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Prof. R.

Shanthini
05 March 2013
1
CP302 Separation Process Principles
Mass Transfer - Set 3
Prof. R. Shanthini
05 March 2013
2
One-dimensional Unsteady-state Diffusion
Ficks First Law of Diffusion is written as follows when C
A
is only a
function of z:
(1)
J
A
= - D
AB
dC
A
dz
J
A
= - D
AB
C
A
z
(39)
Ficks First Law is written as follows when C
A
is a function of z as
well as of some other variables such as time:
Observe the use of ordinary and
partial derivatives as appropriate.
Prof. R. Shanthini
05 March 2013
3
J
A, in
J
A, out
C
A
z+z

J
A, in
= - D
AB
C
A
z
at z
J
A, out
= - D
AB
C
A
z
at z+z
z

Mass flow of species A into the
control volume
= J
A, in
x A x M
A
where
Mass flow of species A out of the
control volume
= J
A, out
x A x M
A
where
A: cross-sectional area

M
A
: molecular weight of
species A
One-dimensional Unsteady-state Diffusion
Prof. R. Shanthini
05 March 2013
4
J
A, in
J
A, out
C
A
z+z

z

A: cross-sectional area

M
A
: molecular weight of
species A
=
C
A
t
Accumulation of species A in the
control volume
x (A x z) x M
A
Mass balance for species A in the
control volume gives,
J
A, in
=
J
A, out
A M
A
A M
A
+
C
A
t
(A z) M
A
One-dimensional Unsteady-state Diffusion
Prof. R. Shanthini
05 March 2013
5
Mass balance can be simplified to
- D
AB
C
A
z
at z
- D
AB
C
A
z
at z+z
=
C
A
t
+ z
C
A
t
=
D
AB
(C
A
/z)
z+z
(C
A
/z)
z
-
z
(40)
The above can be rearranged to give
One-dimensional Unsteady-state Diffusion
Prof. R. Shanthini
05 March 2013
6
In the limit as z goes to 0, equation (40) is reduced to
=

2
C
A
z
2
D
AB
(41)
C
A

t
which is known as the Ficks Second Law.
Ficks second law in the above form is
applicable strictly for constant D
AB
and for
diffusion in solids, and also in stagnant liquids
and gases when the medium is dilute in A.
One-dimensional Unsteady-state Diffusion
Prof. R. Shanthini
05 March 2013
7
=

2
C
A
z
2
D
AB (42)
Ficks second law, applies to one-dimensional unsteady-state
diffusion, is given below:
C
A

t
=


r

D
AB
(43)
Ficks second law for one-dimensional diffusion in radial
direction only for cylindrical coordinates:
C
A

t r

C
A
r

r
=


r

D
AB
(44)
Ficks second law for one-dimensional diffusion in radial
direction only for spherical coordinates:
C
A

t r
2
C
A
r

r
2
One-dimensional Unsteady-state Diffusion
Prof. R. Shanthini
05 March 2013
8
=

2
C
A
x
2
D
AB
Ficks second law, applies to three-dimensional unsteady-state
diffusion, is given below:
C
A

t
+ +

2
C
A
z
2

2
C
A
y
2
=


r

D
AB
Ficks second law for three-dimensional diffusion in cylindrical
coordinates:
C
A

t
r

C
A
r

r
=


r

D
AB
Ficks second law for three-dimensional diffusion in spherical
coordinates:
C
A

t r
2
C
A
r

r
2
+


C
A
r
+


z

C
A
z

r
(45b)
(45a)



C
A

sin
+
1

sin

2

+
1

sin
2

C
A
(45c)
Three-dimensional Unsteady-state Diffusion
Prof. R. Shanthini
05 March 2013
9
Unsteady-state diffusion in semi-infinite medium
z = 0 z =

=

2
C
A
z
2
D
AB (42)
C
A

t
z 0
Initial condition:
C
A
= C
A0
at t 0 and z 0
Boundary condition:
C
A
= C
AS
at t 0 and z = 0
C
A
= C
A0
at t 0 and z


Prof. R. Shanthini
05 March 2013
10
Introducing dimensionless concentration change:
=

2
Y

z
2
D
AB
Y


t
Y =
C
A
C
A0
C
AS
C
A0
Use
and transform equation (42) to the following:
where
Y


t
=
C
A
/ t
C
AS
C
A0

2
Y

z
2
=

2
C
A
/ z
2
C
AS
C
A0
Prof. R. Shanthini
05 March 2013
11
Introducing dimensionless concentration change:
Initial condition:
C
A
= C
A0
becomes Y = 0 at t 0 and z 0
Boundary condition:
C
A
= C
AS
becomes Y = 1 at t 0 and z = 0
C
A
= C
A0
becomes Y = 0 at t 0 and z


Y =
C
A
C
A0
C
AS
C
A0
Use
and transform the initial and boundary conditions to the
following:
Prof. R. Shanthini
05 March 2013
12
Solving for Y as a function of z and t:
Initial condition: Y = 0 at t 0 and z 0
Boundary condition:
Y = 1 at t 0 and z = 0
Y = 0 at t 0 and z

=

2
Y

z
2
D
AB
Y


t
Since the PDE, its initial condition and boundary conditions
are all linear in the dependent variable Y, an exact solution
exists.
Prof. R. Shanthini
05 March 2013
13
Non-dimensional concentration change (Y) is given by:
Y =
C
A
C
A0
C
AS
C
A0
= erfc
z
2 D
AB
t
(46)
where the complimentary error function, erfc, is related to the
error function, erf, by
erfc(x) = 1 erf(x) = 1
2



0

x

exp(-
2
) d
(47)
Prof. R. Shanthini
05 March 2013
14
A little bit about error function:

- Error function table is provided (take a look).
- Table shows the error function values for x values up to 3.29.
- For x > 3.23, error function is unity up to five decimal places.
- For x > 4, the following approximation could be used:

erf(x) = 1
x
exp(-x
2
)
Prof. R. Shanthini
05 March 2013
15
Example 3.11 of Ref. 2: Determine how long it will take for
the dimensionless concentration change (Y) to reach 0.01 at
a depth 1 m in a semi-infinite medium. Assume D
AB
= 0.1
cm
2
/s.

Solution:
Starting from (46) and (47), we get
Y = 1 - erf
z
2 D
AB
t
Using Y = 0.01, z = 1 m (= 100 cm) and D
AB
= 0.1 cm
2
/s, we get

= 1 - 0.01 = 0.99 erf
100
2 0.1 x

t
100
2 0.1 x

t
= 1.8214
t = 2.09 h
Prof. R. Shanthini
05 March 2013
16
Get back to (46), and determine the equation for the mass
flux from it.
J
A
= - D
AB
C
A
z
at z
D
AB
/ t J
A
= exp(-z
2
/4D
AB
t) (C
AS
-C
A0
)

(48)
D
AB
/ t J
A
= (C
AS
-C
A0
)

Flux across the interface at z = 0 is
at z = 0
(49)
Prof. R. Shanthini
05 March 2013
17
Exercise: Determine how the dimensionless concentration
change (Y) profile changes with time in a semi-infinite
medium. Assume D
AB
= 0.1 cm
2
/s. Work up to 1 m depth of
the medium.

Solution:
Starting from (46) and (47), we get
Y = 1 - erf
z
2 D
AB
t
Prof. R. Shanthini
05 March 2013
18
clear all
DAB = 0.1; %cm2/s
t = 0;
for i = 1:1:180 %in min
t(i) = i*60;
z = [0:1:100]; %cm
x = z/(2 * sqrt(DAB*t(i)));
Y(:,i) = 1 - erf(x);
end
plot(z,Y)
xlabel('z (cm)')
ylabel('Non-dimensional concentration, Y')
grid
pause
plot(t/3600,Y(100,:))
xlabel('t (h)')
ylabel('Y at z = 100 cm')
grid
Let us get the
complete profile
using MATLAB
which has a built-
in error function.
Prof. R. Shanthini
05 March 2013
19
t = 1 min to 3 h
Prof. R. Shanthini
05 March 2013
20
Prof. R. Shanthini
05 March 2013
21
Diffusion in semi-infinite medium:
In gas: D
AB
= 0.1 cm
2
/s
Time taken for the dimensionless concentration
change (Y) to reach 0.01 at a depth 1 m is
2.09 h.
In liquid: D
AB
= 10
-5
cm
2
/s
Time taken for the dimensionless concentration
change (Y) to reach 0.01 at a depth 1 m is
2.39 year.
In solid: D
AB
= 10
-9
cm
2
/s
Time taken for the dimensionless concentration
change (Y) to reach 0.01 at a depth 1 m is
239 centuries.