Dept of Chemical and Biomolecular Engineering

CN2125 Heat and Mass Transfer

Dr. Praveen Linga, E5-02-23, 6601-1487
(Radiation, Mass Transfer)
Tutorial/HW Week #9
WWWR Chapters 26-27
ID Chapter 14
Tutorial #9
WWWR #26.17,
26.27, 27.6, 27.22 &
ID #14.33
To be discussed
during the week of
Mar 19 - 23, 2012.
By either volunteer or
class list.
Homework #9
(self practice)
WWWR # 26.22,
27.16 & ID #14.39
Molecular Diffusion
General differential equation


One-dimensional mass transfer without
reaction
0 =
c
c
+ V
A
A
A
R
t
c
N
) (
, , , z B z A A
A
AB z A
N N y
dz
dy
cD N + + =
Unimolecular Diffusion
Diffusivity of gas can be measured in an
Arnold diffusion cell




Assuming
Steady state, no reaction, and diffusion in z-
direction only
We get


And since B is a stagnant gas,

0
,
=
dz
dN
z A
0
,
=
dz
dN
z B
Thus, for constant molar flux of A, when
N
B,z
= 0,


with boundary conditions:
at z = z
1
, y
A
= y
A1
at z = z
2
, y
A
= y
A2

Integrating and solving for N
A,z


) 1 (
) 1 (
ln
) (
1
2
1 2
,
A
A
AB
z A
y
y
z z
cD
N

=
dz
dy
y
cD
N
A
A
AB
z A

=
1
,
since the log-mean average of B is


we get



This is a steady-state diffusion of one gas
through a second stagnant gas;
lm B
A A
AB
p
p p
z z RT
P D
, 1 2
) (
) (
2 1

=
lm B
A A
AB
z A
y
y y
z z
cD
N
, 1 2
,
) (
2 1

=
| | ) 1 /( ) 1 ( ln ) / ln(
1 2
2 1
1 2
1 2
,
A A
A A
B B
B B
lm B
y y
y y
y y
y y
y


=

=
For film theory, we assume laminar film of
constant thickness o,
then, z
2
z
1
= o
and

But we know

So, the film coefficient is then



) (
2 1
, A A
c
z A
p p
RT
k
N =
o
lm B
AB
c
p
P D
k
,
=
) (
2 1
,
, A A
lm B
AB
z A
p p
RTp
P D
N =
o
To determine concentration profile,



if isothermal and isobaric,


integrated twice, we get


0
1
,
=
|
|
.
|

\
|

=
dz
dy
y
cD
dz
d
N
dz
d
A
A
AB
z A
0
1
1
=
|
|
.
|

\
|
dz
dy
y dz
d
A
A
2 1
) 1 ln( c z c y
A
+ =
with boundary conditions:
at z = z
1
, y
A
= y
A1
at z = z
2
, y
A
= y
A2

So, the concentration profile is:


) /( ) (
1 2 1
1
2
1
1
1
1
1
z z z z
A
A
A
A
y
y
y
y

|
|
.
|

\
|

=
|
|
.
|

\
|

Example 1
Pseudo-Steady-State Diffusion
When there is a slow depletion of source or
sink for mass transfer
Consider the Arnold diffusion cell, when
liquid is evaporated, the surface moves,
at any instant, molar flux is


lm B
A A AB
z A
zy
y y cD
N
,
,
) (
2 1

=
Molar flux is also the amount of A leaving


Under pseudo-steady-state conditions,


which integrated from t=0 to t=t, z=z
t0
to
z=z
t
becomes
dt
dz
M
N
A
L A
z A
,
,

=
lm B
A A AB
A
L A
zy
y y cD
dt
dz
M
,
,
) (
2 1

|
|
.
|

\
|

=
2 ) (
/
2 2
, ,
0
2 1
t t
A A AB
A lm B L A
z z
y y cD
M y
t

Example 2
Equimolar Counterdiffusion
Flux of one gaseous component is equal to
but in the opposite direction of the second
gaseous component
Again, for steady-state, no reaction, in the
z-direction,

the molar flux is
0
,
=
z A
N
dz
d
( )
z B z A A
A
AB z A
N N y
dz
dc
D N
, , ,
+ + =
In equimolar counterdiffusion, N
A,z
= -N
B,z


Integrated at z = z
1
, c
A
= c
A1
and at z = z
2
, c
A
=
c
A2
to:



Or in terms of partial pressure,
dz
dc
D N
A
AB z A
=
,
) (
) (
2 1
1 2
, A A
AB
z A
c c
z z
D
N

=
) (
) (
2 1
1 2
, A A
AB
z A
p p
z z RT
D
N

=
The concentration profile is described by


Integrated twice to

With boundary conditions at z = z
1
, c
A
= c
A1
and
at z = z
2
, c
A
= c
A2
becomes a linear concentration profile:


0
2
2
,
= =
dz
c d
N
dz
d
A
z A
2 1
C z C c
A
+ =
2 1
1
2 1
1
z z
z z
c c
c c
A A
A A

Systems with Reaction

When there is diffusion of a species
together with its disappearance/appearance
through a chemical reaction
Homogeneous reaction occurs throughout a
phase uniformly
Heterogeneous reaction occurs at the
boundary or in a restricted region of a phase
Diffusion with heterogeneous first order
reaction with varying area:
With both diffusion and reaction, the process can
be diffusion controlled or reaction controlled.
Example: burning of coal particles
steady state, one-dimensional, heterogeneous

3C (s) + 2.5 O
2
(g) 2 CO
2
(g) + CO (g)
Along diffusion path, R
O2
= 0, then the general
mass transfer equation reduces from


to


For oxygen,


0
sin
1 ) sin (
sin
1 ) ( 1
2
=
c
c
+
c
c
+
c
c
+
c
c
A
A
A Ar A
R
N
r
N
r r
N r
r t
c
| u u
u
u
|
u
0
) (
2
=
dr
N r d
Ar
0
) (
2
2
=
dr
N r d
r O
From the stoichiometry of the reaction,


We simplify Ficks equation in terms of oxygen
only,


which reduces to
COr r O
N N 5 . 2
2
=
r CO r O
N N
2 2
25 . 1 =
) 0
25 . 1
1
5 . 2
1
(
2 2 2 2
2
2 2
+ + =
r O r O r O O
O
mix O r O
N N N y
dr
dy
cD N
dr
dy
y
cD
N
O
O
mix O
r O
2
2
2
2
2 . 0 1+
=

The boundary conditions are:
at r = R, y
O2
= 0 and at r = , y
O2
= 0.21,
Integrating the equation to:



The oxygen transferred across the cross-
sectional area is then:
( )
|
.
|

\
|
=
|
.
|

\
|
042 . 1
1
ln
2 . 0
1
2
2
2
mix O
r O
cD
R
N r
) 042 . 1 ln(
2 . 0
4 4
2
2 2
2
mix O
r O O
cD
R N r W

= = t t
Using a pseudo-steady-state approach to
calculate carbon mass-transfer
output rate of carbon:


accumulation rate of carbon:


input rate of carbon = 0
Thus, the carbon balance is
) 042 . 1 ln(
2 . 0
4
5 . 2
3
5 . 2
3
2
3
2
2 2
mix O
O CO C
cD
R W W W

= = = t
2
4
C C
C C
dV dR
R
M dt M dt

t =
dt
dR
R
M
cD
R
C
C
mix O
2
4 ) 042 . 1 ln(
2 . 0
4
5 . 2
3
0
2
t

t =

Rearranging and integrating from
t = 0 to t = u, R = R
i
to R = R
f
, we get






For heterogeneous reactions, the reaction rate is


( )
) 042 . 1 ln( 12
2
2 2
mix O
f i
C
C
cD
R R
M

u
As s
R r A
c k N =
=
If the reaction is only
C (s) + O
2
(g) CO
2
(g)
and if the reaction is not instantaneous, then


for a first-order reaction, at the surface,


then,
) ( 4
2 2 2 2
s O O mix O O
y y RcD W =

t
c k
N
y
s
R O
s O
2
2
=

=
|
|
.
|

\
|
+
2 2
2
2
1
2
O mix O
s
mix O
r O
y RcD
R k
D
N r
Combining diffusion with reaction process, we
get
R k
D
y RcD
W
s
mix O
O mix O
O

+
=
2
2 2
2
1
4t
Example 3
Diffusion with homogeneous first-order
reaction:
Example: a layer of absorbing liquid, with
surface film of composition A and thickness o,
assume concentration of A is small in the film,


and the reaction of A is


dz
dc
D N
A
AB z A
=
,
A A
c k R
1
=
Assuming one-direction, steady-state, the mass
transfer equation reduces from


to



with the general solution

0
,
=
A z A
R N
dz
d
0
1
2
2
1
= + = +
|
.
|

\
|

A
A
AB A
A
AB
c k
dz
c d
D c k
dz
dc
D
dz
d
z D k c z D k c c
AB AB A
/ sinh / cosh
1 2 1 1
+ =
With the boundary conditions:
at z = 0, c
A
= c
A0
and at z = o, c
A
= 0,



At the liquid surface, flux is calculated by
differentiating the above and evaluating at z=0,
o
AB
AB A
AB A A
D k
z D k c
z D k c c
/ tanh
/ sinh
/ cosh
1
1
1
0
0
=
o
AB
AB A
z
A
D k
D k c
dz
dc
/ tanh
/
1
1
0
0
=
=
Thus,



Comparing to absorption without reaction, the
second term is called the Hatta number.
As reaction rate increases, the bottom term
approaches 1.0, thus

(
(

=
=
o
o
o
AB
AB
A AB
z z A
D k
D k
c D
N
/ tanh
/
1
1
0 ,
0
) 0 (
0
1
0 ,
=
=
A AB
z z A
c k D N
Comparing with

we see that k
c
is proportional to D
AB
to
power.

This is the Penetration Theory model, where
a molecule will disappear by reaction after
absorption of a short distance.
) (
2 1
, A A c z A
c c k N =
2 / 1
AB c
D k
Example 4
2- and 3-Dimensional Systems
Most real systems are two- and three-
dimensional
Analytical solution to general differential
equation with the boundary conditions
Requires partial differential equations and
complex variable theories.
Unsteady-State Diffusion
Transient diffusion, when concentration at a
given point changes with time


Partial differential equations, complex
processes and solutions
Solutions for simple geometries and
boundary conditions
0 =
c
c
+ V
A
A
A
R
t
c
N
Ficks second law of diffusion


1-dimensional, no bulk contribution, no
reaction
Solution has 2 standard forms, by Laplace
transforms or by separation of variables
2
2
z
c
D
t
c
A
AB
A
c
c
=
c
c
Transient diffusion in semi-infinite medium
uniform initial concentration C
Ao
constant surface concentration C
As
Initial condition, t = 0, C
A
(z,0) = C
Ao
for all z
First boundary condition:
at z = 0, c
A
(0,t) = C
As
for t > 0
Second boundary condition:
at z = , c
A
(,t) = C
Ao
for all t
Using Laplace transform, making the boundary
conditions homogeneous
Ao A
c c = u
Thus, the P.D.E. becomes:

with
u(z,0) = 0
u(0,t) = c
As
c
Ao
u(,t) = 0
Laplace transformation yields


which becomes an O.D.E.
2
2
z
D
t
AB
c
c
=
c
c u u
2
2
0
dz
d
D
AB
u
u =
0
2
2
= u
u
AB
D
s
dz
d
Transformed boundary conditions:


General analytical solution:

With the boundary conditions, reduces to


The inverse Laplace transform is then
s
c c
z
Ao As

= = ) 0 ( u
0 ) ( = = z u
z D s z D s
AB AB
e B e A
/
1
/
1
+
+ = u
z D s
Ao As AB
e
s
c c
/
) (

= u
|
|
.
|

\
|
=
t D
z
c c
AB
Ao As
2
erfc ) ( u
As dimensionless concentration change,
With respect to initial concentration


With respect to surface concentration


The error function

is generally defined by
|
|
.
|

\
|
=
|
|
.
|

\
|
=

t D
z
t D
z
c c
c c
AB AB
Ao As
Ao A
2
erf 1
2
erfc
( ) | erf
2
erf =
|
|
.
|

\
|
=

t D
z
c c
c c
AB
Ao As
A As
t D
z
AB
2
= |
( )
t
|
|

d e erf
}

=
0
2
2
The error is approximated by
If | s 0.5

If | > 1

For the diffusive flux into semi-infinite
medium, differentiating with chain rule to the
error function

and finally,
( )
|
|
.
|

\
|
=
3
2
erf
3
|
|
t
|
( )
2
1
1 erf
|
|t
|

= e
( )
t D
c c
dz
dc
AB
A As
z
A
t
0
0

=
=
( )
Ao As
AB
z z A
c c
t
D
N =
=
t
0 ,
Transient diffusion in a finite medium, with
negligible surface resistance
Initial concentration c
Ao
subjected to sudden
change which brings the surface concentration
c
As
For example, diffusion of molecules through a
solid slab of uniform thickness
As diffusion is slow, the concentration profile
satisfy the P.D.E.
2
2
z
c
D
t
c
A
AB
A
c
c
=
c
c
Initial and boundary conditions of
c
A
= c
Ao
at t = 0 for 0 s z s L
c
A
= c
As
at z = 0 for t > 0
c
A
= c
As
at z = L for t > 0
Simplify by dimensionless concentration
change

Changing the P.D.E. to


Y = Y
o
at t = 0 for 0 s z s L
Y = 0 at z = 0 for t > 0
Y = 0 at z = L for t > 0

As Ao
As A
c c
c c
Y

=
2
2
z
Y
D
t
Y
AB
c
c
=
c
c
Assuming a product solution,
Y(z,t) = T(t) Z(z)
The partial derivatives will be


Substitute into P.D.E.


divide by DAB, T, Z to
t
T
Z
t
Y
c
c
=
c
c
2
2
2
2
z
Z
T
z
Y
c
c
=
c
c
2
2
z
Z
T D
t
T
Z
AB
c
c
=
c
c
2
2
1 1
z
Z
Z t
T
T D
AB
c
c
=
c
c
Separating the variables to equal -
2
, the
general solutions are



Thus, the product solution is:


For n = 1, 2, 3,

( )
t D
AB
e C t T
2
1

=
( ) ( ) ( ) z C z C z Z sin cos
3 2
+ =
| |
t D
AB
e z C z C Y
2
) sin( ) cos(
'
2
'
1

+ =
L
nt
=
The complete solution is:


where L = sheet thickness and
If the sheet has uniform initial concentration,


for n = 1, 3, 5
And the flux at z and t is
dz
L
z n
Y e
L
z n
L c c
c c
Y
n
L
o
X n
As Ao
As A
D
|
.
|

\
|
|
.
|

\
|
=

=

}

t t
t
sin sin
2
1
0
) 2 / (
2
2
1
x
t D
X
AB
D
=

|
.
|

\
|
=

1
) 2 / (
2
sin
1 4
n
X n
As Ao
As A
D
e
L
z n
n c c
c c
t
t
t
( )
D
X n
n
Ao As
AB
z A
e
L
z n
c c
L
D
N
2
) 2 / (
1
,
cos
4
t
t

|
.
|

\
|
=
Example 1
Example 2
Concentration-Time charts
Figure F.1 Unsteady-state transport in a large flat slab
Figure F.2 Unsteady-state transport in a long cylinder
Example 3