Several

problems have been covered in various lectures. A few of these with problem statements
with solutions are below.

Lect. No.: 15 Problem : 15A Time : 12:26

The first-order reaction A B was carried out and the following experimental data were obtained
(Table 1). All other conditions for these
experiments were same. Assuming negligible Table 1: Experimental data
external mass transfer resistance, (a) estimate the Measured Rate (obs) Pellet Radius
Thiele modulus and effectiveness factor for each (mol/g cat s) x 105 (m)
pellet and (b) how small should the pellets be made Run 1 3.0 0.01
to eliminate nearly all internal diffusion resistance? Run 2 15.0 0.001
Solution: Part (a)

rA' ( obs ) R 2 c
= 12 = 3 (1 coth 1 1) [1]
De C As

Suppose 11 and 12 are the Thiele Moduli at Run 1 and Run 2 with rA1 and rA 2 being the
corresponding observed reaction rates, R1 and R2 being the corresponding radii. Using Eq. (1), we
obtain

rA' 2 R22 12 coth 12 1

= [2]
rA' 1 R12 11 coth 11 1
Taking the ratio of the Thiele module for runs 1 and 2, we obtain

rAs' c
R1
11 DeC As R1 R 0.01m
= = 11 = 1 12 = 12 = 1012 [3]
12 '
r c R2 R2 0.001m
R2 As
DeC As

Using Eqs. (2) & (3) and introducing the information in Table 1, we obtain

12 coth 12 1
0.05 = [4]
1012 coth (1012 ) 1

Solving which gives 12 = 1.65 and 11 = 1012 = 16.5 . The corresponding effectiveness factors
obtained using Eq. (1) are 2 = 0.856;1 = 0.182

Part (b)
Suppose that operating at an effectiveness factor of 0.95 is sufficient to eliminate most of internal
diffusion resistance.

Using Eq. (1), that is, 12 = 3 (1 coth 1 1) , 13 = 0.9 , where subscript 3 refers to the radius R3 at

which = 0.95 . Using Eq. (2), R3 = R1

13 0.9 4
= ( 0.01) = 5.5*10 m = 0.55mm .
11 16.5
 Lect. No.: 16 Problem : 16A Time : 05:40
For the reaction C + CO2 2CO conducted in a catalytic reactor containing particles of radius
R = 0.7cm with bulk concentration being C As = 1.22 *105 mol / cm3 , the observed reaction rate is
r (obs ) c = 4.67 *109 mol / cm3 sec . After the reaction was conducted, the particles were cut
open and the reacted carbon profiles were measured. These profiles suggested strong diffusional
effects to be present. Verify this observation.

kC A
The rate law, in concentration units is rA = where, CA is the concentration of CO2
1 + K 2CD + K 3C A
(species A) and CD is the concentration of CO at the surface. The constants
K 2 = 4.15 *109 cm3 / mol and K3 = 3.38 *105 cm3 / mol . k is the rate constant. Diffusivity of the
species in the catalyst is given by DeA = 0.1cm 2 / sec .

Solution
Weisz-Prater parameter (CWP) under the given conditions is
rA' ( obs ) c R 2 4.67 *109 *0.7 2
CWP = = 5
= 1.88*103 << 1 [1]
DeAC As 0.1*1.22*10
indicating no internal diffusion limitations present. However the experimental observations suggest
otherwise. Poor prediction by the Weisz-Prater method is due to the fact that CWP in Eq. (1) uses
Thiele modulus expression for a first order reaction when the actual reaction is not first-order.
Therefore, this problem warrants the use of Generalized Thiele Modulus.

Assuming equimolar counter diffusion i.e.; DeA = DeD and that concentration of CO at surface
CDs 0 , the rate expression can be rewritten as,

kCA
rA' = [2]
(1 + 2K2CAs ) + ( K3 2K2 ) CA
Assuming the pellet was infinitely long with C A,eq = 0 , the modified parameter

2
rA' ( obs ) R 2 c ( rAs' )
= = C As

2 DeA ( rA' )dC A

0
1
r ' ( obs ) R 2 c 1 + K3C As 1 + 2 K 2C As 1 + K 3C As
= A 1 ln [3]
2 DeA K 3 2 K 2 C As ( K 3 2 K 2 ) 1 + 2 K 2C As
= 2.5 > 1
So, as observed experimentally, there is a strong internal diffusion limitation.
 Lect. No.: 18 Problem : 18A Time : 00:00
Design a packed bed reactor in which the reaction A B + 2C is being conducted under internal
diffusional limiting conditions and the exit conversion is 0.81. The fluid is being pumped into the
reactor at a superficial velocity of U = 4m / sec . The reaction is being conducted at temperature
T = 260C = 533K and at inlet pressure of P = 4.94atm . Assume DeA = 2.68 108 m 2 / sec ,
k = 51m6 / m2 .mol.sec , b = 2.1106 g / m3 , S a = 410m 2 / g , d p = 0.38cm . Assume rate law
2
rA = k C Ab

Solution

P 4.94
The inlet concentration C Ab 0 = = = 0.113gmol / l
RT 0.082 533
Mole balance for the reactor is given by

d 2 CAb dC
DeA 2
U Ab k " Sa b CAb
2
=0 [1]
dz dz
where is the overall effectiveness factor. It should be noted that in general, for a second order
reaction explicit expression for is usually not available and will be a function of the local
concentration of species A and as a result will be a function of position as well. Assuming the flow
rate through the bed is very large and the axial diffusion can be neglected, that is,
d 2 C Ab dC Ab
DeA 2
<< U , Eq (1) can be simplified to
dz dz

dCAb S C2
k " a b Ab = 0 [2]
dz U
along with the condition at the entrance of the reactor C Ab = C Ab 0 @ z = 0. Analytical solution for
Eq. (2) is usually unavailable due to the dependence of the overall effectiveness factor whose
explicit dependence on the concentration is a priori unknown. However, the reaction under the
specified conditions is internal diffusion controlling. In this regime, the overall effectiveness factor
may be approximated to the effectiveness factor and assumed constant. Under this approximation,
Eq. (2) can integrated to obtain the length required to achieve the desired conversion as

U 1
L= " 1 [3]
b k Sa CAb 0 1 X
Using the expression for 2 for a second order reaction, the effectiveness factor
12 12 12
2 3 2 3 2 3
= = = 7
= 9.47 108
n + 1 n 2 + 1 2 2 + 1 2.59 10
Note that the Thiele Modulus will be a function of position. For the chosen parameters, as the
variation with respect to position is negligible, the Thiele Modulus is evaluated at the inlet
concentration and is assumed constant. << 1 implies strongly internal diffusion limited, therefore
approximating = 9.47 108
 U X 4 0.81
L= "
= 8 6
= 3.62 102 m
b k Sa C Ab 0 1 X 9.47 10 2.110 51 410 0.113 (1 0.81)

Lect. No.: 22 Problem : 22A Time : 13:25

Ref.: -
It is required to determine the value of kL and for a batch absorber using the reaction

A( g ) + 2 B(l ) C (l )
which is first order in A. kL and are expected to be about 10-4 m/s and 200 m2/m3 respectively. Da =
2.5x10-9 m2/s. A choice of liquid phase reactants is available with different rate constants. Determine
what value of k will suit the purpose.

Solution:
Given:
kL = 1 x 10-4 m/s; = 200 m2/m3; Da = 2.5x10-9 m2/s

To find k value at which given condition will satisfies

Thickness of the film:

DA 2.5*109
= 4
2.5*105 m
kL 1*10

. = 200 * 2.5 * 10-5 = 5 * 10-3

by assuming slow reaction regime,
2 k1 2.52 *1010 * k1
M = 0.25k1
DA 2.5*109

We know that, (
P = M / (. ) = 0.25k1 / 5*103 = 50k1 )

Chosen a value of k1 0.2sec 1 gives M = 0.05 and P=10, which satisfies the conditions such
as M << 1 and P >> 1 , also

In general, rate of mass transfer for slow reaction regime is

P
RA = k L aC A*
P + 1
10
= k L aC A* k L aC A*
11
Hence, the value of k1 0.2sec 1 satisfies the condition for slow reaction regime.

Lect. No.: 23 Problem : 23A Time : 06:20

Ref.: -
Part:1 Rate constant of an unknown reaction
An oxidation reaction A + B P , which is first order in oxygen(A) is carried out in a stirred cell
with a flat gas-liquid interface of 132 cm2 at atmospheric pressure with pure oxygen. Over a stirrer
speed range of 60-200 RPM, the rate of absorption was measured to be nearly constant at 1.23x10-5
mol/s, as measured by the difference in the flow rates of gas at inlet and outlet; it was also
independent of the volume of liquid in the vessel. The solubility of A in the liquid phase follows
Henrys law with H = 5.8x10-7 mol/cm3/atm. Find the rate constant of the reaction. (DAB = 2.1x10-5
cm2/s, concentration of B = 0.01 mol/cm3).

Solution:
Given:
VL = 132 cm2
RAVL = 1.23*105 mol / sec
CA* = H * pO2 = 5.8*107 mol / cm3
DA = 2.1*105 cm 2 / sec
CBb = 0.01mol / cm3

To find the rate constant of the reaction

We consider fast reaction regime, for an given information which suggest that, kL various with RPM
leads to RAVL independent of RPM, kL and VL

So, rate reaction expressed as,

RAVL = DA k1 * C A* * VL

1.23*107 = 2.1*105 * k1 *5.8*107 * 132

k1 = 1.229.13sec 1

Lect. No.: 23 Problem : 23B Time : 19:30

Ref.: -
Part:2 Interfacial area by the chemical method.
The same reaction is now conducted in an agitated, bubbling stirred tank, with air instead of oxygen.
From a measurement of the oxygen content in the gas leaving, a rate of absorption of 3.95x10-5 mol/s
was determined with a total dispersion volume of 1700 cm3. Determine the specific interfacial area
per unit volume of the dispersion. Mass transfer co-efficient in such equipment usually varies in the
range of 2-4x10-2 cm/s.

Solution:
Given:
Assume: pO2 = 0.21atm
CA* = H * pO2 = 5.8*107 *0.21
= 1.218*107 mol / cm3
Total dispersion volume = 1700 cm3
k L = 2 4 *102 cm / sec

To find the specific interfacial area per unit volume of the dispersion

Assumed k L = 4*102 cm / sec for an fast reaction regime ( M >3 )

DA k1 2.1*105 *1229.13
We know that, M = =
kL 4 *102
 M = 4.02 > 3

The rate of absorption in fast reaction regime is,

RAVL = DA k1 * C A* * VL

3.95*105 = 2.1*105 *1229.13 *1.218*107 * VL

Total interfacial area (VL) = 2018.56 cm2

2018.56
Interfacial area per unit volume of dispersion (VL) = = 1.19cm2 / cm3
1700

Lect. No.: 26 Problem : 26A Time : 24:10

Ref.: -
Maximum and actual enhancement factors
CO2 is being absorbed from a gas into a solution of NaOH at 20C, in a packed tower. At a certain
point in the tower, the partial pressure of CO2 is 1 bar, and the concentration of NaOH 0.5 kmol/m3.
Other data are as follows: kL = 10-4 m/s; interfacial area per unit volume of packed space is 100 m-1;
C A* = 0.04 kmol/m3; second order rate constant of the reaction k = 104 m3/kmol s, DA = 1.8 x 10-9 m2/s
and DB = 3.06x10-9m2/s. Find the maximum enhancement possible and the actual enhancement. Find
also the actual absorption rate, in units of kmol per sec per unit volume of packed space. The reaction
is:
CO2 + 2 NaOH Na2 CO3 + H 2 O

Solution:
Given:
CBb = 0.5kmol / m3 ; C A* = 0.04kmol / m3 ; k L = 104 m / sec
k1 = 104 m3 / kmol sec ; DA = 1.8 *109 m 2 / sec ; DB = 3.06 *109 m 2 / sec
DB DA = 1.7

(a) To find the maximum enhancement possible

DB CBb 1.7 * 0.5

We know that, q = = = 10.625
DACA* 2 * 0.04

Maximum enhancement factor,

DA
E (1 + q ) = 1.7 *11.625
DB

E 8.91

(b) To find actual enhancement

DA k1CBb 1.8*109 *104 * 0.5

We know that, M = =
kL 1*104
 M = 30 > 10.625 ( = q )

Actual enhancement factor,
E E E E
E= M tanh M
E 1 E 1

First approximation:
E E
For a larger value of M and E , tanh M 1 which lead to

E 1

E E 30
E M = E E
E 1 7.91

E = 8.30 (by trial and error)

Second approximation:
E E 8.91 8.30
tanh M = tanh 30 1
E 1 8.91 1



E E E E
E= M tanh M 8.30
E 1 E 1

(c) To find actual absorption rate, in units of kmol per sec per unit volume of packed space

The Rate of absorption is
RA = k L C A* E = 1*104 * 0.04 *8.3 = 3.32 *105 kmol / m 2 sec

RA a = 3.32*103 kmol / m3 sec

Lect. No.: 12 Problem : 12A Time : 38:35

Ref.: Scott Fogler, pg.: 858
A first-order heterogeneous irreversible reaction is taking place within a spherical catalyst pellet
which is plated with platinum throughout the pellet. The reactant concentration halfway between the
external surface and the centre of the pellet (i.e., r = R/2) is equal to one-tenth the concentration of
pellets external surface. The concentration at the external surface is 0.001 g mol/dm3, the diameter
(2R) is 2 x 10-3 cm, and the diffusion coefficient is 0.1cm2/s.
AB
(a) What is the concentration of reactant at a distance of 3 x 10-4 cm in from the external pellet
surface?

(b) To what diameter should the pellet be reduced if the effectiveness factor is to be 0.8?
Solution:

Given:

CA / CAS = 0.1; CAS = 0.001 g mol/dm3; dp = 2 x 10-3 cm; De = 0.1 cm2/s;

(a) To find the concentration of reactant at a distance of 3 x 10-4 cm in from the external pellet
surface

We know that,

CA 1 sinh 1
= = -----------> (1)
C AS sinh 1

1 sinh 1 0.5
0.1 = 1 = 6 (by trial & error method)
0.5 sinh 1

Dimensionless radius of the catalyst expressed in the form of

r R 3*104 1*103 3*104

= = = = 0.7
R R 1*103
Substituting value of and 1 in eq.(1), we get

CA 1 sinh 1 CA 1 sinh(6 * 0.7)

= = = =
CAS sinh 1 0.001 0.7 sinh 6

C A = 2.36 *104 mol / dm3

Lect. No.: 13 Problem : 12A (Cont.) Time : 00:00

Ref.: Scott Fogler, pg.: 858
(b) To what diameter should the pellet be reduced if the effectiveness factor is to be 0.8
The Thiele modulus is,

k1 c sa k
=R = R 1r
De De

k1r
6 = 1*103 k1r = 3600000sec1
0.1
Calculating Thiele modulus for an effectiveness factor 0.8 is

3
= 0.8 = [1 coth 1 1] 1 = 2
12
The corresponding Thiele modulus expression to calculate diameter of the catalyst particle is,

k1r 3600000
=2=R =R R = 3.4 *104 cm
De 0.1

d p = 6.8 *104 cm

 Lect. No.: 38 Problem : 38A Time : 28:40
Ref.: Scott Fogler, pg.: 971
Conversion using Dispersion and Tank-in-Series Models:

The first-order reaction

AB
is carried out in a 10 cm diameter tubular reactor 6.36 m in length. The specific reaction rate is 0.25
min-1. The results of a tracer test carried out on this reactor are shown in Table T38A-1.

Table T38A-1. Effluent tracer concentration as a function of time

time(min) 0 1 2 3 4 5 6 7 8 9 10 12 14
C (mg/L) 0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0

Calculate conversion using (a) the closed vessel dispersion model, (b) PFR, (C) the tank-in-series
model, and (d) a single CSTR.

Solution:
Given:
d = 10 cm, k = 0.25 min-1

time 0 1 2 3 4 5 6 7 8 9 10 12 14
C(t) 0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
(a) To calculate conversion using the closed vessel dispersion model
Table T38A-2. Calculation to determine tm and 2

time 0 1 2 3 4 5 6 7 8 9 10 12 14
C(t) 0 1 5 8 10 8 6 4 3 2.2 1.5 0.6 0
E(t) 0 0.02 0.1 0.16 0.2 0.16 0.12 0.08 0.06 0.044 0.03 0.012 0
tE(t) 0 0.02 0.2 0.48 0.8 0.80 0.72 0.56 0.48 0.40 0.3 0.14 0
t2E(t) 0 0.02 0.4 1.44 3.2 4.0 4.32 3.92 3.84 3.60 3.0 1.68 0

To find E(t) and then tm, we first find the area under the C curve, which is

C (t ) dt = 50 g min
0

Then = tm = tE ( t ) dt = 5.15 min
0

Using Simpson rule, we find,

2 1
t E (t ) dt = 3 ( 0.0 + 3.0 ) + 2 ( 0.4 + 3.2 + 4.32 + 3.84 ) + 4 (0.02 + 1.44 + 4.0 + 3.92 + 3.6 )
0

2
+ ( 3.0 + 0.0 ) + 4 (1.68 )
3

= 32.63min 2

To obtain the variance, we substituting these values


2
= ( t ) E ( t ) dt = t 2 E ( t ) dt 2
2

0 0

2
2 = 32.63 (5.15) = 6.10min 2

Dispersion in a closed vessel is represented by

2 2
2
= 2 ( Pe 1 + exp ( Pe ) )
Pe

6.1 2
= 2
= 0.23 =
Pe 2
( Pe 1 + exp ( Pe ))
(5.15)

Solving for Pe by trial and error, we obtained Pe = 7.5

(
Next we need to calculate Da, Da = k = (5.15min ) 0.25min 1 = 1.29 )
Using the equation for q and X gives

4 Da 4 (1.29 )
q = 1+ = 1+ = 1.30
Pe 7.5

Then, substitute q and Pe value in conversion expressed for a dispersion model

4q exp ( Pe 2 )
X = 1 2 2

(1 + q ) exp ( qPe 2 ) (1 q ) exp ( qPe 2 )

4 (1.30 ) exp ( 7.5 2 )

X = 1 2 2

(1 + 1.30 ) exp ((1.30 * 7.2 ) 2 ) (1 1.30 ) exp ( (1.30 * 7.2 ) 2 )

X = 0.68

When dispersion effects are present in this tubular reactor, 68% conversion is achieved.

(b) Conversion for Plug flow reactor:

If the reactor were operating ideally as a plug-flow reactor, the conversion would be

X = 1 exp ( k ) = 1 exp ( Da ) = 1 exp ( 1.29 )

X = 0.725

72.5% conversion would be achieved in an ideal plug-flow reactor.

(c) Conversion for tank-in-series:

First calculate the number of tanks in series,

 2
2 ( 5.15)
n= 2 = = 4.35
6.1

To calculate the conversion for first-order for n tanks in series is

1 1 1
X = 1 n
= 1 n
= 1 4.35

(1 + i k ) (1 + ( n ) k ) (1 + (5.15 / 4.35) 0.25)
X = 0.677

67.7% conversion achieved for the tanks-in-series model

(d) Conversion for CSTR:

For a single CSTR,

k 1.29
X = =
1 + k 2.29

X = 0.563

56.3% conversion achieved for the single CSTR.

ADDITIONAL PROBLEMS WITH SOLUTIONS

1. Consider the first order decomposition of A. The following data is given:

L = 4x10 4 m k e = 1.6kJ / m / hr / K De = 5x10 5 m 2 / hr

hT = 160kJ / hr / m2 / K k m = 300m / hr H = 160kJ / molA

C Ab = 20mol / m3 robs = 105 mol / m3 / hr

Answer the following questions:

Is external mass transfer important to consider?

Are there significant limitations due to pore diffusion?

Do we expect significant temperature gradients within the pellet & outside?

SOLUTION:
2. The irreversible gas-phase reaction A B is carried out isothermally over a packed bed
of solid catalyst particles. The reaction is first order in the concentration of A on the
catalyst surface. The feed consists of 50% (mole) A and 50% inerts and enters the bed at a
temperature 300 K. The entering volumetric flow rate is 10 lit/sec The relation between
Sh and Re is Sh= 100 (Re)0.5

As a first approximation one may neglect pressure drop. The entering concentration of A is
1.0M. Calculate the catalyst weight necessary to achieve 60% conversion?


Kinematic viscosity: 0.02 cm2/sec; Particle diameter: 0.1 cm

Superficial velocity 10 cm/s; Catalyst surface area /mass of the catalyst bed: 60 cm2/g. cat

Diffusivity of A 10-2 cm2/sec.

Specific rate constant (k) is 0.01 cm3/sec g cat with E= 4000 cal/mol

SOLUTION

3. (a) Following is the observed reaction rate in an isothermal reactor as a function of
particle size for an elementary first order liquid phase reaction. The bulk concentration (1
mol/lit) is same in each case. Find the approximate value of effective intra-particle
diffusivity. Catalyst density is 1 gm/cc.

(b) The above reaction is performed in a fluidized bed reactor which received the feed at 100
kmol/hr and a conversion of 10% is realized. Predict the conversion if the original particle radius
of 1.8cm of the same catalyst is reduced by half under otherwise similar conditions. Fluidized
bed reactor can be considered to be a perfectly back-mixed reactor for all practical purposes.

SOLUTION:

4. A first order irreversible cracking reaction A = B is performed in a fixed bed reactor on a
catalyst particle size of 0.15 cm. Pure A enters the reactor at a superficial velocity of
2m/s, a temperature of 2000C and pressure of 1 atm. Under these conditions, the reaction
is severely affected by internal diffusion effects. Calculate the length of bed necessary to
achieve 60% conversion.

Data given:
 The intrinsic reaction rate constant calculated by performing experiments with very small
particle size of the same catalyst is 0.0003 m3/g cat. sec.

Effective diffusivity: 1.5 x 10-8 m2/s

Catalyst density: 2 gm/cm3

SOLUTION: