Chemical kinetics &

Reactor Design
Course Code: Ch. E-847
Credit Hours: 3-0
Course Instructor: Dr. Erum Pervaiz

Recommended Books

Recommended Books
Aris R., Elementary Chemical Reactor
Analysis, Prentice-Hall 1969.
Foggler, H. S., Elements of Chemical
Reaction Engineering, Prentice Hall of
India, 1994.
Fromment G.F. and Bischoff K.B.,
Chemical Reactor Analysis and Design,
John Wiley 1994.
Schimdt L., The Engineering of Chemical
Reactions, Oxford, 2005

What is Chemical kinetics& Reactor

Design?

Chemical kinetics and reactor design

is the field that studies the rates and
mechanisms of chemical reactions
and the design of the reactors in
which they take place.

Fundamentals of Chemical
Reaction Kinetics and Design

Classification of chemical reactions

Rate Law
Out put
Kinetics and Mechanisms of reaction
Reactors and Design
Product distribution and Selectivity

Fundamentals/Introduction

Homogenous and Non-homogenous reactions

Elementary and Non-elementary reactions
Reaction Mechanisms (chain reaction
mechanism, Non chain, intermediate formation,
Ion, radicals,

Classification of Reactions
In CRE the most useful scheme is the breakdown
according to the number and types of phases
involved homogeneous and heterogeneous systems.
A reaction is homogeneous if it take place in one
phase alone.
A reaction is heterogeneous if it requires the
presence of at least two phases to proceed.
It is immaterial whether the reaction takes place in
one, two, or more phases; at an interface; or
whether the reactants and products are distributed
among the phases or are all contained within a
single phase.
All that counts is that at least two species are
necessary for the reaction to proceed as it does.

Variables Affecting the Rate of

Reaction
In homogeneous systems the temperature,
pressure, and composition are obvious
variables.
In heterogeneous systems more than one
phase is involved; hence, the problem
becomes more complex. Material may have
to move from phase to phase during
reaction; hence,
rate of mass transfer
rate of heat transfer
10

Chemical Identity
A chemical species is said to have reacted when it
has lost its chemical identity.
The identity of a chemical species is determined by
the kind, number, and configuration of that species
atoms.
1. Decomposition
2.
Combinatio
n
3. Isomerization

Rate of Chemical Reaction

The rate of reaction tells us how fast number of
moles of one chemical species are being consumed
to form another chemical species. The term
chemical species refers to any chemical component
or element with a given identity.
OR
The reaction rate is the rate at which a species
looses its chemical identity per unit volume.
The rate of a reaction (mol/dm 3/s) can be expressed
as either,
The rate of Disappearance: -rA
or as
The rate of Formation (Generation): rA

Reaction Rate
Consider the isomerization

AB

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

EXAMPLE: AB
If Species B is being formed at a rate
of
0.2 moles per decimeter cubed per
second, ie,
rB = 0.2 mole/dm3/s

Types of Reactions:

Single & Multiple

Reactions
Series Reactions

Multiple or complex

Elementary & NonElementary Reactions:

Reaction Rate

For a catalytic reaction, we refer to -rA', which is

the rate of disappearance of species A on a per
mass of catalyst basis.
(mol/gcat/s)

Reaction Rate
Consider species j:
rj is the rate of formation of species j per
unit volume [e.g. mol/dm3/s]
rj is a function of concentration,
temperature, pressure, and the type of
catalyst (if any)
rj is independent of the type of reaction
system (batch, plug flow, etc.)
rj is an algebraic equation, not a
differential equation

Reaction Rate

Parameters affecting rates

of reaction:

Rate law

The rate law does not depends upon the type of

reactor used

Rate Equation:

Reaction Rate
rj is the rate of formation of species j per
unit volume [e.g. mol/dm3/s]
rj is a function of concentration,
temperature, pressure, and the type of
catalyst (if any)
rj is independent of the type of reaction
system (batch, plug flow, etc.)
rj is an algebraic equation, not a
differential equation

Parameters affecting rates of

reaction:

Rate law

The rate law does not depends upon the type of reactor used

Rate Equation

Molecularity & Order of reactions

Molecularity means the number of
molecules involved in chemical reaction.
Its an integer value and not a fraction.
Its usually associated with the elementary
reactions.
Order of a reaction is the power to which
concentrations are raised.
Order of reaction could be a fraction.
They are not necessarily related to the
stoichiometric coefficients.

Rate Equation:
Rate of reaction is influenced by the
concentrations and energy of the
material.

Representation of an
Elementary reaction

Representation of a nonelementary reaction

Free radicals

Ions and polar substances

Molecules
Chain reaction mechanism

Non chain reaction mechanism

Reaction Mechanisms and

Rate Expression

Reaction Mechanism
RM means detail description of a chemical reaction outlining each separate step or
stage.
Mechanism of reaction include stable and unstable intermediates so needs to be
audited continuously.
Reaction steps are sometimes very complex that needs to include thermodynamics
of reaction.
For a reaction energy must be provided to reactants to start the reaction and
breaking of bonds.
Reactant molecules becomes activated due to higher energy contents leading to
unstable activated state or transition complex.
Activation energy is the amount of energy required to raise the reactant molecules
to this state.
This energy also helps to find out the rate of reaction.
Catalyst enables the reactants to convert into products at low energy states by
affecting the reaction rate. Therefore a catalyzed reaction has lower activation
energy then an un-catalyzed reaction.
Reactants will absorb energy to cross this peak and the energy will be released back
when stable products will form. This is called as heat of reaction.

Exothermic Reactions

Endothermic Reactions

Unstable intermediate Reactions

Temperature
Dependence of Rate
The order ofConstants
each
reactant depends on
the detailed reaction
mechanism.
Chemical
reaction
speed up when the
temperature
is
increased.
molecules must
collide to react
an increase in
temperature increases
the
frequency
of
intermolecular
collisions.

Ea
RT

k zpe
z:the collision freq uency
p: steric factor
k Ae

Ea
RT

Ea 1
ln(k) ( ) ln(A)
R T

T(K) and
k

Plot ln(k) vs.

1/T

Arrhenius Equation for Rate

of Reaction and Collision
Theory

Arrhenius Equation

Reaction rate increases with

temperature because:
molecules have more kinetic energy
more collisions occur
greater number of collisions occur with
enough energy to get over the hill

i.e. with energy greater than or equal to Ea

Arrhenius Equation
The Arrhenius Equation relates the value of the rate
constant to Ea and the temperature:
-Ea/RT

k = Ae
where k = rate constant
Ea = activation energy
R = gas constant (8.314 J/mol. K)
T = temperature in Kelvin
A = frequency factor (a constant)
A is related to the frequency of collisions and the probability that the collisions are
oriented favorably for reaction.

Arrhenius Equation
The activation energy of a reaction can be found by
measuring the rate constant at various temperatures
and using another version of the Arrhenius equation .

Example: At 189.7oC, the rate constant for the

rearrangement of methyl isonitrile to acetonitrile is
2.52 x 10-5 s-1. At 251.2oC, the rate constant for the
reaction is 3.16 x 10-3 s-1. Calculate the activation
energy for this reaction.

Arrhenius Equation
Once you find the value for Ea, you can use the
Arrhenius Equation to find the frequency factor (A) for
the reaction.
Once you have the value for Ea and A, you can
calculate the value for the rate constant at any
temperature.
The following two examples illustrate this process.

Example: Using the activation energy obtained in

the previous example, calculate the value for the
frequency factor using k = 2.52 x 10-5 s-1 at 189.7oC
Example: Use the value for the frequency factor (A)
and the activation energy obtained in the previous two
examples to calculate the value of the rate constant at
25oC.

Plot of ln k vs 1/T is a straight line with large

slope for large E and small slope for small E.
High E reactions are very temperature
sensitive and low E reactions are less.
Any given reaction is more temperature
sensitive at a low T than at high temperature.
From Arrhenius law ,the value of frequency
factor or constant does not affect the
temperature.

The Collision Model

The reaction rate depends on:
collision frequency
a probability or orientation factor
activation energy (Ea)

The reaction rate increases as the

number of collisions between reacting
species increase.
Concentration
temperature

Collisions Frequency and

Molecular orientations

Experiments show that the observed reaction rate

is considerably smaller than the rate of collisions
with enough energy to surmount the barrier.
The collision must involve enough energy to
produce the reaction.
The relative orientation of the reactants must
allow formation of any new bonds necessary to
products.

The Collision Model

Collisions must occur in a particular orientation for reactions to occur.

For the reaction: Cl. + H - Br H - Cl + Br.

- Reactions result when atoms/molecules collide with sufficient energy

to break bonds
- Molecules must collide in an orientation that leads to productive bond
cleavage and/or formation

Cl
.

Cl
.

Cl
.

B
r
B
r
H
H

Desired rxn
cannot occur.
Desired rxn
cannot occur.

B
r

Desired rxn can

occur.

BrNO
collision

The Collision Model

Collisions must occur with a specific

minimum amount of energy in order
for a reaction to take place.
Activation energy (Ea)

the minimum energy the reactants must have

for a reaction to occur
the energy difference between the reactants
and the transition state

The Collision Model

Transition state:
a particular arrangement of atoms of
the reacting species in which bonds are
partially broken and partially formed
the state of highest energy between
reactants and products
a relative maximum on the reactionenergy diagram.

Collision theory

Comparison

Chain Reaction Mechanism

Rice Herzfeld reaction mechanism

Gas Phase Decomposition of

Acetaldehyde

Decomposition of Ethane

ENZYME CATALYZED
REACTIONS
Soluble enzymeinsoluble substrate
Insoluble enzymesoluble substrate
Soluble enzymesoluble substrate
The study of enzymes is important because every synthetic and
degradation reaction in all living cells is controlled and
catalyzed by specific enzymes.

Contd.

Acid base catalysis

A catalyst is defined as a substance that influences the rate or the
direction of a chemical reaction without being consumed.
Homogeneous catalytic processes are where the catalyst is dissolved in a
liquid reaction medium.
The varieties of chemical species that may act as homogeneous catalysts
include anions, cations, neutral species, enzymes, and association complexes.
In acid-base catalysis, one step in the reaction mechanism consists of a proton
transfer between the catalyst and the substrate.
The protonated reactant species or intermediate further reacts with either
another species in the solution or by a decomposition process.

Autocatalytic reactions

There are many reactions in which the products formed often act as
catalysts for the reaction. The reaction rate accelerates as the reaction
continues, and this process is referred to as autocatalysis.
The reaction rate is proportional to a product concentration raised to a
positive exponent for an autocatalytic reaction.
Examples of this type of reaction are the hydrolysis of several esters. This
is because the acids formed by the reaction give rise to hydrogen ions that
act as catalysts for subsequent reactions.
The fermentation reaction that involves the action of a micro-organism on
an organic feedstock is a significant autocatalytic reaction. Normally, when
a material reacts, its initial rate of disappearance is high and the rate
decreases continuously as the reactant is consumed.
However, in autocatalytic reaction, the initial rate is relatively slow since
little or no product is formed. The rate then increases to a maximum as the
products are formed and then decreases to a low value as the reactants are
consumed.
Consider the following mechanism for an autocatalytic reaction

GAS-SOLID CATALYTIC
REACTIONS

Consider a gaseous reactant flowing through a bed of

solid catalyst pellets. The physical steps involved are,
the transfer of the component gases up to the catalyst
surface, diffusion of reactants into the interior of the
pellet, diffusion of the products back to the exterior
surface, and finally the transfer of the products from
the exterior surface to the main stream.

Ideal reactor types

Batch Reactors
Flow Reactors

Batch Reactor

To find rate equation from batch

reactor

Usually operated isothermally and constant volume.

Good for small scale laboratory setup
It needs little auxiliary equipments
Usually used for obtaining homogenous kinetic data

Analysis of kinetic data

Integral method of analysis

Differential method of analysis

General Mole Balance

Batch Reactor Mole

Balance

CSTR
Mole Balance

Plug Flow Reactor

Plug Flow Reactor Mole

Balance
PFR:

Theintegralformis:

dF A
FA 0 rA

FA

Thisisthevolumenecessarytoreducetheenteringmolarflowrate(mol/s)from
FA0totheexitmolarflowrateofFA.

Packed Bed Reactor

Mole Balance
PBR
FA0 FA

rdW
A

Theintegralformtofindthecatalystweightis:

dNA
dt

dFA
FA 0 rA

FA

Reactor Mole Balance

Summary