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