Example Problems With Solutions
Example Problems With Solutions
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
De C As
Suppose
= 12 = 3 (1 coth 1 1)
[1]
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
[2]
Taking the ratio of the Thiele module for runs 1 and 2, we obtain
11
=
12
R1
R2
rAs' c
DeC As
'
As
r c
DeC As
R1
R
0.01m
11 = 1 12 =
12 = 1012
R2
R2
0.001m
[3]
Using Eqs. (2) & (3) and introducing the information in Table 1, we obtain
0.05 =
12 coth 12 1
1012 coth (1012 ) 1
[4]
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) ,
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.
The rate law, in concentration units is rA =
kC A
where, CA is the concentration of CO2
1 + K 2CD + K 3C A
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
CWP
[1]
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
kCA
(1 + 2K2CAs ) + ( K3 2K2 ) CA
[2]
Assuming the pellet was infinitely long with C A,eq = 0 , the modified parameter
2
= =
r ' ( obs ) R 2 c
= A
2 DeA
1 + K3C As
K 3 2 K 2
1 + K 3C As
1 + 2 K 2C As
ln
1
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.
[3]
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 ,
Solution
The inlet concentration C Ab 0 =
P
4.94
=
= 0.113gmol / l
RT 0.082 533
DeA
d 2 CAb
dC
2
U Ab k " Sa b CAb
=0
2
dz
dz
[1]
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
, Eq (1) can be simplified to
DeA
<< U
2
dz
dz
dCAb
S C2
k " a b Ab = 0
dz
U
[2]
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
L=
U
1
"
b k Sa CAb 0 1 X
[3]
Using the expression for 2 for a second order reaction, the effectiveness factor
12
12
12
2 3 2 3 2
=
=
=
n + 1 n 2 + 1 2 2 + 1
3
= 9.47 108
7
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
L=
U
X
4
0.81
=
= 3.62 102 m
"
8
6
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
2.5*105 m
4
kL
1*10
. = 200 * 2.5 * 10-5 = 5 * 10-3
by assuming slow reaction regime,
2 k1
DA
2.52 *1010 * k1
=
0.25k1
2.5*109
We know that,
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
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 = DA k1 * C A* * VL
Problem : 23B
Time : 19:30
Solution:
Given:
Assume: pO2 = 0.21atm
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
We know that,
M =
DA k1
kL
M >3
2.1*105 *1229.13
4 *102
M = 4.02 > 3
RAVL = DA k1 * C A* * VL
2018.56
= 1.19cm2 / cm3
1700
Problem : 26A
Time : 24:10
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:
DB DA = 1.7
(a) To find the maximum enhancement possible
We know that, q =
DA
(1 + q ) = 1.7 *11.625
DB
E 8.91
(b) To find actual enhancement
We know that,
M =
DA k1CBb
kL
M = 30 > 10.625 ( = q )
Actual enhancement factor,
E= M
E E
E 1
E E
tanh M
First approximation:
E M
E E
1 which lead to
E 1
E E 30
=
E E
E 1 7.91
E E
8.91 8.30
tanh M
= tanh 30
1
8.91
E= M
E E
E 1
E E
tanh M
8.30
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
Lect. No.: 12
Ref.: Scott Fogler, pg.: 858
Problem : 12A
Time : 38:35
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
0.1 =
1 sinh 1 0.5
CA
CA
1 sinh 1
1 sinh(6 * 0.7)
=
=
=
CAS sinh 1 0.001 0.7 sinh 6
Time : 00:00
(b) To what diameter should the pellet be reduced if the effectiveness factor is to be 0.8
The Thiele modulus is,
=R
k1 c sa
k
= R 1r
De
De
k1r
k1r = 3600000sec1
0.1
6 = 1*103
= 0.8 =
12
[1 coth 1 1] 1 = 2
The corresponding Thiele modulus expression to calculate diameter of the catalyst particle is,
=2=R
k1r
3600000
=R
R = 3.4 *104 cm
De
0.1
d p = 6.8 *104 cm
Lect. No.: 38
Ref.: Scott Fogler, pg.: 971
Problem : 38A
Time : 28:40
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)
C (mg/L)
0
0
1
1
2
5
3
8
4
10
5
8
6
6
7
4
8
3
9
2.2
10
1.5
12
0.6
14
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
C(t)
0
1
5
8
10
8
6
4
3
2.2
(a) To calculate conversion using the closed vessel dispersion model
10
1.5
12
0.6
10
1.5
0.03
0.3
3.0
12
0.6
0.012
0.14
1.68
14
0
0
0
0
0
0
1
1
0.02
0.02
0.02
2
5
0.1
0.2
0.4
3
8
0.16
0.48
1.44
4
10
0.2
0.8
3.2
5
8
0.16
0.80
4.0
6
6
0.12
0.72
4.32
7
4
0.08
0.56
3.92
8
3
0.06
0.48
3.84
9
2.2
0.044
0.40
3.60
14
0
0
0
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
= tm = tE ( t ) dt = 5.15 min
Then
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 )
2
2
3
= ( t ) E ( t ) dt = t 2 E ( t ) dt 2
0
2
2
= 2 ( Pe 1 + exp ( Pe ) )
2
Pe
=
6.1
(5.15)
= 0.23 =
2
( Pe 1 + exp ( Pe ))
Pe 2
q = 1+
4 (1.29 )
4 Da
= 1+
= 1.30
Pe
7.5
X = 1
X = 1
4q exp ( Pe 2 )
(1 + q )
(1 + 1.30 )
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
2 ( 5.15)
n= 2 =
= 4.35
6.1
X = 1
(1 + i k )
= 1
(1 + ( n ) k )
= 1
4.35
X = 0.677
67.7% conversion achieved for the tanks-in-series model
(d) Conversion for CSTR:
For a single CSTR,
X =
k
1.29
=
1 + k 2.29
X = 0.563
56.3% conversion achieved for the single CSTR.
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
L = 4x10 4 m
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:
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
(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:
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: