1-35

Chapter 1

We now define an effectiveness factor to compare the effect of diffusion with that of
reaction within the catalyst particle.

=
rate conversion ideal
rate n converstio actual
=
A,actual
A,ideal
W
W
(1.4-3)


For steady state, the actual conversion rate, W
A,actual
, within the particle can be determined
from either of the following expressions:

W
A,actual
= 4 R
2
(D
A
A
r R
dC
dr
=
) =
2
A
0
4
R
r kC dr

(1.4-4)

The actual conversion rate is determined using the first expression of Eq. (1.4-4)


C
A
= C
R
r
R
) sinh(
) sinh(
R
r

A
dC
dr
=
) sinh( R
R C
R

+ ) cosh( ) sinh(
1
2
r
r
r
r

A
r R
dC
dr
=
=
) sinh( R
R C
R

) sinh(
1
) cosh(
2
R
R
R
R

A
r R
dC
dr
=
=
R
C
R
[ ] ) 1 ) coth( ) ( R R

Let = R =
1/ 2
2
A
kR | |
|
\
D
= Thiele modulus for a first order reaction. Ignoring the minus sign,
the actual conversion of species A is then

W
A,actual
= 4 R
2
D
A
R
C
R
( coth - 1) = 4 R D
A
C
R
( coth - 1) (1.4-5)

The ideal conversion rate, W
A,actual
, is the maximum conversion rate that can be achieved
when the mass transfer rate is much larger than the reaction rate. In this condition, the
concentration of species A everywhere within the bead is the same as the concentration at the
surface (C
R
). Therefore the total conversion rate is simply the total volume
3
4
3
R
| |
|
\
time the
conversion rate per unit volume (kC
R
). The effectiveness factor is introduced since it is
1-36
more convenient to cast mathematical models in dimensionless format to indicate the
minimum number of dimensionless groups that affect the physics. This knowledge is useful
in guiding the design of experiments and in the correlation of data. The Thiele modulus is
essentially the ratio of reaction to diffusion rates.

The effectiveness factor is then.

=
A,actual
A,ideal
W
W
=
A
3
4 ( coth 1)
4
3
R
R
R C
R
kC

D


=
2
A
3( coth 1)
D
kR

=
2
3

( coth - 1) (1.4-6)

We should choose a value of R so that the effectiveness is close to one. This means that the
reaction rate is not limited by the diffusion of species A into the catalyst particle. The
following Matlab statements are used to plot equation (1.4-6).
______ Matlab program to plot =
2
3

( coth - 1)______
% Effectiveness as a function of Thiele modulus
%
phi1=0.1:.1:1;
phi2=2:10;
phi3=20:10:100;
phi=[phi1 phi2 phi3];
ena=3*(phi.*coth(phi)-1)./phi.^2;
loglog(phi,ena)
grid on
xlabel('Thiele Modulus');ylabel('Effectiveness Factor')

----------------------------------------------------------------------------

Figure 1.4-1 plots the effectiveness factor versus the Thiele modulus . We see that has
almost reaches its maximum value as soon as is less than unity. There is no need to reduce
R any further once = 1. The radius of the spherical catalyst particle can then be determined
from the reaction rate constant and the diffusivity of A.

= R =
1/ 2
2
A
kR | |
|
\
D
= 1 R
design
=
1/ 2
A
D
k
| |
|
\


1-37

Figure 1.4-1 The effectiveness factor for first order reaction in spherical catalyst particle.

This is the design R
design
we should use to minimize mass transfer effect. For any R > R
design
,
the conversion of urea will be limited by diffusion, and for R < R
design
, we will find a
conversion rate that is independent of R and independent of D
A
. For R < R
design
, 1,

Conversion rate =
3
4
3
R
| |
|
\
kC
R
=
3
4
3
R
| |
|
\
kC
R


Example 1.4-5 ------------------------------------------------------------------------------

A liquid is in contact with a well-mixed gas containing substance A to be absorbed. Near the
surface of the liquid there is a film of thickness across which A diffuses steadily while
being consumed by a first-order homogeneous chemical reaction with a rate constant k
1
. At
the gas-liquid interface, the liquid solution is in equilibrium with the gas and its
concentration is c
Ai
; at the other side of the film, its concentration is virtually zero. Assuming
dilute solutions, derive an expression for the ratio of the absorption flux with chemical
reaction to the corresponding flux without a chemical reaction.
1


Solution ----------------------------------------------------------------------------------------------

The molar flux of A is given by

1
Benitez, J. Principle and Modern Applications of Mass Transfer Operations, Wiley, 2009, p. 66
10
-1
10
0
10
1
10
2
10
-2
10
-1
10
0
Thiele Modulus
E
f
f
e
c
t
i
v
e
n
e
s
s

F
a
c
t
o
r
1-38

N
A,z
= cD
AB
A
dx
dz
+ x
A
(N
A,z
+ N
B,z
)

For dilute solution, x
A
, is much less than one so that c can be considered to be constant and
the bulk-motion contribution to the flux is negligible. Therefore

N
A,z
= cD
AB
A
dx
dz
= D
AB
A
dc
dz




Making a mole balance around the control volume Sz gives

SN
A,z
|
z
SN
A,z
|
z+z
= 0

Dividing the equation by Sz and letting z 0 yields


, A z
dN
dz
= 0 (E-1)

Substituting N
A,z
= D
AB
A
dc
dz
into equation (E-1) we obtain

D
AB
2
2
A
d c
dz
= 0 =>
2
2
A
d c
dz
= 0 (E-2)

Integrating Eq. (E-2) we obtain

c
A
= K
1
z + K
2
(E-3)

Applying the two boundary conditions: c
A
(z = 0) = c
Ai
and c
A
(z = ) = 0 we have

c
A
= c
Ai
1
z

| |

|
\
(E-4)

The absorption flux without chemical reaction is then

z

Well-mixed gas
Dilute liquid solution
N
A,z
N
A,z+ z
1-39
N
A,z=0
= N
A,z
= D
AB
A
dc
dz

=
Ai AB
c D

(E-5)

Making a mole balance around the control volume Sz with chemical reaction gives

SN
A,z
|
z
SN
A,z
|
z+z
+ Szr
A
= 0

Dividing the equation by Sz and letting z 0 yields


, A z
dN
dz
= r
A
= k
1
c
A
(E-6)

Substituting N
A,z
= D
AB
A
dc
dz
into equation (E-6) we obtain

D
AB
2
2
A
d c
dz
= k
1
c
A
=>
2
2
A
d c
dz
=
1
AB
k
D
c
A
(E-7)

The solution to the homogeneous equation (E-7) in terms of the hyperbolic functions is


c
A
= B
1
sinh
1
AB
k
z
D
| |
|
\
+ B
2
cosh
1
AB
k
z
D
| |
|
\
(E-8)

At z = 0, c
A
= c
Ai
= B
2


At z = , c
A
= 0 = B
1
sinh
1
AB
k
D

| |
|
|
\
+ c
Ai
cosh
1
AB
k
D

| |
|
|
\


Therefore

B
1
= c
Ai

1
1
cosh
sinh
AB
AB
k
D
k
D

| |
|
\
| |
|
\


Eq. (E-8) becomes

c
A
= c
Ai

1
1
cosh
sinh
AB
AB
k
D
k
D

| |
|
\
| |
|
\
sinh
1
AB
k
z
D
| |
|
\
+ c
Ai
cosh
1
AB
k
z
D
| |
|
\


1-40
c
A
= c
Ai

1 1 1 1
1
sinh cosh sinh cosh
sinh
AB AB AB AB
AB
k k k k
z z
D D D D
k
D

| | | | | | | |

| | | |
\ \ \ \
| |
|
\


Using the identity sinh(A B) = sinh(A)cosh(B) sinh(B)cosh(B) we have

c
A
= c
Ai

( )
1
1
sinh
sinh
AB
AB
k
z
D
k
D

| |

|
\
| |
|
\

(E-9)

The absorption flux with chemical reaction is then

(N
A,z=0
)
rxn
= D
AB
A
dc
dz
(z = 0)

(N
A,z=0
)
rxn
= c
Ai
D
AB
( )
1 1
1
cosh
sinh
AB AB
AB
k k
z
D D
k
D

| |

|
\
| |
|
\
(z = 0)

(N
A,z=0
)
rxn
= c
Ai
(k
1
D
AB
)
1/2
coth
2
1
AB
k
D

| |
|
|
\
(E-10)

Therefore, the ratio of absorption flux with chemical reaction to absorption flux without
reaction is given by


( )
A,z=0
rxn
A,z=0
N
N
= c
Ai
(k
1
D
AB
)
1/2
coth
2
1
AB
k
D

| |
|
|
\

Ai AB
c D

( )
A,z=0
rxn
A,z=0
N
N
=
2
1
AB
k
D

| |
|
|
\
coth
2
1
AB
k
D

| |
|
|
\


The Damkohler number, which is the ratio of reaction rate over diffusion rate, is defined as
Da =
2
1
AB
k
D

. Then

1-41

( )
A,z=0
rxn
A,z=0
N
N
= (Da)
1/2
coth (Da)
1/2
(E-10)

We now consider the two limits: (a) the reaction rate is slow compared to the diffusion rate
and (b) the reaction rate is very fast compared to the diffusion rate. When the reaction rate is
slow, Da is small and the series expansion of coth (Da)
1/2
can be truncated to include only
the first two terms, giving


( )
A,z=0
rxn
A,z=0
N
N
= (Da)
1/2
( )
( ) ( )
1/ 2 3/ 2
1/ 2
1
...
3 45
Da Da
Da
(
+ + (
(

(E-11)

When the reaction is very fast, Da is large and coth (Da)
1/2
1. Therefore


( )
A,z=0
rxn
A,z=0
N
N
= (Da)
1/2
(E-12)

Figure E1.4-5 shows the plot of the ratio of absorption flux with chemical reaction to
absorption flux without reaction as a function of the Damkohler number. The approximation
for slow reaction is valid when Da < 1 and the approximation for very fast reaction when Da
> 8.


Figure E1.4-5 Dependence of flux ratio on Da.

1-42
1.5 Diffusion in Porous Solids

In a binary system, if diffusion in porous solids occurs by ordinary molecular diffusion, the
molar flux can be written as:

N
A,z
= cD
AB,eff
A
dy
dz
+ y
A
(N
A,z
+ N
B,z
) (1.5-1)

In this equation, the effective diffusivity, D
AB,eff
, is related to the ordinary diffusivity, D
AB
,
the porosity, , and tortuosity, , by

D
AB,eff
=
AB
D

(1.5-1)

The tortuosity is defined as the ratio of the pore actual length to the length if the pore were
straight in the direction of diffusion. Eq. (1.5-1) is valid if the mean free path, , of the
diffusing species is much less than the pore diameter, d. The Knudsen number, Kn,is defined
as the ratio of the mean free path to the pore diameter:

Kn = /d (1.5-2)

Equation (1.5-1) is valid when Kn < 0.05 for all the diffusing species
2
. In gases, the mean
free path can be estimated from the following equation:

=
2
2
AB
T
P

(1.5-3)

In this equation is the Boltzmann constant and
AB
is the collision diameter of the diffusing
species.

Example 1.5-1
3
------------------------------------------------------------------------------

Estimate the effective diffusivity of hydrogen in ethane in a porous solid with an average
pore size of 4000
o
A, 40% porosity, and tortuosity of 2.5. The gas mixture is at a pressure of
10 atm and a temperature of 373 K. For this system, the ordinary diffusion coefficient is
given by D
AB
= 0.86/P in cm
2
/s with total pressure P in atm. The collision diameters for
hydrogen and ethane are 2.827 and 4.443
o
A
, respectively.

Solution ----------------------------------------------------------------------------------------------


AB
= 0.5(
A
+
B
) = 0.5(2.827 + 4.443) = 3.635
o
A

2
Treybal, R. E., Mass-Transfer Operations, 3
rd
ed., McGraw-Hill, New York, (1980)
3
Benitez, J. Principle and Modern Applications of Mass Transfer Operations, Wiley, 2009, p. 58