REACTION ENGINEERING

EP 319
CHAPTER 4
ISOTHERMAL REACTOR DESIGN
NOOR ROSYIDAH SAJUNI
rosyidah@ucsiuniversity.edu.my
Note: Please make appointment first before
consultations and come fully prepared.

4.1

Design structure for isothermal reactor

(batch, CSTR and PFR)

4.2

Introduction for space time () and Damkohler number

4.3

Design for multiple reactor systems

4.4

Pressure drop in reactor

4.5

Reversible reactions
2

Describe the chemical reaction engineering algorithm for

isothermal reactor design in order to solve chemical
reaction engineering problems

Use the given rate law and feed conditions to design batch
reactors, CSTRs, PFRs for isothermal operation

1.

Apply Mole Balance and Design Equation

V

F jo r j dV F j

dN j
dt

2.

Find Rate Law -rA=k(T)f(Ci)

3.

Use stoichiometry to express as function of X

4.

Combine & evaluate to find VPFR, VCSTR or tbatch

www.themegallery.com

The design pathways for one to follow in the design of isothermal

reactors are as following:
A. MOLE BALANCE
Do balance on species A based on the types of reactor

B. DESIGN EQUATIONS
Determine the design equations based on types of reactor

C. RATE LAW
Determine the rate law in terms of the concentration of the reacting
species

Different types of rate laws

E. COMBINE AND EVALUATE

Combine to calculate the volume to achieve a given conversion or calculate
the conversion achieved in a specified reaction volume

Example for the case of FIRST ORDER GAS PHASE REACTION IN A PFR

10

BATCH
REACTOR

11

4.1 DESIGN STRUCTURE FOR ISOTHERMAL REACTOR

(SCALE UP OF LIQUID PHASE BATCH REACTOR DATA)
Analysis on laboratory scale batch reaction are sometimes
needed in the scale up of laboratory experiments to pilot plant
operation or to full scale production
Data from batch reactor can be used to determined the reaction
time, t needed to achieve a conversion, X for specific reaction
or sometimes to find the reaction rate constant, k
The reactor volume could also be obtained from this equation

12

AB

Given elementary first order reaction,

1. Mole Balance

dX rA

V
dt NA 0

2. Rate Law

rA kC A

3. Stoichiometry (V=V0)

CA

4. Combine

N A N A 0 (1 X)

V
V

dX kC A

V
dt
NA0
dX
k (1 X)
dt

N A 0 (1 X)
V
V
N A0
13

AB

Given elementary first

Order reaction,
dX
kdt
(1 X)
X

5. Integrate

1
0 (1 X) k 0 dt
X

1
1
Where
ln
and k dt kt
(1 X)
1 X
0
0
1
1
Therefore t ln
k 1 X

From the equation above, we can obtain the time of reaction in a batch reactor
with information of the rate constant and conversion, X only for a first order
reaction

14

1.1 DEFINITION OF REACTION RATE

FIRST ORDER REACTION

AB

The first order rate law for the general reaction, is written as

dC A

kCA
dt

dC A

kdt
CA

Integrating above equation to yield

C A0
ln
kt
CA
From the equation above, we can obtain the time of reaction in a batch reactor
with information of the rate constant and initial and final concentration of
reactant A for a first order reaction
15

Given elementary
second Order reaction,

2A B
1. MOLE BALANCE

dX rA

V
dt NA 0

2. RATE LAW

rA kC A

3. STOICHIOMETRY
(V=V0)

CA

NA
N (1 X )
A0
V
V
2

4. COMBINE

dX kC A

dt
N A0

N A 0 (1 X) 2
k
2
V
V
V
N A0

dX
kC A 0 (1 X) 2
dt

16

AB

Given non- elementary

second Order reaction,
dX
kdt
2
C A 0 (1 X)

5. INTEGRATE

1
CA0

1
0 (1 X) 2 k 0 dt
X

1
X
Where

and k dt kt
2
(1 X) 1 X
0
0
Therefore t

1
X
(
)
kC A 0 1 X

From the equation above, we can obtain the time of reaction in a batch reactor
with information of the initial concentration of A, rate constant and conversion,
17
X only for a second order reaction

1.1 DEFINITION OF REACTION RATE

SECOND ORDER REACTION
The second order rate law for the general reaction is given by

dC A
2

kC A
dt

dC A

kdt
2
CA

Separating the variables and integrating gives

1
1

kt
CA CA 0
From the equation above, we can obtain the time of reaction in a batch reactor
with information of the initial and final concentration of A, rate constant only
for a second order reaction
18

ABCD
1. MOLE BALANCE

Given non elementary reaction,

dX rA

V
dt NA 0

Rule :
2. RATE LAW

b
1
a

3. STOICHIOMETRY
4. COMBINE

20

ABCD

Given non elementary reaction

5. INTEGRATE

dX
kdt
C A 0 (1 X)( B X)
X

1
1
k dt

C A 0 0 (1 X)( B X)
0
X

1
1
B X
Where

ln
and k dt kt
(1 X)( B X) B 1 B (1 X)
0
0
1
1
B X
Therefore t
(
ln
)
kC A 0 B 1 B (1 X)

21

Given a gas phase reaction with first order with respect to A

and B

takes place in a batch reactor. 40 mol% of the inlet is from

reactant A. Given the reaction rate constant, k= 15 dm3/mol.s,
CA0 = 5 mol/dm3 and conversion, X = 0. 3.
Find the reaction time if the reaction is conducted in a batch
reactor

22

ABC

GIVEN NON ELEMENTARY

REACTION,

1. MOLE BALANCE

dX rA

V
dt NA 0

2. RATE LAW

rA kC A C B

3. STOICHIOMETRY

N A N A0 (1 X )
CA

C A0 (1 X ) 5(1 X )
V
V
N
N ( X )
0.6
C B B A0 B
C A0 ( B X ) where B
1.5
V
V
0.4
Therefore C B 5(1.5 X )
23

ABC

Given non elementary reaction

2
2
dX
kC
C
(
15
)(
5
)
(
1

X
)(
1
.
5

X
)
(
15
)(
5
)
(1 X)(1.5 X)
A
B
5. INTEGRATE

V
V
dt
NA0
NA0
5

dX
75(1 X)(1.5 X)
dt
dX
dt
75(1 X)(1.5 X)
X

V
V
1
0
N A0 N A0 CA0

1
1
dt

75 0 (1 X)(1.5 X) 0
X

1
1
B X
Where

ln
and dt t
(1 X)( B X) B 1 B (1 X)
0
0
Therefore t

1
1
1 .5 X
1
1
1 .5 0 .3
(
ln
) (
ln
)?
75 1.5 1 1.5(1 X)
75 1.5 1 1.5(1 0.3) 24

We will learn the design structure for 2 different system:

DESIGN STRUCTURE

TUBULAR
REACTOR
(PFR)

CSTR

25

We will learn the CSTR design structure for 2 different system:

CSTR

Liquid Phase Reaction

Constant Volume, (v=v0)

First Order Reaction

Second Order Reaction

26

Design of CSTR
First Order Reaction for
Liquid Phase

27

1.

Design equation of CSTR

2.

When the volumetric flow rate does not change with reaction
(v = vo) for liquid phase reaction, therefore

3.

In terms of the space time,

FA 0 FA
rA

AB
1

C A 0 C A
FA 0 FA (C A 0 0 ) (C A 0 )
V

0
rA
rA
rA

V C A 0 C A

0
rA

28

4.

For the FIRST ORDER irreversible reaction, the rate law is given as

rA kC A

5.

Combine equation 3 and 4 to obtain

6.

Substitute in conversion, X equation to obtain the final equation as

C A 0 C A

kC A

CA0X

kC A 0 (1 X)

k
X

1 k

1 X

k 1 X

From the equation above, We can obtain the conversion in terms of space time
and rate constant for first order for the design of CSTR.
29

Design of CSTR
Second Order Reaction for
Liquid Phase

30

1.

Design equation of CSTR

2.

When the volumetric flow rate does not change with reaction
(v = vo) for liquid phase reaction, therefore

3.

In terms of the space time,

FA 0 X
V
rA

AB
1

C A 0 C A
FA 0 FA (C A 0 0 ) (C A 0 )
V

0
rA
rA
rA

V C A 0 C A

0
rA

31

4.

For the SECOND order irreversible reaction, the rate law is given as

5.

Combine equation 3 and 4 to obtain

6.

Rearrange back to obtain

rA kC A

AB

V C A 0 C A

2
0 kC A

CA0 CA
CA0X
X

2
2
2
2

kC A
kC A0 (1 X) kC A0 (1 X)
or kC A0

2
(1 X)

From the equation above, We can obtain the conversion in terms of space time
32
and rate constant for second order for the design of CSTR.

X
2
kC Ao 1 X

Evaluate

kCAo X 1 2kCAo X kCAo 0

2

1 2kC Ao 1 2kC Ao

2kC Ao

2kC Ao
X

1 2k 1 4k 2
2k
33

CONTINUED:
From the previous equation for first order
From the previous equation for second
order

X
kC A0
2
(1 X)

For first order reaction, the product k and for second order,
the product kCAO is referred to as the reaction
DAMKOHLER NUMBER
A dimensionless number that gives a quick estimate of the
degree of conversion in CSTR
Da = 0.1 or < gives less than 10% conversion and Da=10.0 or
> gives greater then 90% conversion

34

Damkohler Number for FIRST Order Irreversible

Reactions

Damkohler Number for SECOND Order Irreversible

Reactions

35

Given an elementary gas phase reaction

2A B C
takes place in a CSTR at constant temperature of 500 K and
constant pressure of 16.4 atm. Reactant A and B is equal in
molar. Given the reaction rate constant, k = 10 dm6/mol2.s,
FA0 = 5 mol/s and conversion, X = 0.9.
Find the volume of reactor, V

36

2A B C
1.

1
1
B C
2
2

Mole Balance for CSTR

1

2.

Rate Law for elementary reaction

2

3.

Stoichiometry: For gas phase system, the concentration of

reactant A is

3
37

2A B C

1
1
B C
2
2

4. Stoichiometry: Isothermal (T=T0), with no pressure drop

(P=P0)

CA CA0

(1 X)
(1 X)

5. Determine the value of from the equations, yA0 = 0.5

(equal molar)
d c b
y A 0 y A 0 1
a a a

1 1
0.5 1 0.5
2 2

38

A
6.

1
1
B C
2
2

Substitute = -0.5 into equation 4 to obtain

CA CA0

7.

(1 X)
(1 0.5X)

For gas phase system, the concentration of reactant B is

7

8.

Stoichiometry: Isothermal (T=T0), with no pressure drop

(P=P0)

[ B ( b / a ) X ]
CB CA0
(1 X)

8
39

9. We know

1
1
B C
2
2

y
B B0 1 therefore
yA0

[1 0.5 X ]
C B C A0
(1 0.5 X )

10.Subsequently determine CA0

CAO

y A O PO
RTO

0.5(16.4atm)
3

0
.
2
mol
/
dm
0.082dm 3 .atm
500K )
mol.K

10

40

A
11.

Combine in equation 2 previously to obtain the reaction rate as

rA kC AC B kC
2

dm 6

10
2
mol .s

12.

1
1
B C
2
2

A0

(1 X ) 3
(1 0.5 X ) 3
11

mol
[1 0.9]2
0.2
3
2
dm

[1 0.5(0.9)]

The CSTR volume is determined as following

V

FA0 X

rA

5mol / s (0.9)

10

dm

2
mol .s

0. 2

mol
[1 0.9]

dm3 [1 0.5(0.9)]2
2

12

41

Design of Tubular Reactors

(PFR)

42

We will learn the design structure for 2 different system:

Tubular Reactor
P T
0 (1 X) 0
P T0

Liquid Phase Reaction

Constant Volume (v=v0)

First Order
Reaction
-rA = kCa

Second Order
Reaction
-rA = kCa2

Gas Phase Reaction

Variable Volume,

First Order
Reaction
-rA = kCa

Second Order
Reaction
-rA = kCa2
43

1.

Gas and liquid phase reactions generally carried out

in tubular reactors. The integral form
of the design equation as following
(when absence of pressure drop or
heat exchange)

2.

For first order reaction, the rate law

expression is substituted in equation 1

3.

For second order reaction, the rate law

expression is substituted in equation 1

dX
V FA 0
kC A
0

dX
V FA 0
2
0 kC A

44

Design of Tubular Reactors

First Order Reaction

For Liquid Phase

45

3.

For First Order reaction, we know that the rate law expression
is as following:
X
dX
V FA 0
5
kC A
0
C C (1 X)
A

4.

A0

Substitute in the concentration terms into the equation to

obtain
X

FA 0
dX
V FA 0

kC A kC A 0
0

FA 0
1
1
(1 X)dX kC A 0 ln 1 X
0

BY USING INTEGRAL EQUATION, FIND THE FINAL TERM

FOR THE REACTOR VOLUME
46

Design of Tubular Reactors

First Order Reaction

For Gas Phase

47

1.

For gas phase reactions at constant temperature and pressure,

the inlet and outlet volumetric flow rate is expressed as
following
4

4.

Therefore, the concentration can be expressed as a function of

conversion

48

3.

For First Order reaction, we know that the rate law expression
is as following:
X
dX
V FA 0
5
kC A
0

4.

Substitute in the concentration terms into the equation to

obtain
X
X
dX
FA 0
(1 X )
V FA 0

dX

kC A kC A 0 0 (1 X )
0
BY USING INTEGRAL EQUATION, FIND THE FINAL TERM
FOR THE REACTOR VOLUME
49

dX
FA 0
V FA 0

kC A kC A 0
0

(1 X )
0 (1 X) dX

BY USING INTEGRAL EQUATION, FIND THE FINAL TERM FOR THE REACTOR VOLUME

THEREFORE

FA 0
1
V
(1 ) ln
x
kC A 0
1 x
50

Design of Tubular Reactors

Second Order Reaction

For Liquid Phase

51

3.

For Second Order reaction, we know that the rate law

expression is as following:
X

V FA 0
0

4.

dX
kC A

C A C A 0 (1 X)

Substitute in the concentration terms into the equation to

obtain
X

V FA 0
0

FA 0
dX

2
2
kC A
kC A 0

FA 0
1
X
dX

2
0 (1 X) 2
kC A 0 1 X

BY USING INTEGRAL EQUATION, FIND THE FINAL TERM

FOR THE REACTOR VOLUME
52

Design of Tubular Reactors

Second Order Reaction for

Gas Phase

53

6.

For Second Order reaction, we know that the rate law

expression is as following:
X

V FA 0
0

7.

dX
2
kC A

Substitute in the concentration terms into the equation to

obtain
X
X
dX
FA 0
(1 X ) 2
V FA 0

dX
2
2
2
kC A 0 0 (1 X )
0 kC A
BY USING INTEGRAL EQUATION, FIND THE FINAL TERM
FOR THE REACTOR VOLUME
54

dX
FA 0
V FA 0

2
2
kC
kC
0
A
A0

(1 X ) 2
0 (1 X) 2 dX

BY USING INTEGRAL EQUATION, FIND THE FINAL TERM FOR THE REACTOR VOLUME

THEREFORE

2
FA 0
(
1

)
X
2
V
2(1 ) ln(1 X ) X
2
1 X
kC A 0
55

Given an elementary gas phase reaction

2A B
takes place in 2 different reactors (CSTR and PFR) at
constant temperature of 500 K and constant pressure of
8.2 atm. Only reactant A is fed into the system. Given the
reaction rate constant, k = 0.5 dm3/mol.s, CA0 = 0.2 mol/dm3,
v0 = 2.5dm3/s and conversion, X = 0.6.
Find the volume of the each reactor
Subsequently find the reaction time if the reaction is
conducted in a batch reactor
56

2A B

CSTR
1.

MOLE BALANCE

2.

RATE LAW

3.

STOICHIOMETRY

rA kC A

GAS: T =T0 , P =P0

1
B
2

PFR

CA CA0

rA kC A

(1 X )
(1 X )

57

2A B
CSTR
4.

5.

1
B
2

PFR

Determine the value of from the equations, yA0 = 1

d c b
1
1.0 1 0.5
y A 0 y A 0 1
2
a a a

Combine with rate law

rA kC

kC

A0

(1 X) 2
(1 X ) 2
2
kC A 0
2
(1 X )
(1 0.5X) 2

58

2A B
7.

1
B
2

Volume for PFR and CSTR are determined as following

CSTR

PFR

FA 0 X(1 0.5 X )2
V
kC2 A 0 (1 X )2

FA 0
V
kC2 A 0

(1 0.5 X )2

2
(
1

X
)

FINAL EQUATION FOR CSTR

8. Integrate for PFR to obtain

F
V A20
kC A 0

2
[
1

0
.
5
)
X
2
2
(

0
.
5
)[
1

0
.
5
)]
ln(
1

X
)

0
.
5
)
X

FINAL EQUATION FOR PFR

59

2A B

1
B
2

10. Subsequently determine the reactor volume for CSTR

FA0 X (1 0.5 X ) 2
V
kC 2 A0 (1 X ) 2
(0.2 2.5)mol / s )(0.6)[1 0.5(0.6)]2

0.5dm 3 / mol.s (0.2mol / dm 3 ) 2 (1 0.6) 2

?

60

2A B
11.

1
B
2

Subsequently determine the reactor volume for PFR

[1 (0.5)]2 X
2(0.5)[1 (0.5)] ln(1 X) (0.5) X

1 X

(0.2 2.5)mol / s
[1 (0.5)]2 (0.6)
2

2(0.5)[1 (0.5)] ln(1 0.6) (0.5) (0.6)

0.5dm 3 / mol.s(0.2mol / dm 3 ) 2
1 0.6

F
V A20
kC A 0

61

2A B
12.

1
B
2

Subsequently determine the reaction time (batch)

2

Batch

kC A 0 (1 X) 2
dX rA
kC A

V
V
V
dt N A 0
N A0
N A0
X

dX
1
dX
kdt ,
k dt
2
2

C A 0 (1 X)
C A 0 0 (1 X)
0
1 X
kt
CA0 1 X
Therefore time of reaction, t
1
(0.6)
(0.5dm 3 / mol.s)(0.2mol / dm 3 ) 1 0.6
t 15s
t

62

FROM EXAMPLE 4.3 PAGE 171 FOGLER 4RD EDITION

k at 1000 K = 0.072/s and activation energy, Ea = 82 kcal/g.mol

63

B. IDEAL GAS CONSTANT

J
kPa.dm 3 .
dm 3 .atm
R 8.3144
8.314
0.082
mol.K
mol.K
mol.K
cal
Btu
ft 3 .atm
R 1.987
1.987
0.73
o
mol.K
lb mol. R
lb mol.o R

Temperature oF
o
R
K
o
R

= 1.8 x oC + 32
= oF + 459.69
= oC + 273.15
= 1.8 x K

64

SOLUTION
1. Determine the chemical equation

2.

Determine the specified production rate of ethylene (product B) exiting the

reactor

65

SOLUTION
3.

Determine the initial molar flow rate of ethane (reactant A) based on the
molar flow rate of product B, FB and conversion, X = 0.8
3

4.

Design equation for PFR in the absence of pressure drop and isothermal
operation
4

66

SOLUTION

5. Rate Law

6. Stoichiometry: Isothermal (T=T0) with no pressure drop (P=P0),

therefore the concentration of A

(1 X)
C A C A0
(1 X)

67

7. Combine design equation,

rate law and stoichiometry

68

SOLUTION

8. Solve the integral equations based on Appendix A.1 formulation

as shown below
8

9. Since the reaction is isothermal, k can be taken outside the

integral sign before integrating it to obtain
9

69

SOLUTION

10.Subsequently determine CA0

10

70

SOLUTION

11. Determine the reaction rate constant, k at 1100K based on the

info given of k at 1000 K = 0.072/s and activation energy, Ea = 82
kcal/g.mol (ARRHENIUS EQUATION)

11

71

SOLUTION

12. Substitute the values from equation 10-11 in equation 9 with X =

0.8 to obtain

72

DESIGN OF MULTIPLE
REACTOR SYSTEMS

73

First-order reaction, liquid phase (=o)

Mole balance on CSTR-1
V1

FAo FA1

rA X X 1

1k1
C A1

o C Ao C A1
k1C A1

C Ao C A1
C
Ao 1
C A1
C A1

C Ao

1 1k1

74

Mole balance on CSTR-2

o C A1 C A 2
FA1 FA 2
V2

rA X X 2
k 2C A 2
2 k2

C A1 C A 2
C
A1 1
C A2
C A2

C A2

C A1

1 2 k2

C A2

C Ao

1 1k1 1 2 k 2
75

For n-equal sized CSTR in series

All CSTRs are operated at same temperature (k is same
in all reactors)

C
C A1 Ao
1 k

C A1
C A2
1 k

C A2
C A3
1 k

C An

C An 1

1 k

C Ao
C An
n
1 k
1
X 1
1 k n
76

F
V
, FA0i A0
n
n
V
F Xi

A0
n
n rAi

Vi

k
X
1 k
V

o
n

77

1.

If we have n equal sized CSTRs connected

in parallel and the feed is distributed
equally among each reactors, therefore the
individual reactor volume

X1 X 2 .... X n X
rA1 rA 2 .... rAn rA
78

3.

The volume of each individual reactor,

Vi and molar flow rate, FA0i is as
following

79

2.

Conversion (X1 = X2 = = Xn = X) and

rate of reaction (-rA1 = -rA2 = = -rAn =
-rA) are the same in each reactor

k
X

1 k

80

FROM EXAMPLE 4.2 PAGE 163 FOGLER 4RD EDITION

81

SOLUTION 1
1.

Determine the chemical equation

Ethylene Water
oxide
2.

Ethylene
glycol

Determine the specified production rate of ethylene glycol (product C) in lb

mol/min
2

82

SOLUTION
3.

Determine the initial molar flow rate of ethylene oxide (reactant A) based
on the molar flow rate of product C, Fc and conversion, X = 0.8. From the
reaction stoichiometry,

and we know

FC0
c
0 and 1
FA0
a

FC FAo X
3

83

SOLUTION : TO CALCULATE THE VOLUME OF A SINGLE CSTR REQUIRED

4. Design equation for CSTR

5. Rate Law

Given
k=0.311/min

rA kC A

(FIRST
ORDER)

6. Stoichiometry: Liquid Phase (v=v0),

FA FA0 (1 X)
CA

C A0 (1 X)

7. Combine all to obtain

84

8.
V1
V2

Determine the concentration, Cao. It is

determined from the question, 1lbmol/ft3 (M1)
of A is fed to the reactor together with an equal
volumetric solution of water. This indicated the
concentration has changed and we need to find
the new Cao (M2).

V2 2V1
M1V1 M 2 V2
Therefore M1V1 M 2 V2
M1V1 2M 2 V1
1
M 2 (1 lb mol/ft 3 ) 0.5lb mol/ft 3 C A 0
2
85

9. Finally determine the CSTR volume with k =

0.311/min

VCSTR

FA 0 X

kC A 0 (1 X)

7.67 lb mol/min(0.8)

(0.311/min)(0.5 lb mol/ft 3 )(1 0.8)

197.3ft 3 1480gal

86

SOLUTION : TO CALCULATE HOW MANY 800-GAL REACTORS WOULD BE

REQUIRED IF ARRANGED IN PARALLEL AND THE CORRESPONDING
CONVERSION (80% or more)

To determine the number of reactors,

we need to use trial and error method.
Assume 2 800-gal CSTRs were
arranged and subsequently determine
whether its conversion is 80% or
more

87

SOLUTION : TO CALCULATE HOW MANY 800-GAL REACTORS WOULD BE

REQUIRED IF ARRANGED IN PARALLEL AND THE CORRESPONDING
CONVERSION (80% or more)

For 2 800-gal CSTRs arranged in parallel the

conversion achieved can be calculated from
VCSTR

FA 0i X
kC A 0 (1 X)

FA 0
Re member for 2 CSTRs in parallel FA0i
2
7.67ft 3 . / min
(
)X
1ft 3
2

800gal
3
7
.
48
gal
0
.
311
/
min(
0
.
5
lbmol
/
ft
)(1 X )

X 0.81

88

SOLUTION : TO CALCULATE HOW MANY 800-GAL REACTORS WOULD

BE REQUIRED IF ARRANGED IN SERIES AND THE
CORRESPONDING CONVERSION

1. For n 800-gal CSTRs arranged in series

89

SOLUTION : TO CALCULATE HOW MANY 800-GAL REACTORS WOULD

BE REQUIRED IF ARRANGED IN SERIES AND THE
CORRESPONDING CONVERSION

For CSTR in series, we need to determine the final conversion, X 2

VCSTR ,1
800gal(

FA 0 X1
kC A 0 (1 X1 )

1
7.67lbmol / min(X1 )
)
7.48gal (0.311 / min)(0.5lbmol / ft 3 )(1 X1 )

X1 0.68
VCSTR , 2

F ( X X1 )
FA1 FA 2
A0 2
kC A 0 (1 X 2 ) kC A 0 (1 X 2 )

1ft 3
(7.67lbmol / min)(X 2 0.68)

800gal
3
7
.
48
gal
0
.
311
/
min(
0
.
5
lbmol
/
ft
)(1 X 2 )

X 2 0. 9
90

In gas phase reactions, the concentrations is proportional to the

total pressure therefore the effects of pressure drop need to be
considered.
For ideal gas with variable volume, the outlet volumetric flowrate
is given as

P0 T
0 (1 X)

P T0
And for Isothermal (T=T0) operation,

P0
0 (1 X)

P
91

Rate law reduced to the thermodynamic relationship relating

the reacting species concentrations at equilibrium
At equilibrium. the rate of reaction is identically zero for all
species, -rA = 0
For general reaction, aA + bB
cC + dD
the concentrations at equilibrium are related by the
thermodynamic relationship
Concentration Equilibrium constant, Kc
= (mol/dm3)d+c-b-a

92

NON REVERSIBLE
REACTION
2A + B 2C + 2D
Conversion

X = conversion
Ex : X= 0.8

REVERSIBLE REACTION
2A + B 2C + 2D
Xe = equlibrium conversion
X = Xe ( X) where Xe = 0.85
X = 0.8
Ex :

Rate Law

X = 0.85(0.8) = 0.68

-rA = k CA2CB

CC C D
rA k (C A C B )
KC
2

To determine the X or VReactor for

reversible reactions,
must calculate the maximum
conversion that can be achieved at the
isothermal reaction temperature, which is
the equilibrium conversion (Xe) by using
Kc
93

EXAMPLE OF WRITING THERMODYNAMIC EQUILIBRIUM

RELATIONSHIP FOR A REVERSIBLE CHEMICAL REACTION

Therefore the concentration equilibrium constant, Kc for the above reaction

is:

94

kA

For general reaction,

k-A

For the above reversible reaction, the net rate of formation of A is the
sum of rates of formation from the forward reaction and the reverse
reaction
r A = r A, net = r A, forward + r A, reverse
For the forward formation reaction, r A, forward = - k A C A
For the reverse formation reaction, r A, reverse = k -A C B
Therefore for rate of formation of A, r A:
r A = r A, net
= r A, forward + r A, reverse = -k A C A + k -A C B
Therefore for rate of disappearance of A, -r A:
-r A = r A, net = r A, forward + r A, reverse = k A C A - k -A C B

95

We know the rate of disappearance of A, -r A:

-r A = r A, net
= r A, forward + r A, reverse = k A C A - k -A C B
As determined previously the equilibrium constant, Kc is given as,

KC

kA
k A

Therefore the rate law for the above reversible equation becomes

CB
rA k A (C A
)
KC

At equilibrium, -rA = 0, and after rearranging we obtain the equilibrium constant,

Kc as

CB
KC
CA
96

kA

For general reaction,

2A

B+C
k-A

We know: r A = r A, net = r A, forward + r A, reverse

For the forward formation reaction, r A, forward = - k A CA2
For the reverse formation reaction, r A, reverse = k -A CB CC
Therefore for rate of formation of A, r A:
r A = r A, net = r A, forward + r A, reverse = - k A CA2 + k -A CB CC
Therefore for rate of disappearance of A, -r A:
-r A = r A, net = r A, forward + r A, reverse = k A CA2 - k -A CB CC

97

Therefore for rate of disappearance of A, -r A:

2

rA k A C A k A C BC C k A (C A

k A

C BCC )
kA

As determined previously the equilibrium constant, Kc is given as,

kA
Therefore the rate law for the above reversible
k A equation becomes
KC

C BC C
rA k A (C A
)
At equilibrium, -rA = 0, and after
rearranging we obtain
K C the equilibrium
2

constant, Kc as

KC

C BCC
2
CA

98

The gas phase isomerization reaction is given as following:

A 2B
The reversible reaction is to be carried out in a non-isothermal
flow system with pure A as the only feed at 260 oC with total
pressure of the system is 310 kPA. Given the specific reaction
rate, k is 110 s-1 and the constant equilibrium constant,
Kc = 0.77 mol/L. Use R = 8.314 kPa.dm3/mol.K.
1.Determine

the equilibrium conversion, Xe

2.Calculate the CSTR volume necessary to achieve 85% of the
equilibrium conversion (X=0.85Xe) if given the feed rate of A =
30 L/s.
99

SOLUTION
C AO

y AO P
(1)(310)

0.07 mol / L
RTo 8.314(260 273.15)

Stochiometry :
CB

Determine the equilibrium conversion, Xe

CA

FA FAO (1 X)
(1 X)

, y AO (1)(1 1 1) 1, C AO
o (1 X)
(1 X )

2FAO X
FB
2X

C AO
o (1 X)
1 X

In equilibrium
CB2
KC
0.67
CA
( 2X ) 2
C AO
(1 X) 2
0.77
(1 X)
C AO
(1 X)
We get X e 0.856
2

10
0

SOLUTION

Calculate the CSTR volume necessary to achieve 85% of the

equilibrium conversion (X=0.85Xe) if given the feed rate of
A = 30 L/s

X (0.85)(0.856) 0.73

2
CB

rA k C A
K C

(1 X )
(1 0.73)
C A C AO
0.07
0.0109mol / L
(1 X )
(1 0.73)
2X
2(0.73)
C B C AO
0.07
0.0591mol / L
1 X
1 0.73

(0.0591) 2
0.700mol / L.s
Therefore rA 110 0.0109
0.77

VCSTR

FAO X
(0.07)(30)(0.73)

2.19 L
rA
0.700

10
1