2

REACTION ENGINEERING Chapter 4

CKB 20104 4.1 Design structure for isothermal reactor
4.2 Design for multiple reactor systems

Chapter 4
4.3 Pressure drop in reactor
4.4 Reversible reactions

Isothermal Upon the completion of this chapter, students are able to:

Reactor Design • Apply the design structure to batch and flow reactor (CSTR and PFR)
for single configurations in isothermal reactions.
• Apply the design structure for multiple reactor systems.
• Account for pressure drop in the design structure for batch and flow
reactor (CSTR and PFR) for single configurations in isothermal
Dr. Kelly Yong Tau Len reactions.
Sect. of Chemical Engineering Technology UniKL MICET
• Explain the reaction rate and the rate law change in reversible
Tel: 06-5512051, Email: kytlen@unikl.edu.my, reactions and apply the design structure for CSTR.
VLE: CKB20104 – kytlen_MICET

3 4
4.1 Design Structure for Isother mal Reactor
4.1 Design Structure for Isother mal Reactor
Step 3: Stoichiometry
The design pathways for one to follow in the design of Use stoichiometry to express concentrati on as a function of conversion.
isothermal reactors are as following

Step 1: Mole Balance

Determine the design equation (Batch, PFR or CSTR)
X dX X dX F X
tbatch = N A0 ∫ OR VPFR = FA0 ∫ OR VCSTR = A0 Isothermal (To=T)
0 −rAV 0 −rA −rA P0 T
υ = υ 0 (1+ ε X)
P T0

Step 2: Rate Laws CA0 (1− X) P

CA =
Determine the rate law in terms of the concentration of the (1+ ε X) P0
reacting species
Step 4: Combine
2
" CC % Evaluate the algebraic (CSTR) or integral (batch and PFR) equations to
−rA = kC A OR − rA = kC OR − rA = kC AC B OR − rA = $C A − B C '
A
# Kc & determine the reactor volume or the processing time, or conversion

1
5 6

List of Integral Formulations 4.1 Design Structure for Isother mal Reactor
dx 1 (Liquid Phase Batch Reactor)
1. ∫
x
= ln List of
1− X
0
1− X
x2 dx 1 1 formulations Analysis on laboratory scale batch reaction
2. ∫ = −
x1
(1− X ) 2 1− X 2 1− X 1 are provided are sometimes needed in the scale up of
3. ∫
x dx
=
X in Test & laboratory experiments to pilot plant operation
0
(1− X ) 2 1− X Exam!
dX 1 or to full scale production.
4. ∫
x
= ln(1+ ε X ) Download
0
1+ ε X ε
x 1+ ε X
from VLE! Data from batch reactor can be used to
1
5. ∫
0
1− X
dX = (1+ ε )ln
1− X
−ε X determine the reaction time, t needed to
6. ∫
x 1+ ε X
dX =
(1+ ε ) X
− ε ln
1 achieve a conversion, X for the reaction or
0
(1− X ) 2 1− X 1− X sometimes to find the reaction rate constant,
(1+ ε X ) 2 (1+ ε ) 2 X
7. ∫
x
2
dX = 2ε (1+ ε )ln(1− X ) + ε 2 X + k.
0
(1− X ) 1− X
X dX 1 ΘB − X The information obtained from batch reactor
8. ∫ = ln where Θ B ≠ 1
0
(1− X ) (Θ B
−X ) Θ B −1 Θ B 1− X( ) can be used in the design of a flow reactor.

4.1 Design Structure For Isother mal Reactor

7 8

(Liquid Phase Batch Reactor)

List of Integral Formulations
dx 1
1. ∫
x
= ln List of
A→B 1− X 1− X
0
FIRST ORDER reaction formulations
x2 dx 1 1
2. ∫ = −
X dX
x1
(1− X ) 2 1− X 2 1− X 1 are provided
Step 1 (Mole Balance) : t = N A0 ∫
0 −rAV Constant Volume 3. ∫
x dx
=
X in Test &
Step 2 (Rate Law) :− rA = kC A (First order reaction) Batch Reactor
0
(1− X ) 2 1− X Exam!
(V=V 0 ) x dX 1 Download
N A N A0 (1− X ) 4. ∫ = ln(1+ ε X )
Step 3 (Stochiometry) : C A = = C A0 (1− X ) 1+ ε X ε
0

V
=
V0 x 1+ ε X 1
from VLE!
5. ∫ dX = (1+ ε )ln −ε X
0
1− X 1− X
N A0dX N A0 X dX C A0
X X dX
Step 4 (Combine) : tbatch = = ∫ ∫ = ∫ x 1+ ε X (1+ ε ) X 1
V kC A V0 0 kC A
0 k 0 C A0 (1− X ) 6. ∫ dX = − ε ln
0
(1− X ) 2 1− X 1− X
1 X dX 1 # 1 & (1+ ε X ) 2
x (1+ ε ) 2 X
tbatch = ∫ = ln % ( 7. ∫ dX = 2ε (1+ ε )ln(1− X ) + ε 2 X +
k 0 (1− X ) k $ 1− X ' 0
(1− X ) 2
1− X
X dX 1 ΘB − X
8. ∫ = ln where Θ B ≠ 1
0
( )(
1− X Θ B − X ) (
Θ B −1 Θ B 1− X )

2
 4.1 Design Structure For Isother mal Reactor 4.1 Design Structure For Isother mal Reactor
9 10

(Liquid Phase Batch Reactor) (Liquid Phase Batch Reactor)

A→B SECOND ORDER reaction A+ B → C SECOND ORDER reaction

X dX X dX
Step 1 (Mole Balance) : t = N A0 ∫ Step 1 (Mole Balance) : t = N A0 ∫
0 −rAV
0 −rAV Constant Volume Constant Volume
Step 2 (Rate Law) :− rA = kC AC B (Second order reaction)
Step 2 (Rate Law) :− rA = kC A2 (Second order reaction) Batch Reactor Batch Reactor
(V=V 0 ) N A N A0 (1− X ) (V=V 0 )
Step 3 (Stochiometry) : C A = = = C A0 (1− X )
N N (1− X ) V V0
Step 3 (Stochiometry) : C A = A = A0 = C A0 (1− X ) b
V V0 From b Rule : = 1
a
Stoichiometric N B N A0 (Θ B − a X )
N A0 X dX N A0
dX C A0 X X dX Table C = = = C (Θ − X )
Step 4 (Combine) : tbatch = ∫ = ∫= ∫ B
V V A0
0
B

V 0
kC A2 V0
kC A2 k0 0 2
C A0(1− X ) 2 N N C
X dX X dX X dX
Step 4 (Combine) : tbatch = A0 ∫ = A0 ∫ = A0 ∫
1 X dX 1 # X & V 0 kC AC B V0 0 kC AC B k 0 2
C A0 (
(1− X ) Θ B − X )
tbatch = ∫ 0 (1− X )2 = kC %$ 1− X ('
kC A0 A0 1 X dX 1 * 1 $ Θ − X '-
tbatch = ∫ 0 (1− X ) Θ − X = kC ,, Θ −1 ln && Θ (1−
B
)/
kC A0 ( B ) A0 + B % B X ) )(/.

11 12

List of Integral Formulations Example 1

dx 1
1. ∫
x
= ln List of
0
1− X 1− X Given a liquid phase reaction takes place in a batch
formulations
2. ∫
x2 dx
=
1
−
1
are provided
reactor. The reaction is first order with respect to A
x1
(1− X ) 2 1− X 2 1− X 1
x dx X in Test & and first order with respect to B
3. ∫ =
(1− X ) 2 1− X Exam!
A+B→C
0

x dX 1 Download
4. ∫ = ln(1+ ε X )
0
1+ ε X ε
x 1+ ε X 1
from VLE!
5. ∫
0
1− X
dX = (1+ ε )ln
1− X
−ε X 60 mol% of the inlet is reactant B. Given the reaction
6. ∫
x 1+ ε X
dX =
(1+ ε ) X
− ε ln
1 rate constant, k = 10 dm3/mol.s and initial
0
(1− X ) 2 1− X 1− X concentration of A is 12 mol/dm3 and 30% of A
(1+ ε X ) 2 (1+ ε ) 2 X
7. ∫
x
2
dX = 2ε (1+ ε )ln(1− X ) + ε 2 X +
1− X
converted.
0
(1− X )

8. ∫
X dX
=
1
ln
ΘB − X
where Θ B ≠ 1
Find the reaction time.
0
( )(
1− X Θ B − X )Θ B −1 Θ B 1− X ( )

3
13 14

Solution Solution
A+B→C SOLUTION
SOLUTION Step 4 (Combine):
X dX N A0 X dX N X dX
Step 1 (Mole Balance) : t = N A0 ∫ tbatch = ∫ = A0 ∫
0 −rAV V 0 kC AC B V0 0 kC AC B
Step 2 (Rate Law) : − rA = kC AC B (Second order reaction) C A0 X dX 1 X dX
= ∫ 2
= ∫
N N (1− X )
Step 3 (Stochiometry) : C A = A = A0 = C A0 (1− X ) = 12(1− X )
k 0
C A0 (
(1− X ) Θ B − X) kC A0 0
(
(1− X ) θ B − X )
V V0
1 * 1 $ Θ − X '-
b = , ln && B )/
N B N A0 (Θ B − a X ) kC A0 ,+ Θ B −1 % ΘB (1− X ) )(/.
CB = = = C A0 (Θ B − X )
V V0 1 * 1 $ 1.5− X '- 1 * 1 $ 1.5− 0.3 '-
= , ln & )/ = , ln & )/
0.6 b (10)(12) +1.5−1 % 1.5(1− X ) (. 120 +1.5−1 % 1.5(1− 0.3) (.
where ΘB = = 1.5 AND = 1
0.4 a tbatch = 0.002s
Therefore C B = 12(1.5− X )

15 16

4.1 Design Structure For Isother mal Reactor

CSTR (Liquid Phase CSTR)

A→B FIRST ORDER reaction

Liquid Phase Reaction Gas Phase Reaction FA0 − FA
Constant Volume (υ = υ 0) Variable Volume Step 1 (Mole Balance) : V = Liquid Phase Reaction
−rA Constant Volume (υ = υ0 )
Step 2 (Rate Law) : − rA = kC A (First order reaction)
First Order Second Order First Order Second Order FA FA0 (1− X )
Step 3 (Stochiometry) : C A = = = C A0 (1− X )
Reaction Reaction Reaction Reaction υ υ0
! P $! T $ FA0 − FA FA0 X
4.1 Design Structure υ = υ0 (1+ ε X) # 0 &## && Isothermal Step 4 (Combine) :VCSTR =
kC A
=
kC A0 (1− X )
" P %" T0 %
For Isother mal Reactor !P $
(CSTR) υ = υ0 (1+ ε X) # 0 &
"P%

4
17 18

4.1 Design Structure For Isother mal Reactor 4.1 Design Structure For Isother mal Reactor
(Liquid Phase CSTR) (Liquid Phase CSTR)
A→B FIRST ORDER reaction • For FIRST ORDER LIQUID PHASE reaction, the
product τk is referred to as the reaction
FA0 − FA FA0 X DAMKOHLER NUMBER, Da
Step 4 (Combine) :VCSTR = =
kC A kC A0 (1− X )
υ0 X 1 X " X %
Therefore, VCSTR = υ 0 = FA0 / CA0
τ= Da = τ k = $ '
k (1− X ) k (1− X ) # 1− X &
V V 1 X
Space Time, τ = CSTR ⇒ CSTR = • A dimensionless number that gives a quick estimate
υ0 υ0 k (1− X )
of the degree of conversion in CSTR
1 X
Therefore, τ = Space time, τ in terms of • Da = 0.1 or < gives less than 10% conversion and
k (1− X ) Conversion, X in a CSTR
for 1st order Liquid phase Da =10.0 or > gives greater than 90% conversion

19 20

4.1 Design Structure For Isother mal Reactor 4.1 Design Structure For Isother mal Reactor
(Liquid Phase CSTR) (Liquid Phase CSTR)
A→B SECOND ORDER reaction A→B SECOND ORDER reaction

FA0 − FA FA0 − FA F X
Step 1 (Mole Balance) : V = Step 4 (Combine) :VCSTR = 2
= 2 A0
−rA Liquid Phase Reaction kC A kC A0 (1− X ) 2
Constant Volume (υ = υ0 )
Step 2 (Rate Law) : − rA = kC 2A (Second order reaction) υ0 X
Therefore, VCSTR = υ 0 = FA0 / CA0
F F (1− X ) kC A0 (1− X ) 2
Step 3 (Stochiometry) : C A = A = A0 = C A0 (1− X )
υ υ0 VCSTR V 1 X
Space Time, τ = ⇒ CSTR =
FA0 − FA FA0 X υ0 υ0 kC A0 (1− X ) 2
Step 4 (Combine) :VCSTR = =
kC A2
kC A0 (1− X ) 2
2 1 X
Therefore, τ = Space time, τ in terms of
kC A0 (1− X ) 2 Conversion, X in a CSTR
for 2nd order Liquid phase

5
21 22

4.1 Design Structure For Isother mal Reactor 4.1 Design Structure For Isother mal Reactor
(Liquid Phase CSTR) (Liquid Phase CSTR)
• For SECOND ORDER LIQUID PHASE reaction, the Remember that DAMKOHLER
product τkCA0 is referred to as the reaction
DAMKOHLER NUMBER, Da NUMBER, Da can be calculated and
used ONLY for
1 X X
τ=
kC A0 (1− X ) 2
Da = τ kC A0 = LIQUID PHASE reactions
(1− X ) 2
And ONLY for rate law
• A dimensionless number that gives a quick estimate
of the degree of conversion in CSTR FIRST ORDER (-rA = kCA)
• Da = 0.1 or < gives less than 10% conversion and and
Da =10.0 or > gives greater than 90% conversion
SECOND ORDER (-rA = kCA2)

23 24

Check Your Understanding 1 4.1 Design Structure For Isother mal Reactor
(Gas Phase CSTR)
A→B FIRST ORDER reaction
Derive the Final Equation to find
VCSTR if given the rate law as Step 1 (Mole Balance) : V =
FA0 − FA !P $
υ = υ0 (1+ ε X) # 0 &
−rA "P%
–rA = kCACB Step 2 (Rate Law) : − rA = kC A (First order reaction)
with both A and B in Liquid phase Step 3 (Stochiometry) : C A =
FA
=
FA0 (1− X ) C (1− X )
= A0
"P % "P %
and the chemical equation given υ
υ0 (1+ ε X) $ 0 ' (1+ ε X) $ 0 '
#P& #P&
as FA0 − FA FA0 X (1+ ε X) " P0 %
Step 4 (Combine) :VCSTR = = $ '
A+ Bà C kC A kC A0 (1− X ) # P &

6
25 26

4.1 Design Structure For Isother mal Reactor Check Your Understanding 2
(Gas Phase CSTR)
A→B SECOND ORDER reaction
Derive the Final Equation to find
F − FA
Step 1 (Mole Balance) : V = A0
!P $
υ = υ0 (1+ ε X) # 0 &
VCSTR if given the rate law as
−rA "P%

Step 2 (Rate Law) :− rA = kC 2A (Second order reaction)

–rA = kCACB
Step 3 (Stochiometry) : C A =
FA
=
FA0 (1− X ) C (1− X )
= A0
with both A and B in Gas phase
υ "P % "P %
υ0 (1+ ε X) $ 0 ' (1+ ε X) $ 0 ' and the chemical equation given
#P& #P&
2
as
FA0 − FA FA0 X (1+ ε X) 2 " P0 %
Step 4 (Combine) :VCSTR =
kC 2A
= $ '
kC 2A0 (1− X ) 2 # P &
A+ Bà C

27 28

4.1 Design Structure For Isothermal Reactor

PFR (Liquid Phase PFR)
A→B FIRST ORDER reaction
X Liquid Phase
Liquid Phase Reaction Gas Phase Reaction dX Reaction
Step 1 (Mole Balance) : VPFR = FA0 ∫
Constant Volume (υ = υ 0) Variable Volume −rA Constant Volume
0
(υ = υ0 )
Step 2 (Rate Law) : − rA = kC A (First order reaction)
FA FA0 (1− X )
First Order Second Order First Order Second Order Step 3 (Stochiometry) : C A = = = C A0 (1− X )
Reaction Reaction Reaction Reaction υ υ0
! P $! T $ Step 4 (Combine) :
4.1 Design Structure υ = υ0 (1+ ε X) # 0 &## &&
" P %" T0 %
Isothermal
X
dX F X
1 FA0 1
for Isother mal Reactor !P $
VPFR = FA0 ∫ = A0 ∫ (1− X )dX = kC ln
kC A kC A0 1− X
(PFR) υ = υ0 (1+ ε X) # 0 &
"P%
0 0 A0

7
29 30

4.1 Design Structure For Isothermal Reactor 4.1 Design Structure For Isothermal Reactor
(Liquid Phase PFR) (Liquid Phase PFR)
A→B SECOND ORDER reaction A+ B → C SECOND ORDER reaction
X
X Liquid Phase dX
dX Step 1 (Mole Balance) : VPFR = FA0 ∫ Liquid Phase Reaction
Step 1 (Mole Balance) : VPFR = FA0 ∫ Reaction
0 −rA Constant Volume (υ = υ0 )
0 −rA Constant Volume
(υ = υ0 ) Step 2 (Rate Law) :− rA = kC AC B (Second order reaction)
Step 2 (Rate Law) : − rA = kC 2A (Second order reaction) FA FA0 (1− X )
Step 3 (Stochiometry) : C A = = = C A0 (1− X )
F F (1− X ) υ υ0
b
Step 3 (Stochiometry) : C A = A = A0 = C A0 (1− X ) b Rule : = 1
υ υ0 FA0 (Θ B − X) a
FB a
CB = = = C A0 (Θ B − X )
Step 4 (Combine) : υ υ0
X
dX F X
1 F # X & Step 4 (Combine) :
VPFR = FA0 ∫ 2
= A02 ∫ 2
dX = A02 % ( X
dX F X 1 F * 1 $ Θ − X '-
0 kC A kC A0 0 (1− X ) kC A0$ 1− X ' VPFR = FA0 ∫ = A02 ∫ dX = A02 , ln && B )/
0 kC AC B kC A0 0 (1− X )(Θ B − X ) kC A0 ,+ Θ B −1 % ΘB (1− X ) )(/.

31 32

4.1 Design Structure For Isothermal Reactor 4.1 Design Structure For Isothermal Reactor
(Gas Phase PFR) (Gas Phase PFR)
A→B FIRST ORDER reaction A→ B SECOND ORDER reaction
X
X dX !P $
dX Step 1 (Mole Balance) : VPFR = FA0 ∫ υ = υ0 (1+ ε X) # 0 &
Step 1 (Mole Balance) : VPFR = FA0 ∫ 0 −rA "P%
0 −rA !P $
υ = υ0 (1+ ε X) # 0 & Step 2 (Rate Law) :− rA = kC A2 (Second order reaction)
Step 2 (Rate Law) :− rA = kC A (First order reaction) "P%
FA FA0 (1− X ) C (1− X )
FA FA0 (1− X ) C (1− X ) Step 3 (Stochiometry) : C A = = = A0
Step 3 (Stochiometry) : C A = = = A0 υ #P & #P &
υ #P & #P & υ0 (1+ ε X) % 0 ( (1+ ε X) % 0 (
υ0 (1+ ε X) % 0 ( (1+ ε X) % 0 ( P
$ ' $P'
$P' $P' 2
X X
dX F #P & (1+ ε X ) 2
Step 4 (Combine) : Step 4 (Combine) :VPFR = FA0 ∫ 2
= A02 % 0 ( ∫ dX
X 0 kC A kC A0 $ P ' 0 (1− X ) 2
dX F # P & X (1+ ε X ) F #P & 1
VPFR = FA0 ∫ = A0 % 0 ( ∫ dX = A0 % 0 ((1+ ε )ln −εx 2
kC A kC A0 $ P ' 0 (1− X ) kC A0 $ P ' 1− x F #P & # (1+ ε ) 2 X &
0 = A02 % 0 ( % 2ε (1+ ε )ln(1− X ) + ε 2 X + (
kC A0 $ P ' $ 1− X '

8
33 34

Example 2 Solution
Given an elementary gas phase reaction
2A → B SECOND ORDER reaction

2A → B SOLUTION :

Step 1 (Mole Balance) : VPFR = FA0 ∫

X
dX
0 −rA
takes place in a PFR at constant temperature of Step 2 (Rate Law) :− rA = kC A2 (Second order reaction)
500 K and constant pressure of 8.2 atm. Pure A FA FA0 (1− X ) C A0 (1− X )
is fed into the system. Given reaction rate Step 3 (Stochiometry) : C A = = =
υ υ0 (1+ ε X) (1+ ε X)
constant as 0.5 dm3/mol.s, initial concentration of X
dX F X
(1+ ε X ) 2
Step 4 (Combine) :VPFR = FA0 ∫ = A0 ∫ dX
A as 0.2 mol/dm3, initial flow rate of 2.5 dm3/s 0 kC A2 kC 2A0 0 (1− X ) 2
and conversion of A as 60%. F # (1+ ε ) 2 X &
= A02 % 2ε (1+ ε )ln(1− X ) + ε 2 X + (
Find volume of the PFR kC A0 $ 1− X '

35 36

Solution Check Your Understanding 3

2A → B SECOND ORDER reaction

Substitute in the value

Solve Example 3 again to
F "
VPFR = A02 $ 2ε (1+ ε )ln(1− X ) + ε 2 X +
kC A0 #
(1+ ε ) 2 X %
1− X &
" %
' ε = y δ = (1) $ 1 −1' = −0.5
A0
find Volume of PFR but this
" mol % " dm3 %
$ 0.2 3 ' × $ 2.5 '"
s &$
#2 &

)1+ (−0.5)+ (0.6) %

2
time assume both A and B
are in Liquid phase
# dm & # )1+ (−0.5)+ ln )1− 0.6+ + (−0.5) 2 (0.6) + * , '
= 2$
2(−0.5) * , * , ''
" )1− 0.6+
dm3 %" mol % $# * , &
$ 0.5 '$ 0.2 3 '
# mol.s &# dm &
VPFR = 24.6dm3

9
37

4.2 Design for Multiple Reactor System

38
4.2 Design for Multiple Reactor System
(Design of CSTRs in Series)
(Design of CSTRs in Series)
A→B FIRST ORDER LIQUID PHASE
FA0 − FA1 FA0 − FA1 FA0 X 1
VCSTR,1 = = =
−rA1 k1C A1 k1C A0 (1− X 1 )
υ0 X 1
VCSTR,1 =
k1 (1− X 1 )
VCSTR,1 1 X1
Space Time, τ 1 = =
υ0 k1 (1− X 1 )
τ 1k1
We can rearrange to obtain X 1 =
(1+ τ 1k1 )
" τ 1k1 %
Since C A1 = C A0 (1− X 1 ) = C A0 $1− '
# (1+ τ 1k1 ) &
Therefore outlet concentration from 1st reactor
C A0
C A1 =
1+ τ 1k1

39 40

4.2 Design for Multiple Reactor System 4.2 Design for Multiple Reactor System
(Design of CSTRs in Series) (Design of CSTRs in Series)
A→B FIRST ORDER LIQUID PHASE A→B FIRST ORDER LIQUID PHASE
F −F υ (C − C A2 )
VCSTR,2 = A1 A2 = 0 A1 For n equal-sized CSTRs connected in series:
−rA2 k2C A2
VCSTR,2 (C − C A2 ) C A0
= τ 2 = A1 C An =
υ0 k2C A2 (1+ τ k) n
C A1 In terms of conversion:
We get C A2 =
1+ τ 2 k2 1
X = 1−
C A0 (1+ τ k) n
Outlet concentration from 1st reactor,C A1 =
1+ τ 1k1 The rate of reaction in the nth reactor is:
C A0 C A0
Therefore, C A2 = −rAn = kC An = k n
(1+ τ 1k1 )(1+ τ 2 k2 ) (1+ τ k )
If both reactors equal size (τ 1 = τ 2 ) and isothermal (k1 = k2 )
C A0
Outlet concentration from 2nd reactor, C A2 =
(1+ τ k) 2

10
 42

4.3 Pressure Drop in Reactor 41 4.4 Reversible Reactions

1. At equilibrium, the rate of reaction is identically zero
1. In liquid phase, effect of pressure drop can be for all species, –r A = 0.
ignored. 2. For general reaction,
2. In gas phase, the concentrations is
aA + bB ⇔ cC + dD
proportional to the total pressure therefore
the effects of pressure drop need to be the concentrations at equilibrium are related by the
considered. thermodynamic relationship for equilibrium constant,
Kc.
3. For ideal gas with variable volume, the outlet c d d+c−b−a
CCe C De " mol %
volumetric flowrate is given as KC = a b
⇒$ 3'
C Ae C Be # dm &
!P $
υ = υ0 (1+ ε X) # 0 & 3. Remember for reversible reaction, concentration
"P% and conversion, X are evaluated at EQUILIBRIUM!

43 44

Example 3 4.4 Reversible Reactions

Given the chemical equation as following: 1. For general reversible reaction, kA
A⇔ B
k− A

2A ⇔ B + 2C 1. The rate of disappearance of A, –rA for elementary reaction

Therefore the concentration equilibrium
constant, Kc for the above reaction is
−rA = −rA,net = −rA, forward − rA,reverse = k AC A − k− AC B
rate constant of forward reaction k A
KC =
rate constant of reverse reaction k− A
=

2 ( "k % +
C BeCCe Therefore; − rA = k AC A − k− AC B = k A *C A − $$ − A '' C B -
KC = 2
*) # k A & -,
C Ae ( C +
−rA = k A *C A − B -
) KC ,

11
45 46

4.4 Reversible Reactions Example 4

1. For general reversible reaction, kA The gas phase isomerization reaction is given as
2A ⇔ B + C following:
k− A
2A ⇔ B
1. The rate of disappearance of A, –rAfor elementary reaction The reversible reaction is to be carried out in a
−rA = −rA,net = −rA, forward − rA,reverse = k AC A2 − k− AC BCC isothermal constant pressure flow system with pure A
at 260 oC with total pressure of the system is 310 kPa.
rate constant of forward reaction k A
KC = = Given the reaction rate constant is 110 s -1 and the
rate constant of reverse reaction k− A
equilibrium constant as 0.8 mol/L. Use R = 8.314
" k % kPa.dm3/mol.K.
Therefore; − rA = k AC A2 − k− AC BCC = k A $$C A2 − − A C BCC ''
# kA & Determine the equilibrium conversion and calculate the
" 2 CC % CSTR volume necessary to achieve 85% of the
−rA = k A $$C A − B C '' equilibrium conversion if given the feed rate of A as 30
# KC &
L/s.

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4.4 Reversible Reactions 48
4.4 Reversible Reactions
Step 1: Determine the equilibrium conversion, Xe Step 2: CSTR volume necessary to achieve 85% of the
y P (1)(310) mol equilibrium conversion (X = 0.85Xe)
C AO = AO = = 0.07
RTo 8.314(260 + 273.15) L Actual conversion, X = (0.85)(0.096) = 0.0816
1 b 1 C AO (1− X ) mol (1− 0.0816) mol
ε = y AOδ = (1)( −1) = −0.5 AND = CA = = 0.07 = 0.067
2 a 2 (1− 0.5X ) L #$1− (0.5× 0.0816)%& L
F F (1− X e ) C AO (1− X e )
Stochiometry: C A = A = AO = mol
υ υ o (1+ ε X e ) (1− 0.5X e )
0.5C AO X (0.5)(0.07 L )(0.0816) mol
b CB = = = 0.00298
FB FAO X e 0.5FAO X e 0.5C AO X e (1− 0.5X ) #1− (0.5× 0.0816)%
$ & L
CB = = a = =
υ υ o (1+ ε X e ) υ o (1+ X e ) (1− 0.5X e ) ' C * 1' 0.00298 * mol
Therefore − rA = k ))C 2A − B ,, = 110 ) (0.067) 2 − , = 0.084
0.5C AO X e KC + s( 0.8 + L.s
(
CB (1− 0.5X e )
In equilibrium' KC = = 0.8 = 2 From the quadratic ' mol *' L *
C 2A C AO (1− X e ) 2 equation we obtain ) 0.07 ,) 30 , (0.0816)
F X ( L +( s +
(1− 0.5X e ) 2 X e1 = 0.096 or X e2 = 1.90. VCSTR = AO = = 2.04L
Why do we choose −rA mol
Solve to get X e = 0.096 Xe = 0.096??? 0.084
L.s

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