free basis, that is
y 2 =
y2
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
1
+
y 3
D 13
y
where y 2 =
y 3 =
+y3
y3
+y3
0.15
= 0.21
0.15 + 0.565
0.565
= 0.79
0.15 + 0.565
10
Therefore D 1m P =
1
0.21
0.79
+
1.874 1.945
= 1.93 m 2.Pa/sec
Since P = 1.2 * 10 5 Pa,
1.93
D 1m =
1.2 * 10
= 1.61 * 10 5 m 2 sec
D 2m =
y 1
D 21
1
+
y 3
D 23
y1
Where y 1 =
y1 + y3
0.285
= 0.335
0.285 + 0.565
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
11
A =
CD
AB
dy A
+ y
dz
12
(N
+ N B ) --- (1)
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
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.
13
NA = CD
dy A
+ y
dz
AB
A (N A
+ N B)
Since N B = 0,
NA = CD
AB
CD
AB
dy A
+ y
dz
Rearranging,
NA =
1 y
dy A
dz
------------ (3)
Z2
y A2
Z1
y A1
d z = C DAB
NA =
CD
Z
AB
dy A
1 y A
1 y A2
--------------(4)
ln
1
y
A1
B, lm
B2
ln y
y
B2
B1
B1
Since y B = 1 y A ,
14
B, lm
(1 y
A2
) (1 y
ln y
A2
A1 )
y A1
A1
ln y
y
A2
A2
y A1
------- (5)
C D AB ( y A1 y A2 )
Z 2 z1
y B, lm
-------------------- (6)
n
p
, and
=
V
RT
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.
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:
Figure
12. Oxygen is diffusing in a mixture of oxygen-nitrogen at 1 std atm, 25C.
Concentration of oxygen at planes 2 mm apart are 10 and 20 volume %
respectively. Nitrogen is non-diffusing.
(a) Derive the appropriate expression to calculate the flux oxygen. Define
units of each term clearly.
(b) Calculate the flux of oxygen. Diffusivity of oxygen in nitrogen = 1.89 * 10
5
m 2/sec.
Solution:
15
N A = Nx A + J
A ---------------------------------- (1)
= D AB
dCA
dz
----------------------------------------- (2)
N A = Nx A D AB
dCA
----------------------------- (3)
dz
NA = NA +NB
) CCA
D AB
dCA
dz
Rearranging the terms and integrating between the planes between 1 and 2,
dC A
dz
C A2
=
cD
C A1 N C C N + N
AB
A
A
A
B
-------------- (4)
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
16
---------------------------- (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)
(
1.89 * 10 5 )(1.01325 * 10 5 ) 1 0.1
NA =
ln
= 4.55 * 10
1 0 .2
kmol/m .sec
17
at any given instant in that period, the molar flux in the gas phase may be
evaluated by
CD
AB
(y
zy
A1
A2 )
------------------ (1)
B, lm
where
A,L
A,L
A
dz
dt
-------------------------- (2)
under Psuedo steady state conditions, equations (1) & (2) can be equated to give
A,L
A
CD
dz
=
dt
AB
A1
(y
zy
A2 )
--------------- (3)
B, lm
dt =
t =0
A,L y B, lm M
CD
AB
(y
Zt
A1 y
A2 )
z dz
Zt 0
yielding
t =
A,L y B, lm M
CD
AB
( y A1 y A2 )
A
2
t
z
2
2
t0
-------- (4)
AB
A,L y B, lm
M A C ( y A1 y A2 ) t
2
t
z
2
2
t0
18
D AB =
A, L y Blm
MAC y
where y B, l m =
A1
A1
Z
2
2
t0
figure
y B2
ln
y B1
p A1
P
y B1 = 1 y A1
= 0.0754
y A2 = 0
Therefore y B, lm =
C =
2
t
y B 2 y B1
y B2 = 1 y A2
A2
7.64
101.3
y B1 = 1 0.0754 = 0.9246
y B = 1 y A2 = 1
1 0.9246
= 0.9618
1
ln
0.9246
P
1.01325 * 10 5
=
RT
8314 * (273 + 39.4 )
= 0.039 k mol /m3
Therefore
D AB
0.08 2 0.02 2
850 * 0.9618
whose molar latent heats of vaporization are essentially equal, stipulates that the
flux of one gaseous component is equal to but acting in the opposite direction
from the other gaseous component; that is, NA = - NB.
The molar flux NA, for a binary system at constant temperature and pressure is
described by
N
N
or
=CD
=D
AB
dy A
+ y A (N A + N B )
dz
dC A
+ y A (N A + N B )
dz
AB
------- (1)
=D
dC A
dz
AB
----------------- (2)
For steady state diffusion Equation. (2) may be integrated, using the boundary
conditions:
CA = CA1
at z = z1
and z = z2
CA = CA2
Giving,
Z2
NA d z = D
C A2
dC
AB
Z1
C A1
from which
2z1
AB
(C
A1
A2 )
------------------- (3)
nA
p
= A . Therefore Equation. (3) becomes
V
RT
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.
20
d
(N A ) = 0 (Since NA is constant over the diffusion path).
dz
And from equation. (2)
= D
d
dz
AB
d CA
.
dz
AB
d CA
= 0 .
d z
Therefore
or
CA
dz
= 0.
C
C
A
A1
A1
A2
zz1
z1 z 2
-------------- (5)
Calculation:
For steady state equimolar counter diffusion, molar flux is given by
NA =
D AB
RT z
(p A 1 p A 2 ) --------------------------- (1)
21
Therefore;
NA
6.75 * 10 5
(55 15 ) kmol
=
8.314 * 298 * 0.03
m 2 . sec
kmol
= 3.633 * 10 5
m 2 sec
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 20C. 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)
1.6 * 10 5 =
D AB
(15 5 )
i) N A = C D AB
dy
dz
+y
(N A + N B )
Given
NB = - NA
dy
Therefore N A = C D AB
dz
= D AB
dCA
dz
pA
where pA is the partial pressure of A; such
RT
that p A + p B = P)
Therefore N A = D A B
d (p A RT )
dz
(i.e.)
D AB d p A
RT
N A d z =
Z1
NA =
D AB
RT z
dz
D AB
RT
(p A1 p A2 )
P A2
d pA
P A1
---------------------------------- (1)
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
23
0.275 * 10 4
1.5 * 1.01325 * 10 5 0.5 * 1.01325 * 10 5
8314 * 273 * 0.2
k mol
= 6.138 * 10 6 2
m sec
NA =
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
+y
(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
+y
+ 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
y A2
Z1
y A1 1 0.25 y A
N A d z = CD AB
dy
[ (
dx
1
a + b x = b ln (a + b x )
1
N A z = C D AB
ln 1 0.25 y
0.25
24
)]
y A2
A y
A1
NA=
1 0.25 y A 2
---------------------------------- (2)
ln
1 0.25 y A 1
4 CD AB
z
Given:
p
2 * 1.01325 * 10 5
C=
=
= 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
Substituting these in equation (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
dy
dz
+ y
dy
(N A + N B )
NB = 0
Therefore N A = CD AB
dz
+ y
Z2
y A2
Z1
y A1 1 y A
N A d z = CD AB
dy
1 y A2
ln
Z
1 y A1
0.0893 * 0.275 * 10 4
=
0 .2
=
NA
CD AB
25
1 0.25
ln 1 0.75
kmol
= 1.349 * 10 5
m 2 . sec
N A = C D AB
dy
dr
+y
(N A + N B )
N A = C D AB
Rearranging,
NA =
dy
dr
C D AB d y
1 y A
dr
+y
NA
__________ (1)
AN A
= AN A
__________ (2)
r + r
4 r
NA
r + r
4 r
NA
= 0
or
NA
lim
r 0
ss
d
r
dr
r + r
NA
= 0
NA = 0
__________ (3)
N A = constant
__________ (4)
Integrating,
N A = r 02 N A 0
C D AB d y A
= r 02 N A 0
dr
1 y A
r 02 N A 0
dr
r
= C D AB
dy
1 y
__________ (5)
Boundary condition :
At r = r 0
y A = y AS
And
At r =
y A = y A
Therefore equation (5) becomes,
r 02
NA 0
] yy
1
= C D AB ln (1 y A )
r r0
A
AS
Simplifying,
NA 0 =
C D AB
r0
1 y A
ln
1 y A S
__________ (6)
Time required for complete evaporation of the droplet may be evaluated from
making mass balance.
4
r3 L
0
3
M A
d r0
__________ (7)
= 4 r0 2 L
MA dt
4 r 02 N A 0 =
d
dt
1 y A
L d r0
=
ln
1 y AS
MA dt
C D AB
r0
__________ (8)
Initial condition :
When t = 0 r 0 = r 1
Integrating equation (8) with these initial condition,
d t = M
A
t =
MA
1
C D AB
1
1 y
ln
1 y
0
A
AS
r 12
1
2 C D AB
1 y
ln
1 y
r0 d r0
r1
__________ (9)
AS
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)
occurs at the surface of the particle. During combustion of coal, the reaction
CO 2
C + O2
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
reaction, and its flux is zero. i.e. N N = 0 .
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 gas is the diffusivity of O 2 in the gas mixture.
2
28
Since N N
(1) becomes
N O 2 = C D O 2 gas
d yO2
__________ (2)
dr
d
r
dr
NO2 = 0
__________ (3)
Integrating,
Where r 0 is the radius of coal particle at any instant, and N O s is the flux of O 2
2
at the surface of the particle.
Substituting for N O from equation (2) in equation (4),
2
C D O 2 gas
Boundary condition :
At r = r 0
And
d yO2
dr
= r 02 N O 2 s
__________ (5)
yO2 = yO2s
At r =
yO2 = yO2
r 02
NA 0
r0
dr
r
= C D O 2 gas
which yields
NO2s =
C D O 2 gas
r0
(y
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
iz zero. (i.e.,) y O s = 0 .
2
yO2
And also at some distance away from the surface of the particle
= y O = 0.21 (because air is a mixture of 21 mole % O 2 and 79 mole
2
% N 2)
With these conditions, equation (6) becomes,
29
NO2s =
0.21 C D O 2 gas
____________ (7)
r0
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
= 0 ---------------------------- (1)
r+r
d r 2N A
dr
)=0
N A = CD AB
dy
dr
+ y
(N A + N B )
N A = CD AB
N A = CD AB
N A = CD AB
dy
dr
d
dr
[ (
+ y
NA
yA
1 y A
d ln 1 y
)]
dr
30
4 r
WA
WA
dr
r
( (
CD AB d ln 1 y
))
dr
2
= 4 D AB C d ln 1 y
Boundary condition:
At r = R
0.555
= 7.303 * 10 4
760
ln (1 y A) = - 7.3 * 10 4
yA = 0
ln (1-y A) = 0
At r =
Therefore W A
dr
r
= 4 D AB C
WA
WA
d [ln (1 y A ) ]
7.3 *10 4
[ (
)]
1
0
r = 4 D AB C ln 1 y A 7.3 *10 4
R
1
0
= 4 D AB C 0 + 7.3 * 10 4
+
W A = 4 R D AB C * 7.3 * 10 4
1.01325 * 10 5
P
=
C =
8314 * 318
Gas cons tan t * T
= 0.0383 kmol/m 3
Initial rate of evaporation:
Therefore W A = 4 * 3.142 * 2 * 10 3 * 6.92 * 10 6 * 0.0383 * 7.3 * 10 4
= 4.863 * 10 12 kmol/sec
= 1.751 * 10 5 mol/hr.
3.5.5 Diffusion in Liquids:
Equation derived for diffusion in gases equally applies to diffusion in
liquids with some modifications. Mole fraction in liquid phases is normally written
as x (in gases as y). The concentration term C is replaced by average molar
.
M av
density,
31
N A = constant , N B = 0
NA=
D AB
z x BM
x A1 x A2
M av
X BM =
X B 2 X B1
X
ln B 2
X B 1
D AB
NA=
(C A1 C A2 ) =
D AB
x A1 x A 2
Z M av
NA =
D AB
z
(x A1 x A2 )
x B, lm
=
M avg
x A1 =
x A2
(0.1 74 )
= 0.026
(0.1 74 + 0.9 18 )
(0.04 74 )
=
(0.04 74 + 0.96 18 )
= 0.010
32
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 M1 + 2 M 2
=
2
M avg
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)
1 x A2
ln
1 x A1
(1 0.01 ) (1 0.026 )
(i.e.) x B,lm =
1 0.01
ln
1 0.026
0.016
=
= 0.982
0.0163
D AB
x A1 x A2
Therefore N A =
2 M avg
x B, lm
ln x B 2 x B1
=
=
=
=
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)
N A = D AB
dCA
____________ (2)
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
NA rA = 0
dz
____________ (3)
A B
rA = kC A
____________ (4)
with the substitution from equation (4) and (2) in equation (3),
dCA
d
+ kCA = 0
D AB
d z
dz
For constant Diffusivity,
D AB
CA
dz
+ kCA = 0
____________ (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.
34
The constant C
C A0
tan h
is equal to C
A0
, and C
is equal to
D AB
C A = C A 0 cos h
C A 0 sin h k
z
D AB
tan h k
z
D AB
D AB
_______ (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
tan h
cos h
D AB
____________ (8)
Substituting z = 0 in equation (8) and from equation (2),
NA
Z=0
D AB C A 0
D AB
tan
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
35
D AB
N A = D AB
dCA
dz
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
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.
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
z
__________ (1)
37