Chapter 6

Exercise 1:
part a)
For a first-order reaction (Equation 6.3.33),

CA
sinh( )

C AS sinh( )

(1)

where R
p
If

r 0.5 R p ,

= 0.5

Also, if CA = 0.25CAS, 0.25

Therefore, use and to find from equation (1).

0.25

sinh

(2)

1
sinh( )
2

Therefore, = 4.131.
Now that is known,
CA
sinh( 4.131 )

C AS
sinh( 4.131)

Now we can find the lim

0

(3)

CA
.
C AS

Use LHopitals Rule:

CA
cosh(4.131 )
lim
0.133
0 C
0
sinh( 4.131)
AS
lim

6.1

part b)
For a first order reaction in a spherical catalyst pellet (Equation 6.3.39),

3
1
1

tanh

(1)

Therefore, if = 0.7, equation (1) can be used to find the Thiele modulus for this new
pellet:

= 2.77
Since R p

k
e and we know the Thiele modulus at two different conditions, the
DTA

following ratio can be utilized to find the radius of the new pellet.

R p1

k
e
DTA

Rp2

k
e
DTA

(2)

The rate constant and the effective diffusivity do not change:

R p1
1

2
R p2

(3)

From part (a) = 4.131, and at = 0.7, =2.77

Rp2
R p1

0.67

Exercise 2:
For a reversible, isothermal, first-order reaction [Equation (6.3.65)],

CA
C AS
K 1

x
cosh

C
xp

K 1 cosh( )

where C = CA + CB.

6.2

(1)

Since we can assume that C AS 0.9(C A C B ) or CAS = 0.9C,

x
cosh
x
p

cosh( )

C AS

C AS

CA
C AS
0.9( K 1)
0.9( K 1)

(2)

or

CA
1
1

1
C AS
0.9( K 1)
0.9( K 1)

where x p

let x p

x
cosh
x
p

cosh( )

(3)

k1 1 K

e
DTA
K

(4)

k1
1
e
DTA

Notice that as K goes to infinity:

lim lim

1 K
lim
K
K

1
1 1
K

lim

CA

1
1

lim
1
K

C AS
0.9( K 1)
0.9( K 1)

x
x
p
cosh(1)

cosh

(5)

Therefore,

lim

CA

C AS

x
x
p
cosh(1)

cosh

The result of a plot of

x
CA
vs x for many values of K and is shown below. Notice
C AS
p

that the reaction actually produces A for K = 0.001 and = 100.

6.3

1.2

CA/CAS

0.8

0.6
K=0.1 Thiele Modulus=3.3166

0.4

K=1 Thiele Modulus=1.414

K=5 Thiele Modulus=1.095
Limit as K->infinity (Thiele Modulus->1)

0.2

K=.0001 Thiele Modulus=100

0
0

0.2

0.4

0.6

0.8

x/xp

Exercise 3:
Notice that the flux to the surface must equal the rate of reaction at steady state.
Flux Area k c (C AB C AS ) Area

(1)

Use a 1 cm2 basis for the external surface area

2 1L
-6
Flux Area 2 cms (0.1 0.098) mol
L (1 cm )( 1000cm 3 ) = 4x10 mol/s

Flux Area 4 x10 6

mol
s

observed rate

To calculate the intraphase effectiveness factor, one needs the maximum rate of reaction.
That is based on the concentration of A at the surface, CAS.
Thus,
2
2
mol
rmax kC AS
(1.8 molLs )(0.098 mol
L ) 0.0173 Ls

For a volume basis of 1 cm3,

6.4

5 mol
1L
rmax (1 cm 3 ) 0.0173 mol
(1 cm 3 )( 1000cm
3 ) 1.73 10
Ls
s

Therefore the intraphase effectiveness factor is the following:

4 10 6 mol
robs
s

0.23
5 mol
rmax 1.73 10 s
Exercise 4:
part a)
The maximum temperature difference across a film is given by Equation (6.2.32):
Tmax

k c H r C AB
ht

(1)

Therefore, the maximum temperature difference is

Tmax

kJ
mol
0.5 minm (150 molO
)(
2
)
m3
2

0.5 minkJK m2

300 K

Since Tmax occurs when CAS = 0,

mol O2
robs k c (C AB C AS ) k c C AB (0.5 minm )(2 mol
3 ) 1 2
m
m min

part b)
For first-order reaction on a nonporous pellet,
C AS

k c C AB

(1)

k kc

where in this case,

100

k 10 6 exp
R T
g s

(2)

6.5

After substituting equation (2) into equation (1)

C AS

m
(0.5 min
)(2 mol
)
m3

m
0.5 min
10 exp
3 kJ

(8.314x10 mol K )TS

6

kJ
100 mol

(3)

Equation (3) has two unknowns (CAS and TS ), therefore other equations are needed.
robs (H r ) ht (TB TS )

(4)

where the observed rate is

robs k c (C AB C AS )

(5)

After substituting equation (5) into equation (4) and inserting the known values,
kJ
m
(0.5 min
)(2 mol
C AS )(150 mol
) 0.5 minkJK m 2 (773 K TS )
m3

(6)

Therefore, after solving equation (6) and equation (3) simultaneously,

TS = 1061 K
CAS = 0.0805 mol m-3
The actual rate under these conditions is given by the following equation:
r k c (C AB C AS ) 0.960 mmol
2
min

Exercise 5:
part a)
For a first order reaction in a spherical catalyst pellet the Thiele modulus is (Equation
(6.3.29)) the following:
Rp

k
e
DTA

(1)

6.6

Therefore, in order to find the Thiele modulus, the effective diffusivity must be known.
The Bosanquet equation (Equation (6.3.2)) can be used to find DTA since the Knudsen and
molecular diffusion coefficients are known:
1
1
1

DTA
D AB D KA

DTA 8.37 10 3 cms

(2)
2

The effective diffusivity is then calculated with the following equation:

e
DTA

P DTA

Therefore, DTA

(3)

(0.5)(8.37 10 3 )
1.05 10 3
4

cm 2
s

After substituting the effective diffusivity into equation (1),

5.0s 1
2 10 m
13.8
2
2 2
(1.05 10 3 cms )( 1001 2mcm2 )
3

part b)
For a first-order reaction in a spherical catalyst pellet (Equation 6.3.39), the effectiveness
factor is

3
1
1

tanh

(4)

Since the Thiele modulus was found in part (a), the effectiveness factor is found from
equation (4).
0.202

part c)
At steady state, the rate of mass transfer = rate of reaction. Therefore,
k c (C AB C AS ) kC AS

(5)

6.7

After solving for CAS and substituting for known values,

C AS

(32s 1 )(0.01 mol

L )

0.0097 mol
L
1
1
k c k 32s (0.202)(5s )
k c C AB

part d)
The overall effectiveness factor, o, is the following:

observed rate kC AS (0.202)(0.0097 mol

L )

0.196
max rate
kC AB
0.01 mol
L

Exercise 6:
The flux through a boundary layer is the following (assuming that there is perfect mixing
in the bulk):
N A k c (C AB C AS ) k c C A

(1)

where A is SO2.
At steady state, the mass flux is equal to the observed rate of reaction. Therefore
C A

robs

(2)

kc

Since the observed rate is known for each mass velocity, only the mass transfer
coefficient needs to be determined in order to find CA.
The mass transfer coefficient is given by the following Colburn J factor equation:
k c 0.817 Re 1 / 2 u Sc 2 / 3

(3)

where Sc = 1.28 in this case.

The Reynolds number, Re, is a function of the mass velocity, G, in the following manner:
Re

u dp

Gd p

(4)

The diameter of the particle, dp, is given by the following equation:

6.8

d p2 dh

d 2
2

(5)

where d is the diameter of the cylindrical pellet, and h is the length of the cylindrical
pellet.
Therefore, the effective diameter of the particle is:
dp

dh

d2
(3.2) 2
(3.2)(3.2)
3.92 mm
2
2

The Reynolds number can now be determined as a function of G.

Re

1cm
G * (3.92 mm)( 10mm
)

1.339

g
hr cm

(0.2928 hr cm
g )G
2

Next, find the velocity, u, as a function of G.

u

(6)

where is the density of the gas. Since the reaction is carried out in excess air, is taken
to be the density of air at the reaction temperature (480oC):

Latm
G (0.08206 mol
K )(753 K )

(1 atm)(28.9

g
mol

2139 cmg G
3

Now the mass transfer coefficient can be determined from equation (3):
k c ( cm
hr )

0.817(0.2928 G ) 1 / 2 (2139 G )
2739 G 1 / 2
1.28 2 / 3

Finally CA can be determined from equation (2).

C A ( cmmol3 )

gcat
robs ( hrmol
)
0
.
8
(
)
gcat
cm 3
1

1 / 2 cm
hr

2739 G ( )18.75(cm )

The concentration gradient is then plotted below:

6.9

(7)

Concentration Gradient x107

(m ol/cm 3)

1.8
1.7
1.6
1.5
1.4
1.3
1.2
1.1
1
0

50

100

150
200
G (g/hr cm 2)

250

300

Next, to determine the temperature gradient, T, one must realize that the heat flux is
equal to the rate heat is produced by reaction.
Therefore,
ht (TB TS ) ht T robs ( H r )

(8)

where Hr = -30 kcal mol-1.

From equation (7), r, can be written in terms of the mass velocity (or the mass
transfer coefficient) and G.
Therefore, the temperature gradient can be determined as long as the heat transfer
coefficient, ht, is known.
A correlation of the heat transfer coefficient is needed.
The correlation that was used here is a function of the j factors. It was combined with
equation (8) to yield the following equation for the temperature gradient:
jD
j H

Pr

Sc

2/3

H r

c p

C A

y fa

(9)

where is the density of the fluid (in this case air), A is SO2, yfa is the following

6.10

y fa

(1 X A A i ) (1 X As A i )
1 i X A
A

(10)

ln

1 i X s
A
A

Tem perature Gradient (K)

here we assumed that the ratio of jD to jH was assumed to be 0.5. The surface temperature
was assumed to be 753 K. The assumption was a good one since the temperature
gradient was relatively small. The temperature gradient as a function of the mass
velocity, G, is the following:
15
14
13
12
11
10
0

50

100

150

200

250

300

G (g hr -1 cm -2)

At higher flow rates, G, there are less external diffusion limitations. The error in
neglecting external temperature gradient is calculated in the following way:
E
k at surface k S A exp
R T
g S

and

k at bulk k B A exp
RT
g B

while the ratio of the rate constants is

E 1
kS
1

exp

kB
R g TS TB

(11)

Since TB is 753 K, and using the greatest temperature gradient from the data:

6.11

kS
1.46
kB

Therefore, the percent error is

% error

kS kB
32%
kS

For first-order kinetics,

robs kC A

The error associated with ignoring external concentration gradients is calculated in the
following way:
r at surface rS k S C AS whereas,

r at bulk rB k B C AB

The ratio of the rates is the following (using the largest concentration gradient):
mol
7.83 10 7 cm
3
rS k s C s

(1.46)
1.19
mol
rB k B C B
9.58 10 7 cm
3

Therefore, the % error is

% error

rS rB
16 %
rS

Exercise 7:
part a)
For a first-order reaction in a spherical catalyst pellet, the Thiele modulus is the
following:
Rp

k
e
DTA

(1)

6.12

The ratio of Thiele moduli for two different particle sizes can be determined since the rate
constant and the effective diffusivity do not change:
1
R
P1
2 RP 2

(2)

In addition, the observed rate can be written in terms of the effectiveness factor:
robs kC AS

(3)

Again, the ratio of the rate of reaction at two different pellet sizes can be determined,
noting that the surface concentration and the intrinsic rate constant, k, do not change.
robs ,1
robs , 2

1
2

(4)

A comparison of two large spheres yields,

1 0.03 cm

0.3
2
0.1 cm

(5)

1
0.8

3.2
2 0.25

(6)

For strong diffusional limitations, the effectiveness factor is 1/. Notice that the ratio of
the two Thiele moduli in equation (5) is approximately 1/0.3. Therefore we can estimate
that the large particles are in the strong diffusion control regime.
Now for the smallest two pellets,
1 0.003 cm

0.3
2
0.01 cm

(7)

while
1 2.5

1.39
2 1.8

(8)

Therefore we can estimate that the small pellets are not in the strong diffusion control
regime.
From a plot of the observe rate vs. the radius of the particle on a log scale, we can
estimate the Thiele modulus.

6.13

Observed Rate (m ol hr -1 cm -3)

10

0.1
0.001

0.01
Rp (cm )

0.1

By noticing that at on a plot of effectiveness factor vs. Thiele modulus (like that in Figure
6.3.10) at =1, the effectiveness factor does not change much with Rp. At a particle
diameter of 0.02 cm, 1. Additionally, at very high diffusion control regimes (where a
plot of the effectiveness factor vs. the Thiele modulus is linear with negative slope)
0.1. Therefore, 0.1 for a rate of 0.25 mol hr-1 cm-3.
The effective diffusivity and the intrinsic rate constant can be estimated from equations
(1) and (3).
cm
k 46 scm
3
cat
3

DTAe 4.6 10 3 cms

part b)
For a cylinder, the characteristic length parameter is the following (equation 6.3.48):
Lp

Vp
Sp

Rp
Rp
xp

(1)

where xp is half of the length of the cylinder.

Therefore, in this case Lp = 0.1 cm.
The Thiele modulus defined in terms of the length parameter is

6.14

o L p

k
e
DTA

(2)

and the effectiveness factor is

tanh( o )
o

(3)

Therefore, o = 10 and = 0.1

The observed rate can then be calculated from equation (3).
robs = 0.00069 mol cm-3 s-1
Exercise 8:
Since the rate of reaction (and CAS) was calculated at a very low conversion, (3.9%), the
following equations for the Thiele modulus and the effectiveness factor can be used:

RP
3

k1 1 K

e
DTA
K

(1)

tanh o
o

(2)

where k1 is the rate constant for the forward reaction.

In order to find the rate constant, k1, notice that the observed rate is a function of k1:
robs k1C AS

(3)

There are three equations (equations (1)-(3)) and three unknowns (,o, and k1).
After simplification, equations (1) and (3) reduce to the following:
o 1.63 k 1

(4)

k1 0.67 s 1

(5)

6.15

Notice that in both equations (4) and (5), the units on k1 are s-1. After solving the three
equations simultaneously,

= 0.511
k1 = 1.312 s-1

Exercise 9:
part a)
In order to test for external diffusion effects use the Mears Criterion.
For no external diffusion influence,
robs R p
k c C AB

0.15

(1)

Notice that the Mears Criterion is a dimensionless quantity.

CAB can be calculated from the observed rate using the following equation:
robs k obs C AB

For example, if Rp = 0.63 mm,

C AB

8.64 10 6

kmol
kgcat s

m3
kgcat s

0.33 10

0.0262 kmol
m3

Therefore, for Rp = 0.63 mm,

kgcat
3
kmol
(8.64 10 6 kgcat
s )(0.63 10 m)(1000 m 3 )

(5.69 10 4 ms )(0.0262 kmol

)
m3
Therefore, external diffusion affects the measured rate.

6.16

0.365 0.15

Similarly for Rp = 0.17 mm,

CAB = 0.011

kmol
m3

and

robs R p
k c C AB

0.169 0.15

Therefore, external diffusion affects the measured rate here as well.

In order to test for internal diffusion effects, use the Weisz-Prater Criterion:
robs R p2
e
D AB
C AS

1.0 for no significant internal diffusion effects

The effective diffusivity can be calculated by

p
1.9 10 4

e
D AB
D AB

cm 2
s

0.5
5

1.9 10
5.0

cm 2
s

The concentration of A at the surface, CAS, can be calculated by noting that the observed
rate must be equal to the mass transfer rate:
k obs C AS k c (C A C AS ) S p

(2)

After solving equation (2) for CAS:

k
C AS C AB 1 obs S p
kc

(3)

For Rp = 0.63 mm, CAS = 22.9 mol m-3

For Rp = 0.17 mm, CAS = 10.4 mol m-3
Since the surface concentrations are known, the Weisz-Prater Criterion can be used to
determine if internal diffusion effects are important.
For Rp = 0.63 mm,

robs R p2
e
D AB
C AS

(8.64 10 6
(1.9 10 5

cm
s

kmol
kgcat s

)(0.63 10 3 m) 2

)( 1001 2mcm 2 )(0.0229 kmol

)
m3

6.17

m
0.0788 kgcat
3

However, the Weisz-Prater criterion is a dimensionless quantity. Use the density to make
the quantity dimensionless.

m
(0.0778 kgcat
)(1000 kgcat
) 78.8
m3
3

Therefore, there are significant internal diffusion effects.

Similarly for Rp = 0.17 mm,

C AS 0.0104 kmol
m3
robs R p2
e
D AB
C AS

17.11

Therefore, there are significant internal diffusion effects in this case.

part b)
Recall that the effectiveness factor can be related to the Thiele modulus through Equation
(6.3.39)

3
1
1

tanh

(4)

The Thiele modulus , is

Rp

k
e
DTA

(5)

where k is the intrinsic rate constant.

Additionally, the internal effectiveness factor is:

robs
kC AS

(6)

where is the density of the catalyst.

e
e
DTA
Note that D AB
since this is liquid phase.

6.18

Solving equations (4)-(6) simultaneously will yield the Thiele Modulus, the effectiveness
factor and the intrinsic rate constant, k, for each pellet size.
For Rp = 0.63 mm,

= 0.106 and = 27.2 and k = 3.56 s-1

Similarly for Rp = 0.17 mm,

= 0.379 and = 6.74 and k = 2.95 s-1

part c)
The overall effectiveness factor, o, is given by the following equation:

k C
observed rate
obs AB
max rate in bulk fluid
kC AB

(7)

For Rp = 0.63 mm,

3

0.33 10 kgcats (1000

k
o obs
k
3.56 s 1
m3

kgcat
m3

0.093

Similarly for Rp = 0.17 mm,

o 0.356

Exercise 10:
For zero order kinetics,

r k

(1)

The material balance for differential element of a slab catalyst particle at steady state is
0 rate of A in ( rate of A out) (rate of generation of A)

2
0 N A x R pore
(N A

x x

2
R pore
) (k 2R pore x )

6.19

(2)
(3)

where x is the length dimension down the catalyst pore,

2
R pore
is the area of diffusion and 2R pore is the surface area of reaction.

Therefore, the differential equation representing the slab catalyst particle is the following:

2R pore
dN A
2k
k

2
dx
R pore
R pore

(4)

However, Ficks law is

N A D

dC A
dx

(5)

where D is the diffusivity.

After substituting equation (5) into equation (4),
D

d 2C A
2k

2
R pore
dx

(6)

In order to non-dimensionalize equation (6),

CA
and x / L
C AS
the length of the pore.

let

where CAS is the concentration of A at the surface and L is

Therefore,
d 2
2k L 2

R pore DC AS
d 2

let

(7)

2k L 2
R pore DC AS

(8)

The boundary conditions must be determined prior to solving equation (7). The system is
split into two different regions within the pore, one where A is present (Region I) and one
where A is not present (Region II).
let ex be the point where A is not present (extinguished) in the pore.

6.20

For Region I,
d 2
2 and the boundary conditions are the following for 0 ex :
d 2
1 at 0
0 at ex
d
0 at ex
d

Solving the differential equation and using the boundary conditions result in the
following relationship;

2 ex2
2 2
2 ex
2
2

(9)

At = 1,
ex

Plotting vs. for = 0.1, 1, and 10:

1.2
1
0.8

0.1

0.6

0.4

10

0.2
0
0

0.2

0.4

0.6

0.8

1.2

As increases, A is depleted in a shorter distance in the pellet. Therefore, zero order

kinetics is a bad approximation because it assumes KCA>>1 which is not true as CA goes
to zero.

6.21

Exercise 11:
The effectiveness factor for a first-order reaction in a spherical catalyst particle is the
following (Equation 6.3.39):

3
1
1

tanh( )

(1)

The Thiele Modulus, , is given by the following (Equation 6.3.29):

Rp

k
e
DTA

(2)

Since the rate is given as

E
PB
R g T

( r ) PHo k1o K o exp

(3)

the first-order rate constant is

E

R g T

k PHo k1o K o exp

(4)

Substituting the known constants, the rate constant is

2.7 kcal
mol

3 kcal
(1.99 10 molK )(423K )

k (685 torr)(4.22 gcatmol

)(4.22 10 11 torr 1 ) exp
storr
k 3.015 10 6

mol
gcat s torr

A first-order rate constant must have units of inverse time. Therefore, the density of the
catalyst and the ideal gas law must be used.
The concentration of benzene at reaction conditions is

CB

PB
75 torr

2.84 10 6
Latm 760torr 1000cm 3
R g T (0.08206 molK )( 1atm )( 1L )(423K )

6.22

mol
cm 3

k (3.015 10 6

mol
gcat storr

gcat
1cm total pellet
1
1cm
)(1.88 cm
)(
)(
75
torr
)

299
s
3 )(
3
6
0.5cm void space 2.8410 mol
3

This assumes that 50% of the volume of the catalyst is void space.
Now the Thiele modulus and the effectiveness factor are determined from equations (2)
and (1) respectively.
22.8
0.126

Equation 12:
part a)
The observed rate of reaction is a function of the effectiveness factor.
robs r

(1)

where r is the rate in the absence of diffusion effects.

In order to find the observed rate of reaction, both the effectiveness factor and the rate in
the absence of diffusion effects must be determined.

r kC AS (0.93s 1 )(3.25 10 2

mol
L

) 3.02 10 2

mol
Lsec

The effectiveness factor can be determined by the following equation:

3
1
1

tanh( )

(2)

where the Thiele modulus is given by:

Lp

k
e
DTA

(3)

e
here Lp is 0.2 cm, k = 0.93 s-1, and DTA
= 0.015 cm2 s-1.

Therefore,

6.23

 1.57 and 0.867

Substituting the effectiveness factor into equation (1) gives

robs 2.62 10 2

mol
Lsec

part b)
The rate constant at a different temperature can be determined by the Arrhenius form of k:
E 1
1

R g T2 T1

k 2 k1 exp

(1)

Therefore, the rate constant is

1000cal
20 kcal
1
1
1
mol kcal
k 2 0.93s exp

22.8s
cal
1.98 molK 423 373
1

Therefore, the rate without diffusion effects at 423 K is

r kC AS ( 22.8s 1 )(3.25 10 2

mol
L

) 0.74 Lmol
sec

From equations (3) and (2), the effectiveness factor can be determined.
7.8
0.335

Therefore, the observed rate is

1
robs r (0.335)(0.74 mol
Ls ) 2.48 10

mol
Lsec

part c)
The observed activation energy can be determined from the following equation:
E 1
1

R g T2 T1

k 2 k1 exp

where k1 and k2 are the observed rate constants.

6.24

E = 14000 cal mol-1

part d)

150
7.8

4.97
100 1.57
Therefore, the diffusion limitation goes up a lot with the temperature increase.
Problem 13:
First find an average concentration of C6H12 (A) in the reactor. Assuming no volume
change upon reaction, an average value of a the mole fraction of A is the following:
0.155

X A (0.2) 1
0.815
2

since the conversion in the reactor is 15.5%.

Therefore, the average concentration of A is the following:
1atm
)
X A Ptot (0.1845)(1.480MPa )( 0.101MPa
5 mol
CA

4
.
65

10
3
cm3
Latm
1000cm
Rg T
(0.08206 mol
)(
705
K
)(
)
K
1L

The observed rate constant can be calculated in the following way:

k obs

5 mol
robs 2.98 10 gcats
cm 3

0.641 gcat
s
5 mol
CA
4.65 10 cm3

The effectiveness factor can be written in terms of rate constants:

k C
k
observed rate
obs AS obs
rate in absence of diffusion
kC AS
k

Since the effectiveness factor is known, the intrinsic rate constant is

k

k obs
0.641

1.53

0.42

The effective diffusion coefficient can be determined if the Thiele modulus is known.

6.25

e
TA

R p2 k

(1)

The Thiele modulus can be found from the effectiveness factor using the following
equation:

3
1
1

tanh( )

(2)

Therefore = 5.94
Substituting the Thiele modulus into equation (1)
gcat
cm
(0.32 / 2) 2 (cm 2 )(1.53 gcat
s )(1.332 cm 3 )(
3

e
DTA

5.94 2

1
)
0.59 0.00249 cm 2
s

Since the dominant mode of transport is Knudsen diffusion, equation (6.3.1) can be used
to determine the Knudsen diffusivity.
T
DKA (9.7 10 3 )( R pore )
MA

1/ 2

(3)

where DKA is in cm2 s-1.

If Vg is the volume of the cylindrical pore and Sg is the surface area of the pellet, then the
radius of the pore is
R pore

2V g
Sg

40

After substituting the radius of the pore into equation (3), the Knudsen diffusivity is
DKA = 1.12 x 10-2 cm2 s-1
Equation (6.3.20) can be used to determine the tortuosity:
e
DKA

(6.3.20)

D KA

e
e
DKA
Note that since the dominant mode of diffusion is Knudsen diffusion, DTA
.

6.26

 2.65

Exercise 14:
From equation (6.4.10), the mass Biot number is:
Bim

x p kc
e
DTA

(1)

1.2

0.0001

Bim

Effectiveness Factor

0.001
0.01
0.1

0.8

1
10

0.6

100

0.4
0.2
0
0

10

Thiele Modulus

For all values of the effectiveness factor the Biot number is significant. But for high
values of the Thiele modulus, the effectiveness factor is less dependent on the Biot
number.
Exercise 15:
Figure 1:
Since the cyclohexene concentration declines linearly over time, the reaction rate is zero
order with respect to the bulk phase concentration of cyclohexene (cyclohexene = A).
Therefore, neither the mass transfer of cyclohexene to the surface [ N i k i (C AB C AS ) ]
nor the rate at which it adsorbs on the catalyst surface is rate controlling. Most likely, the
catalyst surface is saturated with cyclohexene.

6.27

Figure 2:
At low loadings, the rate is proportional to catalyst, which is consistent with intrinsic
kinetics. However, at high catalyst loadings, the rate is independent of catalyst which
suggest that the observed rate is dictated solely by mass transfer of dihydrogen from the
gas to the liquid.
Figure 3:
At the lower stirring speed the rate is mass transfer limited at all temperatures. At the
higher stirring speed, the rate could be the intrinsic rate up to the break point where again
mass transfer limitations exist.

6.28