Chemical Engineering Kinetics

and Reactor Design

Assoc. Prof. Dr. Duangkamol Na-Ranong

Department of Chemical Engineering
Faculty of Engineering
King Mongkut’s Institute of Technology Ladkrabang

2024-1-W01
 CHAPTER 1: Mole Balance
1. The Rate of Reaction
2. General Mole Balance Equation
3. Ideal Reactors:
 Batch Reactors
 Continuous Flow Reactors:
- Continuous Stirred Tank Reactor (CSTR)
- Plug Flow Reactor (PFR)
- Packed Bed Reactor (PBR)
 Semi-Batch Reactors
After completing this chapter, you will be able to:
• Describe and define the rate of reaction.
• Derive the general mole balance equation.
• Apply the general mole balance equation to the four most common types
of industrial reactors.
Assoc. Prof. Dr. Duangkamol Na-Ranong
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 Chemical Reaction
A chemical reaction has taken place when a detectable number
of molecules of one or more species have lost their identity and
assumed a new form by a change in the kind or number of
atoms in the compound and/or by a change in structure or
configuration of these atoms.

In this classical approach to chemical change, it

is assumed that the total mass is neither created
nor destroyed when a chemical reaction occurs.
AB
However, when considering the individual
mT  constant species involved in a particular reaction, we do
mA  mB  speak of the rate of disappearance of mass of a
minert  constant particular species.

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 1. Reaction Rate or Rate of Reaction
• The reaction rate tells how fast a number of moles of one
chemical species are being consumed to form another chemical
species.
• Chemical species refers to any chemical component or element
with a given identity.
• The identity of a chemical species is determined by the kind,
number, and configuration of that species’ atoms.
Kind
Number
Configuration

As a consequence of the different configurations, these two isomers

display different chemical and physical properties. Therefore, we
consider them as two different species.
Assoc. Prof. Dr. Duangkamol Na-Ranong
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The rate of disappearance of a species (A) is the number of A
molecules that lose their chemical identity per unit time per unit
volume through the breaking and subsequent re-forming of
chemical bonds during the course of the reaction.
In order for a particular species to “appear” in the system, some
prescribed fraction of another species must lose its chemical
identity.
There are three basic ways a species may lose its identity:

Decomposition
Combination

Isomerization

Assoc. Prof. Dr. Duangkamol Na-Ranong

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 The reaction rate can be expressed as either:
 The rate of Disappearance of reactant: -ri
or
 The rate of Formation (Generation) of product: ri

 The reaction rate is usually defined based on reacting volume

(mol/dm3/s).
 The reaction rate of a solid catalytic reaction may be defined
based on
 mass of catalyst as ri’, -ri’ (mol/gcat/s) or
 reacting surface as ri’’, -ri’’ (mol/(m2cats)

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Ex. 1a : Consider a simple isomerization reaction
1A 1B
rA = the rate of formation of species A per unit volume
-rA = the rate of a disappearance of species A per unit volume
rB = the rate of formation of species B per unit volume

If Species B is being formed at a rate of 0.2 moles per decimeter

cubed per second, i.e.,
rB = 0.2 mol/dm3/s

Then A is disappearing at the same rate: -rA = 0.2 mol/dm3/s

The rate of formation (generation of A) is: rA = -0.2 mol/dm3/s

-rj = -(rj)

Assoc. Prof. Dr. Duangkamol Na-Ranong

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Reaction rate depends on
- Reaction conditions (T, C, P)
- Type of catalyst

• IMPORTANT NOTE:
- The rate of reaction does not depend on (size, shape, type,….) reactor
- dCA/dt is not the rate of reaction
- Rate of reaction is an algebraic equation.

- Power Law is the simplest form of rate of reaction.

- It must be determined from experiment.

Assoc. Prof. Dr. Duangkamol Na-Ranong

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 2. General Mole Balance
1. Specify the system boundary
Fj0 Nj Fj 2. Choose one of the species “j ”
Gj
V: system volume

Nj number of mole of “j” in the system volume

Gj rate of generation of “j” within the system
Fj molar flow rate of “j”; with subscript “0” means into, w/o “0” means out
The general mole balance on species j in a system volume (V)
 Molar Flow  Molar Flow   Molar Rate   Molar Rate 
 Rate of    Rate of   Generation    Accumulation 
       
 Species j in   Species j out   of Species j   of Species j 
dN j
Fj0  Fj  Gj 
dt
 mol   mol   mol   mol 
       
 time   time   time   time 
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 Rate of Generation of Species “j”
rj is a function of If all varibles are spatially uniform:
- T, Cj Gj  rj V
- Catalytic activity
dN j
Fj0  Fj  rj  V 
dt
If NOT!!
V1 V2
Limits of M to   V  0
rj1 rj 2 M
G j   ( rj, i  V ) 
V
 rj,i dV
G j2  rj2 V2 i 1
G j1  rj1V1
V dN j
Fj0  Fj   rj dV 
dt
Divide the system volume into
M elements (i = 1, 2, ..., M)
M
Gj, i   rj,i Vi
i 1

Assoc. Prof. Dr. Duangkamol Na-Ranong

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3. Ideal Reactor: What is a reactor?
 Equipment used to carry out a chemical reaction in a safe manner.

AB
A AB AB

Types of reactor
 Phase of materials inside: Homogeneous vs. Heterogeneous
 Existing of catalyst: Catalytic vs. Non-catalytic reactor
 Operation mode: Batch, Semi-Batch, Continuous
 Operation mode and Fluid dynamics inside the reactor:
- Batch
- Continuous Stirred Tank Reactor (CSTR)
- Plug Flow Tubular Reactor (PFR or TR)
- Packed Bed Reactor (PBR)
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 Batch reactor

 Application of a batch reactor

- Small-scale operation
- Testing new processes that have not been fully developed.
- Manufacture of expensive products
- Processes that are difficult to convert to continuous operations.
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 Batch reactor
 Advantages:
High conversion can be obtained by leaving the reactant in the reactor
for long periods of time.
 Disadvantages:
- High labor costs per batch
- Variability of products from batch to batch
- Difficulty of large-scale production

Mixing pattern
in a batch reactor
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Continuous Stirred Tank Reactor (CSTR)
(vat or backmix reactor)

A CSTR is primarily used for liquid-

phase reactions.

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 Continuous Stirred Tank Reactor (CSTR)
 Advantages:
- Good temperature control is easily maintained.
- Cheap to construct
- Reactor has large heat capacity
- Interior of reactor is easily accessed
 Disadvantages:
- Conversion of reactant per volume of reactor is small
compared to other flow reactors.
- Dead-zones, where no mixing occurs, can develop.
- Reactants may bypass if outlet placed improperly.
- Difficulty of large-scale production

Assoc. Prof. Dr. Duangkamol Na-Ranong

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Tubular Reactor of Plug Flow Reactor (PFR)
The reactor is heated by high pressure
steam which has a temperature of 470
K and is fed into the reactor at point 1
and leaves the reactor at point 2. The
reactants flow through the tubes.

Tubular reactors are used most often for gas-phase

reactions.
The reactants are continually consumed as they flow
down the length of the reactor. In modeling the
tubular reactor, we assume that the concentration
varies continuously in the axial direction through the
reactor. Consequently, the reaction rate, which is
generally a function of concentration, will also vary
axially. There is no radial variation in reaction rate, and the
reactor is referred to as a plug-flow reactor (PFR).
Assoc. Prof. Dr. Duangkamol Na-Ranong
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 Tubular Reactor of Plug Flow Reactor (PFR)
 Advantages
- Easily maintained since there are no moving parts.
- High conversion rate per reactor volume.
- Mechanically simple.
- Unvarying product quality. Tubular reactors can also be used as
bioreactors or for small scale production.
- Good for studying rapid reactions.
- Efficient use of reactor volume.
- Good for large capacity processes.
- Low pressure drops.
- Tubes are easy to clean.

 Disadvantages
- Difficult to control reactor temperature
- Hot spots may occur within the reactor (exothermic reaction)
- Difficult to control due to temperature and composition variations
Assoc. Prof. Dr. Duangkamol Na-Ranong
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 Packed Bed Reactor (PBR)

A fluid-solid heterogeneous catalytic reaction occurs on the surface of the catalyst.

The greater the mass of a given catalyst, the greater the reactive surface area.

Assoc. Prof. Dr. Duangkamol Na-Ranong

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 Batch reactor
Operation: No feed and outlet streams during the reaction
Assumption: Perfect mixing

t  0; N A  N A0 t  t1 ; N A  N A1

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 3.1. Design Equation of a Batch Reactor
General mole balance 1. Perfect mixing  G j  rj  V
dN j 2. No feed and outlet streams
Fj0  Fj  Gj 
dt  Fj, 0  0 and Fj  0
d Nj
 rj V
dt

Consider isomerization of species A: A  B

1
dt  d Nj
rj  V

We should know the time (t1) required to N A1 N A0

1 1
- reduce the number of moles of A to NA1 or t1   rAV
dN A    rAV
dN A
- form NB1 moles of B N A0 N A1

Assoc. Prof. Dr. Duangkamol Na-Ranong

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 Concentration in a Batch Reactor
Nj
Cj 
V
Liquid phase:
Cj is commonly given in terms of molarity.

Gas phase:
Cj can be calculated from the state (temperature and pressure) inside the
batch reactor with assumptions of an ideal gas.

Pj yj PT yj P Cj = concentration of j
Cj   
RT RT RT Pj = pressure of j,
PT, P = total pressure
R = ideal gas constant
T = temperature
yj = mole fraction of j
Assoc. Prof. Dr. Duangkamol Na-Ranong
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 Batch Reactor
Constant volume or Variable volume batch reactor

dNA d (C A  V )
 rAV  rAV
dt dt

Consider the generic reaction:

t  0; N A  N A,0 t  t1 ; N A  N A,1
a AbB
 c C  d D

Constant volume batch reactor: V  V0

d (C A  V0 ) dC A dC A
 rAV0 V0  rAV0  rA
dt dt dt

Variable volume batch reactor: V  V0

d (C A  V ) dC A dV dC A
 rAV V  CA  rAV  rA
dt dt dt dt

Assoc. Prof. Dr. Duangkamol Na-Ranong

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Ex. 1-2b: The liquid phase cis-trans isomerization of 2-butene. The reaction is to be
carried out isothermally in a batch reactor. Assuming the reaction rate is first order
with respect to concentration of cis-2-butene and k is 0.01 s-1.
Calculate the time necessary to consume 95% of cis-2-butene in a 1000 dm3
constant-volume batch reactor with initial concentration (CA0) of 0.5 mol/dm3.
Calculate concentration of each species in the reactor at the end of reaction.
Show the change in concentration of each species in the batch reactor along the
reaction time.
1. Select specific species:

2. Mole balance:

3. Rate law:
4. Combine and solve the equations:

Assoc. Prof. Dr. Duangkamol Na-Ranong

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 Concentration in a Continuous Flow Reactor
Fj,0 Fj
Fj
Cj  Cj,0 Continuous Flow Reactor Cj

0 

Liquid phase: Cj is commonly given in terms of molarity.

Gas phase:
Cj can be calculated from the state (temperature and pressure) of the
streams of the continuous flow reactor with assumptions of an ideal gas.

Pj yj PT yj P Cj = concentration of j
Cj   
RT RT RT Pj = pressure of j,
PT, P = total pressure
R = ideal gas constant
T = temperature
yj = mole fraction of j

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Ex. 1-3: Using the ideal gas law to calculate CA0 and FA0
A gas of pure A at 830 kPa (8.2 atm) enters a reactor with a volumetic flow
rate, v0, of 2 dm3/s at 500 K. Calculate the entering concentration of A, CA0,
and the entering molar flow rate, FA0.

yA0  1
yA 0 P0
P0  830 kPa CA 0  ? CA 0 
RT0
0  2 dm /s
3

T0  500 K FA0
FA0  ? CA0 
0
FA0  CA0 0

Assoc. Prof. Dr. Duangkamol Na-Ranong

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Continuous Stirred Tank Reactor (CSTR)
Fj,0
Cj,0
0
V
Fj
Cj


Operation: Continuous mode

Assumption: - Steady-state
- Well-mixed

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 3.2. Design Equation of a CSTR
General mole balance Calculate volume necessary to reduce
d Nj the molar flow rate from FA0 to FA.
Fj0  Fj  G j 
dt
F  FA CA0 0  CA 
V  A0 V
Fj0  Fj  rj V  0 ( rA)exit ( rA)exit

Fj0  Fj
V
 rj 1. Continuous mode Fj0 and Fj  0

dN j
Fj,0 2. Steady-state 0
dt
Cj,0 3. Well-mixed G j  rj V
0 - Uniform T & Ci
rj V Fj - Toutlet = Tin reactor
Cj - Ci, outlet = Ci, in reactor
rj  f n (Cj, T ) 

Cj0 , T0 or Cj , T
Assoc. Prof. Dr. Duangkamol Na-Ranong
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Ex. 1-4: How large is the reactor volume? (CSTR)
Reconsider the liquid phase cis–trans isomerization of 2–butene (A  B). The
reaction is first order in A (–rA = kCA) and is carried out in a continuous stirred
tank reactor. The volumetric flow rate, , is constant, i.e.,  = 0.
1. Derive an equation relating the reactor volume to the entering and exiting
concentrations of A, the rate constant k, and the volumetric flow rate .
2. Determine the reactor volume to reduce the exiting concentration to 10%
of the entering concentration, i.e., CA = 0.1CA0, when the volumetric flow
rate is 10 dm3/min and the specific reaction rate, k, is 0.23 min-1.
1. Select specific species:
Fj,0
2. Mole balance:
Cj,0
0 3. Rate law:
rj V Fj 4. Combine and solve the equations
Cj
rj  f n (Cj, T ) 

Assoc. Prof. Dr. Duangkamol Na-Ranong 36

 3.3. Design Equation of a PFR
General mole balance 1. Continuous mode Fj0 and Fj  0
d Nj
Fj0  Fj  Gj  dN j
dt 2. Steady-state 0
V
dt
Fj0  Fj   rj dV  0 V
3. Highly turbulent Gj   rj dV

Fj0 V Fj
- T & Ci vary along the length of reactor
Fj Fj
V V
V
V V  V
- No variation of T & Ci in radius direction

Fj  Fj  rj V  0
V V V
rj  f n (z)
Fj  Fj d Fj
lim V V V
 rj  0  rj
V  0 V dV
Reconsider isomerization of A:
Calculate volume necessary to reduce the AB
molar flow rate from FA0 to FA1.
1 FA1
1
dV  dFA V1   dFA
rA FA0 rA

Assoc. Prof. Dr. Duangkamol Na-Ranong

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Packed Bed Reactor (PBR)
Fluid-solid heterogeneous catalytic reactions occurs on the
surface of the catalyst. The greater the mass of a given
catalyst, the greater the reactive surface area.
The reaction rate is defined based on mass of solid catalyst,
W, rather than on reactor volume, V.

Fj  Fj  rjW  0
W W W

Fj  Fj d Fj
lim W W W
 rj  0  rj
W  0 W dW

Calculate catalyst weight necessary to reduce FA0 to FA1.

FA1
1
W1  
FA0
rA
dFA
Quiz 2
Assoc. Prof. Dr. Duangkamol Na-Ranong
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Ex. 1-5: How large is the reactor volume? (PFR)
Reconsider the liquid phase cis–trans isomerization of 2–butene (A  B). The
reaction is first order in A (–rA = kCA) and is carried out in a plug flow reactor.
The volumetric flow rate, , is constant, i.e.,  = 0.
1. Sketch the concentration profile. (CA, CB - V)
2. Derive an equation relating the reactor volume to the entering and exiting
concentrations of A, the rate constant k, and the volumetric flow rate .
3. Determine the reactor volume to reduce the exiting concentration to 10%
of the entering concentration, i.e., CA = 0.1CA0, when the volumetric flow
rate is 10 dm3/min and the specific reaction rate, k, is 0.23 min-1.

FA0 AB FA Along the reactor, FA  (FA0 to FA)

  0 -rA increases with CA
1. Select specific species:
FA  CA   FA  CA 0
2. Mole balance:
3. Rate law: Along the reactor, FA 
4. Combine and solve the equations  CA 
 -rA 
Assoc. Prof. Dr. Duangkamol Na-Ranong 40
 Review of Chapter 1 (p.25)
Table S-1 Summary of Reactor Mole Balances
Operation Mole Balance
Reactor
Assumption Differential form Algebraic form Integral form
N A,0
Batch No inlet, outlet dN A 1
Spatially uniform dt
 rAV t1  N  rAV dN A
A,1

CSTR Continuous Op. FA,0  FA

FA,0
Steady-state  V 
Spatially uniform  rA
FA

PFR Continuous op. dFA

FA,0
1
Steady-state  rA V1   dFA
FA,0 V FA dV  r
Plug flow FA,1 A

Well mixed in “r”

direction
FA,0
PBR Continuous op. dFA 1
FA,0 W FA
Steady-state dW
 rA W1  F  rA dFA
A,1
Well mixed in “r”
direction
Assoc. Prof. Dr. Duangkamol Na-Ranong
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