CHAPTER 4

ISOTHERMAL REACTION DESIGN:

PART 1

Norzita
Mohd Asmadi Ngadi
Bin Mohammed Yussuf
Faculty of Chemical & Energy Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Contents

Design structure for isothermal reactors

Scale-up liquid-phase batch reactor

data to the design of a CSTR

Tubular reactors

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 Topic Outcomes

Week Topic Topic Outcomes

4 Isothermal Reactor Design It is expected that students are able to:

• Design structure for isothermal • Describe the algorithm that allows

reactors solving chemical reaction for isothermal
reaction
• Scale-up of liquid-phase batch
reactor data to the design of a • Determine size of batch reactor, CSTR,
CSTR PFR, and PBR for isothermal operation
given the rate law and feed conditions.
• Tubular reactors

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 Overview
This chapter brings all the material in the preceding 3
chapters together to arrive at logical structure for the
design of various types of reactors

By using this structure, one should be able to solve

reactor engineering problems through reasoning
rather than memorization of numerous equations
together with the various restrictions and conditions
under which each equation applies.

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Isothermal Reaction Design Algorithm

General Mole Balance Chapter 1

Apply mole balance to specific

reactor design equation– Batch,
CSTR, PFR, PBR
Chapter 2
Is rate of law –rA=f(X) given?
Yes

Combine all design equation and rate law

Size of reactor

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 Cont.
No information of rate of
law –rA=f(X) Chapter 3

Use the stoichiometry to Gas (with or without pressure drop)

express concentration as a
function of conversion Or Liquid phase

Chapter 4
Obtain the rate law
–rA=f(X) from the
stoichiometry

Combine all design equation, rate

law and stoichiometry

Size of reactor
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Algorithm for Isothermal Reactor

‘Algorithm’: procedure/step for solving a problem

Isothermal reactor – is not involved energy balance

The STEPS are

1. Mole balances
2. Rate laws: – r = k(fn C)
3. Stoichiometry: concentration for species
4. Combine: to calculate V or X

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Design Structure for Isothermal Reactors
Mole balance equations

Rate laws
rate vs. concentration

Stoichiometry
(to find concentration vs X)

Combine and evaluate

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 Batch Operation
Calculate time necessary to achieve given conversion X
for irreversible 1st & 2nd order reaction run in a batch
reactor.
A→B

dX
Mole balance : NA0 = −rA V0
dt

Rate laws : − rA = kC A − rA = kC 2A

NA
Stoichiometry : CA = = C A0 (1− X )
V0
dX dX
Combine : = k (1− X ) = kC A0 (1− X )
2

dt dt
1 1 1 X
t = ln t=
kC A0 (1− X )
Integrate :
k 1− X
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Typical Cycle Time in a Batch Reactor

Activity Time (h)

1. Charge feed to the reactor and agitate, tf 1.5 – 3.0
2. Heat to reaction temperature, te 0.2 – 2.0
3. Carry out reaction, tR (varies)
4. Empty and clean reactor, tC 0.5 – 1.0

Total time excluding reaction 3.0 – 6.0

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 Typical Reaction Times

Order of magnitude time to achieve 90% conversion in a batch reactor:

Reaction time First-Order Second-Order

tR k (s-1) kCA0 (s-1)
Hours 10-4 10-3
Minutes 10-2 10-1
Seconds 1 10
Milliseconds 1000 10,000

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 Example: Batch Data
It is desired to design a CSTR to produce 200 million pounds of ethylene glycol per
year by hydrolyzing ethylene oxide.

However, before the design can be carried out, it is necessary to perform and analyze
a batch reactor experiment to determine the specific reaction rate constant.

Since the reaction will' be carried out isothermally, the specific reaction rate will need to
be determined only at the reaction temperature of the CSTR.

At high temperatures there is a significant by-product formation, while at temperatures

below 40°C the reaction does not proceed at a significant rate; consequently, a
temperature of 55°C has been chosen.

Since the water is usually present in excess, its concentration may be considered
constant during the course of the reaction. The reaction is first-order in ethylene oxide.

O H2S O4 CH2 OH
+ H2O
H2C CH2 CH2 OH
A + B C
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Example: Batch Data (Cont.)
In the laboratory experiment, 500 mL of a 2 M solution (2 kmol/m3) of ethylene oxide in
water was mixed with 500 mL of water containing 0.9 wt % sulfuric acid, which is a
catalyst. The temperature was maintained at 55°C. The concentration of ethylene
glycol was recorded as a function of time (Table). From these data, determine the
specific reaction rate at 55°C.

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 Solution: Batch Data
1 dNA
Mole balance : = rA
V dt

Rate laws : − rA = kC A

Stoichiometry :

Species Symbol Initial Change Remaining Concentration

C A = C A0 (1− X )
CH2 OH
NA = NA0 (1− X )
O
H2C CH2
+ HA
2O − NA0 X
NA0CH OH
2

NB = NA0 (ΘB − X ) C B = C A0 (ΘB − X )

CH2 OH
O
+ H2O B ΘB NA0 − NA0 X
H2C CH2 CH2 OH
CH2 OH
+ H2O C 0 + NA0 X NC =NA0 X C C =C A0 X
CH2 OH

NT0 NT = NT0 −NA0 X

C B  C A0 ΘB = C B0
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Solution: Batch Data (Cont.)
NA NA t= 0, CA = CA0
CA = =
V V0
C A0
ln = kt
1 dNA d(NA /V0 ) dC A CA
= =
V dt dt dt
Conc. of ethylene oxide at any time t

dC A C A = C A0 e −kt
Combine : − = kC A
dt
From reaction stoichiometry
Isothermal operation
NC = NA0 X = NA0 − NA
CA dC A t
− =  kdt
C A0 C 0
A

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Solution: Batch Data (Cont.)
Liquid-phase, V = V0
NC NC
CC = = = C A0 − C A
V V0
(
C C = C A0 1− e −kt )
–k

C A0 − C C
ln = −kt
C A0

ln10 2.3
k= = = 0.311min −1
t2 − t1 8.95 − 1.55

(
− rA = 0.311min −1 C A )
This rate law can be used in the
design of an industrial CSTR
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 CSTR Design Equation
CSTR with a liquid-phase reaction:

Single CSTR mole balance

FA0 X
Design equation: V=
(− rA )exit
V C A0 X
= =
Space time:
0 (− rA )exit

Rate law (1st order): − rA = kC A

Stoichiometry: C A = C A0 (1− X )

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 CSTR
FA0 X V C A0 X
V=
(− rA )exit
; =
0
=
(− rA )exit − rA = kC A C A = C A0 (1 − X )

1 X  k
Combining: =   X=
k  1− X  1+ k

C A0
CA =
1+ k Damköhler Number

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 Damköhler Number
Dimensionless number that can give us a quick estimate of the
degree of conversion that can be achieved in CSTR

− rA0 .V
Da =
FA0

kC A0 .V
1st order irreversible Da = =  .k
reaction  0 .C A0

kC 2A0 .V
2nd order irreversible reaction Da = =  .kC A0
0C A0

Gives a quick estimate of the degree of Da < 1 X < 10%

conversion Da > 1 X > 90%

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 CSTR in Series (Cont.)
Concentration flowing to the 2nd
reactor
C A0
C A1 =
1+  1k1 CA0
CA1 CA2
X1 X2

Design equation the 2nd reactor

FA1 − FA2 C − C A2
V2 = = υ 0 A1
− rA2 k 2C A2
-rA1 -rA2
V1 V2
C A0
C A2 =
So,
(1+  1k1 )(1+  2k 2 )
C A0
If the reactor have the same size and C A2 =
temperature (1+ k )2
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CSTR in Series (Cont.)
C A0
C A2 =
(1+ Da )2
In term of Damköhler number

C A0
For n reactors C An =
(1+ Da )n

C A0
C A0 (1− X ) =
Conversion
(1+ Da )n
1
X = 1− n equal size, same T
(1+ Da )n  1 =  2 = ..... =  n = 
k1 = k 2 = ..... = k n = k
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 CSTR in Series
When Damköhler number is above 1, a high conversion in few
reactors

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 CSTR in Parallel
X1
FA01
Let’s consider identical reactors with the
feed equally distributed, than conversion
factors and the reaction rates are the
same
FA0
Xi
FA0i

 Xi  V FA0i  X i 
Vi = FA0i   or =  
 − rAi  n n  − rAi 
Xn

So, the situation is identical to a single

reactor with the size equal to the total
volume of all reactors.

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 Summary: CSTR
FA0 .X
Mole balance : V=
− rA

Rate laws : − rA = kC A − rA = kC 2A

V
Space time : 
0

Parallel
 .k (1 + 2Da) − 1+ 4Da
X= X=
1+  .k 2Da
Conversion :
Series
1
X = 1− Da=.k.CA0 (2nd order)
(1 +  .k)n

Number of reactors
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 Example: CSTR Data

The elementary gas-phase reaction

(CH3)3COOC(CH3)3 → C2H6 + 2CH3COCH3

is carried out isothermally in a flow reactor with no pressure drop. The

specific reaction rate at 50°C is 10-4 min-1 (from pericosity data) and the
activation energy is 85 kJ/mol. Pure di-tert-butyl peroxide enters the
reactor at 10 atm and 127°C and a molar flow rate of 2.5 mol/min.

Calculate the reactor volume to achieve 90% conversion in:

a. CSTR
b. PFR

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 Solution: CSTR Data
a. CSTR A → B + 2C

FA0 X
Mole balance : V=
− rA

Rate laws : − rA = kC A ε = y A0 δ = 1(2 + 1− 1) = 2

C A0 (1− X )
Stoichiometry : CA =
(1+ εX )
P 10 mol
: C A0 = A0 = = 0.3
RT (0.082 )(400 ) dm3
FA0 X (1+ εX )
Combine : V=
C A0k (1− X )

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Solution: CSTR Data (Cont.)

85000  1 1 
 − 
k = 10 − 4 e 8.31  323 400 
= 0.044

V=
(2.5mol/min)(0.9 )(1+ 2(9) )
(0.044m −1 )(0.3mol/dm3 )(1− 0.9 )

V = 4772dm3

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Tubular Reactor: Liquid Phase
dX
Design equation: FA0 = −rA
dV
X
In the ABSENCE of pressure drop: V = FA0 dX
0 − rA

⎯→ products
Consider a 2nd order reaction: A ⎯

Rate law: − rA = kC 2A

Stoichiometry: C A = C A0 (1− X )

F X dX  X kC A0 Da 2
V = A02
kC A0 0
=
(1− X )2 kC A0 (1− X )
X= =
1+ kC A0 1+ Da 2

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Tubular Reactor: Gas Phase
For T, P constant, the concentration is a function of conversion

FA FA C A0 (1− X )
Stoichiometry: C A = = =
  0 (1+ εX ) (1+ εX )

Rate law: − rA = kC 2A

X
FA0 (1 + εX)2
2 
Combining: V = dX
kC A0 0 (1 − X)
2

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Tubular Reactor: Gas Phase (Cont.)

Integral equation in APPENDIX A.1

Reactor volume for a 2nd order gas-phase reaction

0  (1 + ε )2
X
V= 2ε(1+ ε )ln(1− X ) + ε X +
2

kC A0  1− X 

Divide both sides by cross-sectional area of the reactor

0  (1 + ε )2
X
L= 2ε(1+ ε )ln(1− X ) + ε X +
2

kC A0 A c  1− X 

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Tubular Reactor: Gas Phase (Cont.)
if ε<0: i.e. number of moles
↓: volumetric flow rate ↓,
the residence time↑, so X↑

if ε>0: i.e. number of moles

↑ : flow rate ↑, the
residence time ↓, so X ↓

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Summary: Tubular Reactors (Gas Phase)

X
dX
Mole balance : V = FA0 
0
− rA

Rate laws : − rA = kC A − rA = kC 2A

(1 − X)
Stoichiometry : C A = C A0
(1 + εX)

X
F
X
(1 + εX) FA0 (1 + εX)2
2 
V= dX
Combine : V = A0

kC A0 0 (1 − X)
dX
kC A0 0 (1 − X)
2

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 Example: (Cont. from CSTR)

V = FA0 
X dX FA0 X (1+ εX ) dX
Combine :
0
=
− rA kCA0 0 (1− X )

FA0  1 
=  (1 + ε )ln − εX 
kC A0  1− X 

 2.5mol/min   1 
V =  (1+ 2 )ln − 1.8 
(
 0.044min 0.3mol/dm
−1 3
)( )   1− 0.9 

(
= 189.4dm 3 (5.11) )
V = 967dm3

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 CHAPTER 4
PRESSURE DROP IN REACTORS

Norzita Ngadi
Faculty of Chemical & Energy Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia

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Pressure Drop & the Rate Law
In the liquid phase pressure drop doesn’t lead to
any significant volume and therefore concentration
changes can be neglected.

In the gas phase can be an important factor

P0 T
Volumetric flow:  = 0 (1+ εX )
P T0
If isothermal T0=T
Fj FA0 (j +  j X ) C A0 (j +  j X ) P T0
Cj = = =
  (1 + X ) P0 T (1 + X ) P0 T
P T0
0
Chap. 3

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Pressure Drop & the Rate Law
To account for pressure drop we have to use dX
FA0 = −rA'
DIFFERENTIAL FORM of the equation dW

Rate law: − rA' = kC 2A 2A ⎯

⎯→ B + C

C A0 (1− X ) P T0
2
 C A0 (1− X ) P T0 
Stoichiometry: C A = − r = k
'

(1 + X ) P0 T A
 (1 + εX ) P 0 T 

For isothermal operation:

2 2
dX 1  C A0 (1− X ) P T0  kC A0  (1− X ) P 
= k  =
dW FA0  (1+ εX ) P0 T  0  (1+ εX ) P0 

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 Pressure Drop (Cont.)

Right hand is a function of only conversion and pressure

dX
= F1 (X, P )
dW

Need to relate the pressure drop to the catalyst weight in

order to determine the conversion as a function of catalyst
weight:

P = f (W )

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 Ergun Equation
Pressure drop in a packed porous bed is described by Ergun
equation:

dP G  1− Φ  150(1 − Φ)μ 
=−  3  + 1.75G 
dz ρgc Dp  Φ   Dp 

dominant for laminar flow dominant for turbulent flow

 : Porosity = volume of void/total volume

Dp : Particle diameter
G = u : Superficial mass velocity,  – gas density
gc : Conversion factor, = 1 for metric system

Ergun equation: Bird et al., (1960). Transport Phenomena. p. 200 Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Pressure Drop in PBR (Cont.)
We are now going to calculate pressure drop through the bed:

Steady state,
• •
m0 = m  ρ0 0 = ρ

 P0  T  FT
 =  0    Chapter 3
 P  T0  FT0

 P  T0  FT0
ρ = ρ0   
 P0  T  FT

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Pressure Drop in PBR (Cont.)
dP G (1− Φ ) 150(1 − Φ)μ  P0  T  FT
=−  + 1.75G   
dz ρ0 gc DpΦ 3  Dp  P  T0  FT0

dP P0 T FT
= −β 0
dz P T0 FT0

G(1 − Φ) 150(1 − Φ)μ 

β0 = 3 
+ 1.75G 
ρ0 gc DpΦ  Dp 

In terms of catalyst weight: W = (1 − Φ )A c z  ρc

More interested
in W than z

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 Multiple Reactions/ Membrane Reactors

Is just the product of the solid density Fraction of solids

The bulk density of the catalyst, ρb = ρc (1−  )

Change the variables in terms of catalyst β0

α=−
A c (1− Φ )P0

dP β0 P0  T  FT dP α T P0  FT 
=−   =−  
dW A c (1− Φ )ρc P  T0  FT0 dW 2 T0 P/P0  FT0 

dy α T FT
Let , y = P/P0 ; =−
dW 2y T 0 FT0 Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Single Reactions PBR
 FA0 
FT = FT0 + FA0 δC = FT0 1+ δX 
 FT0 
Chapter 3
FT
= 1+ εX
FT0

ε = − ve : P  <  = 0
dP α T P0 ε = + ve : P  >  = 0
=− (1+ εX )
dW 2 T0 P/P0

dP dX
Must be solved = F2 (X, P ) = F1 (X, P ) Previous slide
simultaneously dW dW
dy α T FT
Let , y = P/P0 ; =−
dW 2y T 0 FT0 Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Analytical Solution (Special Case)
If  = 0 and isothermal

2P d(P/P0 ) d(P/P0 )
2
dP α P0
=− = −α = −α
dW 2 P/P0 P0 dW dW

Integrating with P = P0 at W = 0 yields

2
P  P
= (1− αW)
1/2
  = 1− αW
 P0  P0
Pressure drop parameter

In terms of reactor length, z

1/2
P  2β 0 z 
= 1− 
P0  P0 

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Reaction with Pressure Drop
Consider 2nd order isothermal reaction

A→B

dX
Mole balance : FA0 = −rA'
dW

y = (1− αW)
1/2
Rate laws : − rA' = kC 2A

NA P
Stoichiometry : C A = = C A0 (1 − X )
V0 P0

Combine :
dX kC 2A0
=
dW FA0

(1− X )2 (1− αW)1/2
2

FA0 dX
= (1− αW)dW
Separating
:
variables kC A0 (1− X )
2 2

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Reaction with Pressure Drop (Cont.)
Integrating with limit X = 0, W = 0, and substituting for FA0 = CA0 0

0 X αW
= W−
kC A0 1− X 2

kC A0 W  αW 
1− 
0  2 
X=
kC A0 W  αW 
1+ 1− 
0  2 

Solving for catalyst weight

1− 1− (2 0 α)/kCA0 X/(1− X )

1/2
W=
α

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 Example
The elementary isomerization

A→B

is carried out at 20 atm in a fluidized CSTR

containing 100 kg of catalyst where 50%
conversion is achieved

It is proposed to replace the CSTR with a packed bed reactor

The entering pressure was 20 atm and the exit pressure was found to be 10 atm.

a. What would be the conversion if No pressure drop?

b. What will be the conversion in the new PBR with pressure drop?

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 Tutorial 1
The irreversible gas phase reaction

A + B → 2C

is carried out in a PBR. The reaction is non-elementary in that it is first order in A

and zero order in B. The feed is equal molar in A and B and the pressure at the
entrance is 10 atm and the pressure at the exit is 2 atm.
What is the conversion exiting the reactor?

Additional Information
FA0 = 100 mol/s
k = 1 dm3/kg.s
CA0 = 1 mol/dm3

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Spherical Packed-bed Reactor
Advantages
• Suitable for pellet catalyst use
• Pressure drop in the reactor is minimum
• Inexpensive to build
• Most economical shape for high pressure

dy β0
= − (1 + εX)
dz P0 y For y=P/Po

Cross sectional area: A c = π[R 2 −(z − L) 2 ]

 1 1 
Catalyst weight: W = ρc(1 −  )V = ρc(1 −  ) π R 2 z − (z − L) 3 − L3 
 3 3 

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Pressure Drop in Pipes
Normally the pressure for gases flowing through pipes
without packing can be neglected

The pressure drop along the length of the pipe

dP du 2fG 2
= −G −
dL dL ρD

Where :
D = pipe diameter, cm
u = average velocity of gas, cm/s
f = Fanning friction factor
G = u, g/cm2.s

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Pressure Drop in Pipes (Cont.)
Replace u = G/, T and FT = constant, and combine with,

 P  T  F P dP 2 dP 2fG 2
Previous ρ = ρ0   0  T0 ρ = ρ0 −G + =0
slide  P0  T  FT P0 dL PdL D

Integration, P = P0 when L = 0, assumption: f = not vary

P02 − P 2 P  L P  P02 − P 2 P L
= G 2 0  2f + ln 0  = 2fG 2 0
2 ρ0  D P  2 ρ0 D

Rearranging,
1/2
P  4fG 2 V 
= (1− αp V )
1/2
= 1−  4fG 2 V
P0  ρ0P0 A c D  αp =
ρ0P0 A c D

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Unsteady State Operation
of Reactors

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Unsteady State Operation of Stirred Reactors

reactor start-up Semibatch w. cooling reactive distillation

During the start up of a reactor:

Slow addition of component B to a large quantity of A e.g. when

reaction is highly exothermic or unwanted side reaction can occur at high
concentration of B.

One of the products is vaporized and withdrawn continuously.

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Startup of CSTR
Conversion doesn’t have any meaning in startup so we have to use
concentrations.
dNA
FA0 − FA + rA V =
dt
For liquid phase with constant overflow (V = V0), and using  = V0/ 0
dC A
C A0 − C A + rA = 
dt

For the 1st order reactions, –rA = kCA

dC A 1+ k C A0 C A0   t 
+ = CA = 1 − exp  − (1 + k ) 
dt   1+ k     

E.g. to reach 99% steady state concentration

ts = 4.6
C 
C A = A0 , ts = 4.6
1+ k 1+ k ts = 4.6/k
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
 Semibatch Reactors
Semibatch reactors could be used e.g. to
improve selectivity

A + B ⎯⎯→
kD
D rD = kC A2 C B

A + B ⎯⎯→
kU
U rU = kC AC B2

Selectivity:
rD k D C A
S D/U = = Chap. 6
rU k U C B

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Eqn. in Terms of Concentrations
A+B→C
For component A 0, CB0
dNA
rA V =
B
dt
In terms of concentration

d(C A V) VdC A dV
rA V = = +CA
dt dt dt A

Semibatch reactor volume as a function of time

V = V0 +  0 t

VdC A dC A 0
− 0C A + rA V = = rA − C A
dt dt V
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Eqn. in Terms of Conc. (Cont.)
For component B
dNB
= rB V + FB0
dt

In terms of concentration

d(C B V ) VdC B C B dV
= + = rB V +  0C B0
dt dt dt

dC B  (C − CB )
= rB + 0 B0
dt V

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Eqn. in Terms of Moles
Solve semibatch problems by leaving the mole balance equations in
terms of the no. of moles of each species (NA, NB, NC, & ND)

dNA dNB
rA V = = rB V + FB0 V = V0 +  0 t
dt dt

Definition of concentration for batch system

NA NB
CA = CB =
V V

E.g. –rA = kA CA CB

dNA NA NB dNB NA NB
= −k = −k + FB0
dt V0 +  0 t dt V0 + ν 0 t

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Eqn. in Terms of Conversion
Consider
A +B  C +D
• B is fed to a vat containing only A initially; 1st order reaction in
A & 1st order reaction in B

The number of moles of A remaining at any time, t,

NA = NA0 − NA0 X

Species B,

t
NB = NB i +  FB0 dt − NA0 X
0

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Eqn. in Terms of Conversion (Cont.)
For constant molar flow rate Reversible 2nd order reaction, rate law

 C C 
NB = NB i + FB0 t − NA0 X - rA = k  C A C B − C D 
 KC 

Mole balance on species A, Conc. of reactants as a function of X

and t
dNA NA NA0 (1- X )
rA V = CA = =
dt V V0 + 0 t
NB N + FB0 t − NA0 X
Number of moles of C and D, e.g., CB = = Bi
V V0 + 0 t

NC = NC i + NA0 X NC NA0 X
CC = =
V V0 + 0 t

ND NA0 X
CD = =
V V0 + 0 t

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Eqn. in Terms of Conversion (Cont.)
dNA  C C 
NA = NA0 − NA0 X rA V = - rA = k  C A C B − C D 
dt  KC 

Combine → substituting for the concentrations → dividing by NA0


dX k (1 − X )(NBi + FB0 t − NA0 X ) − NA0 X 2 /K C
=
( )
dt V0 + 0 t

Needs to be solved numerically to determine the conversion as a

function of time.

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Equilibrium Conversion
Reversible reactions carried out in semi batch reactor

A +B  C +D

The maximum attainable conversion will change as the reaction

proceeds because more reactant is continuously added to the reactor.

 C C 
Rate law: - rA = k C A C B − C D 
 KC 

If the reaction were allowed to reach equilibrium after feeding species

B for a time t, the equilibrium conversion,

 NCe  NDe 
  
C Ce C De V  V  = NCe NDe
KC = =
C Ae C Be  NAe  NBe  NAeNBe
  
 V  V 
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Equilibrium Conversion (Cont.)
KC =
(NA0 X e )(NA0 X e )
NA0 (1 − X e )(FB0 t − NA0 X e )
NA0 X 2e
KC =
(1− X e )(FB0 t − NA0 X e )

Rearrange,

NA0  X 2e 
t=  K C X e + 
K C FB0  1− X e 

Or
2
 FB0 t    FB0 t  F t Equilibrium
K C 1+
  − K C 1 +
  − 4(K C − 1)K C B0 conversion in a
 NB0    NB0  NB0
Xe = semibatch reactor
2(K C − 1)

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

 Example 2
The irreversible liquid phase acid catalyzed isomerization reaction A ⎯H⎯ ⎯→ B
2 SO 4

is carried out isothermally in a semibatch reactor.

A 2 molar solution of H2SO4 is fed at a constant rate of 5 dm3/min to a reactor that initially
contains no sulfuric acid. The initial volume of pure A solution in the reactor is 100 dm3.
The concentration of pure A is 10 mol/dm3. The reaction is first order in A and first order
in catalyst concentration and the specific reaction rate is 0.05 dm3/mol min–1. The
catalyst, of course, is not consumed during the reaction.

a) Obtain an analytical solution for the number of moles of A, NA and the concentration
of A, CA, as a function of time. What is the concentration of A and of H2SO4 after 30
minutes?

Additional Information

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia