Problem 4.7 (Fogler third edition).

The elementary reaction in the gas phase,

(CH3)3COOC(CH3)3→C2H6+2CH3COCH3

is carried out isothermally in a flow reactor without pressure drop. The speed of
specific reaction at 50°C is 10-4min-1and the activation energy is 85 kJ/mol.
Pure ditert-butyl peroxide enters the reactor at 10 atm and 127 °C at a rate of
molar flow rate of 2.5 mol/min. Calculate the volume of the reactor and the necessary residence time.
to achieve a 90% conversion in:

a) A CSTR

b) A PFR

c) Suppose that the reaction is reversible with Kc = 0.025 mol2/dm6and calculate the conversion
in equilibrium. Then repeat parts (a) and (b) to achieve a conversion that is of
90% of the equilibrium conversion.

Solution:

A = (CH3)3COOC(CH3)3
B = C2H6
C = CH3COCH3
The reaction is,

A B+2C

IMPORTANT NOTE: Based on the stoichiometry of the reaction, 1 mole of

reactant converts into 3 moles of product. Since the reaction is in the gas phase, this
it implies that as the reaction progresses there will be a change in volume, specifically
an expansion so that the pressure remains constant. Therefore, it should be
Use the stoichiometric table for variable volume (slides session 4).
Let us remember that under these circumstances, when the volume changes based on the
conversion, only the molar concentration is different because it depends on the
volume. However, neither molar flows nor the number of moles are affected.
for that volume. If the reaction were to take place in the liquid phase, the table would be used
stoichiometric for constant volume.

a)

T2= 127°C = 400 K

k|323 K= 10-4min-1
FA0= 25 mol/min
X= 0.9
P = 10 atm
EA= 85 kJ/mol

1) Design equation of the CSTR reactor:

FA0 X
V        (1a)
 rA
2) Law of speed
-rA=kCA-------(2a)
A temperature correction of the kinetic constant must be made through the
Arrhenius equation:
E 1 1
k k1 exp A         (3a)
R T1 T 2
Substituting values in (3a):
J
85000
k  10 min 
4 1
exp mol 1 
J
1
0.044 min1
323K 400K
8.31
mol K
3) Stoichiometry (STOICHIOMETRIC TABLE for continuous flow systems with
variable volume, slides session 4)

CA0(1 X) P T 0
CA        (3a)
(1 X) P0 T
The process is isothermal and therefore,
(T0/T) = 1
There is no pressure drop (isobaric process),
(P/P0= 1
There is a change in volume:
Only A is allowed in, so yTo= 1
= yA = (1) (2+1-1) = 2

After making those assumptions, the molar concentration is as follows,

C A 0 (1 X)
CA        (4a)
(1 2X)
Combination

Substituting (4a) into (2a):

kCA 0 (1 X)
 rA        (5a)
(1 2X)
Substituting (5a) into (1a)
FA0 X 1  2X 
V        (6a)
kCA 0 (1 X)
To know CA0the ideal gas law can be used,
 P 10 atm mol
C A0 0.3049 3
RT dm3 ATM dm
0.082  400K
mole K
Substituting values in (6a)
mol
(0.9)1  2  0.9
2.5
min
V 4696dm3
1 mol
0.044 0.3049 3 (1 0.9)
min dm

b)

1) Design equation of the PFR reactor (slides session 1),

dX rA
       (1b)
dVFA0
Kinetic law
-rA=kCA-------(2a)
3) Stoichiometry
C A 0 (1 X)
CA        (4a)
(1 2X)
Combination

Substituting (4a) in (2a):

C A 0 (1 X)
 rA        (5a)
(1 2X)
Substituting (5a) into (1b)
dX kCA0 1 x 
       (2b)

dVFA01 2X 
Applying the method of separation of variables to equation (2b),
 1  2X  kC
A0
dx dV
 1 X  FA0
 X1  2X  kCA0 V
dX dV       (3b)
0  1 X  FA0 0
Integrating (3b),
1 X kCA0 V
3ln
1 x
 2x |0
V
FA0 0
|
1 kCA0
3ln  2x V       (4b)
1 x FA0
Isolating V from (4b),
FA0 1
V 3ln  2x       (5b)
kCA0 1 x
Substituting values in (5b),
mol
2.5
min 1
V 3ln  2  0.9 952.8dm3
1 mol 1  0.9
0.044 0.3049
min dm3

d)

A B+2C

Determination of the conversion at equilibrium:

1) Equation of the equilibrium constant

CBCC2
Kc        (1d)
CA

Stoichiometry

Stoichiometric table:

Species Entry Change Exit

A CA0 CA0X CA= CA0(1 -X)
B 0 CA0X CB= CA0X)
C 0 2CA0X CC= 2CA0X

As there is a change in volume, and the reactor operates isothermally and without pressure drops.
considerable, and with a value of = 2, it is given
C A 0 (1 X)
CA        (2d)
(1 2X)

C A0 X
CB        (3d)
(1 2X)

2CA0 X
CC        (4d)
(1 2X)
Substituting (2d), (3d), and (4d) into (1d)
2
C A0 X eq 2CA0 X eq
2 3
(1 2X eq ) (1 2X eq) 4CA0X eq
Kc      (5d)
C A0 1  X eq   1  2Xeq  2 (1 X eq )
(1 2X eq )

Substituting known values in (5d)

 2
mol
4 0.3049 X eq3
mol dm 3
0.025 6      (6d)
dm  1  2Xeq  2(1 X eq)
Developing (6d)
0.47186Xeq-0.075Xeq -0.025 = 0-------(7d)

Finding the roots of (7d)

Xeq0.5122
Xeq -0.2561 - 0.1945i
Xeq-0.2561 + 0.1945i

The conversion at equilibrium is then:

Xeq 0.5122

The conversion at equilibrium is the maximum conversion that can be obtained, then the
the required conversion is 90% of the maximum (according to the proposal of
problem), that is to say:

X = 0.9(Xeq(0.5122)(0.9) = 0.461

For the CSTR in part (a), the calculations previously described must be repeated but now with a
target conversion of
X= 0.461
and a new kinetic law that includes the equilibrium constant (Kc).

1) Design equation of the CSTR reactor:

FA0 X
V        (1a)
 rA

Kinetic equation
CBCC2
 rA k CA        (8d)
Kc
The value of k corrected is
k = 0.044 min-1

3) Stoichiometry

The concentrations of products and reactants are given by the equations,

 C A0 (1 X)
CA        (2d)
(1 2X)

C A0 X
CB        (3d)
(1 2X)

2CA0 X
CC        (4d)
(1 2X)

Combination

Substituting (2d), (3d) and (4d) in (8d)

C A0 X 2CA0 X
2 3
C A 0 (1 X) (1 2X) (1 2X) kCA0 4CA0X
 rA   1 X   2
       (9d)
(1 2X) Kc (1 2X) 1 2X) Kc

Substituting (9d) into (8d)

FA0 X
V       ( 10d)
2 3
kCA0 4CA0X
 1 X   2
(1 2X) (1 2X) Kc
Substituting values in (10d)
mol
2.5  0.461
min
V 1143dm3
2
1 mol mole
0.044 0.3049 3 4 0.3049 0 .4613
min dm dm3
 1  0.461  
 1  2  0.461 mol 2
 1  2  0.461 0.025
2

dm6

For the PFR of part (b)

1) Reactor design equation.

dX rA
       (1b)
dVFA0
2) Kinetic equation
CBCC2
 rA k CA        (8d)
Kc

3) Stoichiometry
 C A0 (1 X)
CA        (2d)
(1 2X)

C A0 X
CB        (3d)
(1 2X)

2CA0 X
CC        (4d)
(1 2X)

Combination
Substituting (2d), (3d), and (4d) into (8d)
2 3
kCA0 4CA0X
 rA  1 X          (9d)
1 2X) (1 2X) 2Kc
Substituting (9d) in (1b)
2 3
dX 1 kCA0 4CA0X
 1 X         1 1d
dV FA0(1 2X) (1 2X) 2Kc
Applying the method of separable variables to (11d)
kCA0  1  2X 
dV dX
FA0 4CA0X 3
2
 1 X   2
(1 2X) Kc

kC
V A0 X  1  2X 
dV dX       (12d)
0 FA0 0
4CA02X 3
 1 X   2
(1 2X) Kc
Substituting known values in (12d):
1 mole
0.044 0.3049 3
min dm V X  1  2X 
dV dX
mole 0 0 2
2.5
min  4 0.3049mol3 X 3
dm
 1 X  
mol 2
(1 2X) 2 0.025
dm6

V X  1  2X 
5.3662 10 3dV dX      ( 13d)
0 0
14.8742X3
 1 X  
1 2X) 2
Numerically integrating the second term of (13d)
Using the formula for 10 points:
X9 3
f(X)dX h f0 3f1 3f2 2f3 3f14 3f5 2f6 3f7 3f8 f9      ( 14d)
0 8
X 9 X 0
h
9
Using equation (14d), it is obtained that:
 0.461  1  2X 
dX 1.4099
0
14.8742X3
 1 X  
(1 2X)2
Integrating (13d) and solving for V from it:
1
5.3662 10 3 V 1.4099
dm3
1.4099
V 262.737dm3
1 3
5.3662 10
dm3

This example, in addition to showing how to obtain the volume of flow reactors
I continue when there is variable volume, it also aims to show the
implication of not considering equilibrium when sizing a reactor.