Chemical Reaction Engineering

Subject Code:Ch.E-325

Cr. h: (3-1) 4

Course Instructor: Dr. Erum Pervaiz

 Course Contents
• Overview/Introduction of CRE.
• Rate Law, Rates of reactions/Reaction Kinetics of elementary
reactions.
• Homogenous reactions in ideal reactors &the Kinetics of
homogenous reactions (Modeling of reactions).
• Design of Ideal Reactors.
• Single Reactions and ideal reactors for single reactions.
• Design for multiple reactions
• Flow patterns contacting& Non ideal flows.
• Non homogenous reactions (heterogeneous reactions & the
design).
• Reactions catalyzed by solids.
• Temperature and pressure effects
 Text/Reference Books
• Fundamentals of Chemical Reaction Engineering by Mark E. Davis
(California Institute of Technology) and Robert J. Davis(University of
Virginia)
• Chemical Reaction Engineering by Octave Levenspiel
• 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
 CLOs of CRE
Comprehend the main concepts of reactions and
mechanisms to find the kinetics of different
reactions.
Describe ideal reactors based on their design
equations to evaluate their performance for
single and multiple reactions.
Extend the concepts of reaction kinetics for
heterogeneous reactions to modify the design
parameters related to solid catalyzed reactions.
 Significance
• Chemical Engineering/Role of Chemical
Engineer
• Significance of Chemical Reaction Engineering
 Chemical Reaction Engineering
Chemical Reaction Engineering is the heart of virtually every
chemical process. It separates the chemical engineer from
other engineers.
Chemical Reaction Engineering (CRE) is the field that studies
the rates and mechanisms of chemical reactions and the
design of the reactors in which they take place.
Reactor design uses information, knowledge, and experience
from a variety of areas-thermodynamics, chemical kinetics,
fluid mechanics, heat transfer, mass transfer, and economics.
 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.
 Reactor
• Chemical reactors are vessels designed to contain chemical
reactions.
• It is the site of conversion of raw materials into products
and is also called the heart of a chemical process.
• Reactors are designed based on features like mode of
operation or types of phases present or the geometry of
reactors.
• They are thus called:
– Batch or Continuous depending on the mode of operation.
– Homogeneous or Heterogeneous depending upon the phases
present.
 Reactor Design
FA0 FA

In – Out + Generation = Accumulation

dN A
FA0  FA  G A 
dt
 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.
Types of Reaction
Contd.
 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
 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. Combination

3. Isomerization
Classification of Reactions
 single & multiple reactions

Series Reactions

Multiple or complex
elementary & non-elementary reactions
 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/dm3/s) can be expressed as either,
The rate of Disappearance: -rA
or as
The rate of Formation (Generation): rA
 Reaction Rate
Consider the reaction AB

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: AB
If Species B is being formed at a rate of
0.2 moles per decimeter cubed per second, i.e,

rB = 0.2 mole/dm3/s
 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/g. cat/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
 The nature of the species involved in the reaction
 Concentration of the species
 Temperature
 Catalytic activity
 Nature of the contact of reactants
 Wavelength of incident radiations

Rate law
rA=f (CA, T, P, Cat….)

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.
Representation of an Elementary reaction
Elementary and Non-Elementary Reactions

Chemical Reaction rarely proceed in one step. In a

conventional single step writing of the stoichiometric
equation of a chemical reaction, only initial and final
states of the reaction system are indicated.
In case of multistep reactions the rate of overall
reaction is determined primarily by the slowest step.
It is customary in chemical kinetics to class all the
reactions as the elementary and Non-elementary
reactions
 Elementary and Non-Elementary Reactions

 In elementary reaction, the individual reaction steps which

contribute to the overall reaction are termed as elementary
reactions.
 The reaction in which the molecules react exactly as the
stoichiometric equation written for a reaction, is called as an
elementary reaction.
 In non-elementary reaction, the reactions in which formation
of product from the original reactants occur through a series
of steps are called as non- elementary reactions.
 For non-elementary reactions there is difference between
order and stoichiometric coefficient .
 Elementary and Non-Elementary Reactions

 Elementary reactions are single step reactions whereas non elementary

reactions are multistep reactions , i.e , such reactions occur through a
series of reaction steps.
 Elementary reactions are simple in nature whereas the non elementary
reactions are complex in nature.
 For elementary reactions the order agrees with the stoichiometry
whereas for non elementary reaction ,the order does not agrees with
the stoichiometry(i.e., there is a difference between order and
stoichiometric coefficient)
 For an elementary reaction, the order of reaction must be an integer
whereas for a non elementary reaction, the order of reaction may be an
integer or have a fractional value
 Reaction Mechanism
Most practical reactions occur as a series of elementary steps
challenges:
Determination of appropriate series of steps
Calculation of reaction rate for the overall reaction
– information about 'intermediate' species is vital in these analyses
– the mechanisms might not be unique
Typical assumptions used in development of rate equations from mechanisms are:
– initially, reactions can be considered irreversible
– one of the steps of the mechanism can be considered 'rate controlling'
– intermediate concentrations can be assumed to be not changing with time
– some of the reversible steps can be assumed to have net rate to be zero.
typical intermediates in such mechanisms are:
free radicals (one or more unpaired electrons, e.g. H.)
ionic intermediates
enzyme-substrate complexes
* the intermediates are typically highly reactive, unstable molecules
Representation of a non-elementary reaction

Free radicals

Ions and polar substances

Molecules
Chain reaction mechanism

Non chain reaction mechanism

 Chain Reaction
• The essential feature of the chain reaction is the
propagation step.
 Testing Kinetic Models
Two problems make the search for the correct mechanism
of reaction difficult.
– First, the reaction may proceed by more than one
mechanism, say free radical and ionic, with relative
rates that change with conditions.
– Second, more than one mechanism can be consistent
with kinetic data.
Type 1. An unseen and unmeasured intermediate X usually present at such small
concentration that its rate of change in the mixture can be taken to be zero. Thus, we
assume

Type 2. Where a homogeneous catalyst of initial concentration Co is present in two forms,

either as free catalyst C or combined in an appreciable extent to form intermediate X, an
accounting for the catalyst gives
Proposing a Mechanism
Biological Catalysts/Enzymatic reactions

• Enzymes: large protein molecule that

contains one or more active sites where
interactions with substrates occur
• Enzymes are highly specific (lock and key)
ENZYME CATALYZED REACTIONS
ENZYME CATALYZED REACTIONS
Assumptions
 Types of Rates
• Initial Rates
– Rates measured at the beginning of the reaction,
which is dependent on the initial concentrations
of reactants.
• Instantaneous Rates
– Rates measured at any point during the reaction.
• Average Rates
– An overall rate measured over a period or time
interval.
 Rate of reaction between phenolphthalein with excess base

Instantaneous Rate: Rate of decrease in

• Experimental Data for the [Phenolphthalein]
Reaction Between
Phenolphthalein and Base
• Concentration of
Phenolphthalein (M) Time (s)
– 0.0050 0.0
– 0.0045 10.5
– 0.0040 22.3
– 0.0035 35.7
– 0.0030 51.1
– 0.0025 69.3
– 0.0020 91.6
– 0.0015 120.4
– 0.0010 160.9
– 0.00050 230.3
– 0.00025 299.6
– 0.00015 350.7
– 0.00010 391.2
Decomposition of Nitrogen Dioxide
Decomposition of Nitrogen Dioxide
 Average Rate
• Consider the following reaction at 300oC:
2 NO2(g)  2 NO(g) + O2(g)

• The initial concentration of NO2 is 0.0100 mol/L and its

concentration after 150 s is 0.0055 mol/L.
• What are the average rates of this reaction during the first
150 s and during the second 150 s?
- [NO 2 ]
Average rate =  t
- (0.0055 mol/L - 0.0100 mol/L) 0.0045 mol/L
150 s 150 s

= 3.0 x 10-5 mol/(L.s)

 Average rate during the second 150 s
Average rate = - [NO 2 ]
t
= - (0.0038 mol/L - 0.0055 mol/L)
150 s
= 0.0017 mol/L
150 s
= 1.1 x 10-5 mol/(L.s)
Average rate decreases as reaction progresses because
the reactant concentration has decreased
 2 NO2  2 NO  O2
Rate Law [ NO2 ]
Average Rate  
t
• Rate=k[NO2]n Instantaneous Rate= -
d [ NO2 ]
• The concentration of the dt
products do not appear
in the rate law.
• The value of the
exponent n must be
determined by
experiment; it cannot be
written from the
balanced equation.
2N2O5→4NO2+O2

d [ N 2O5 ]
R  k[ N 2O5 ]
dt
 Types of rate laws
• Integrated Rate Law: how the concentration of species in the
reaction depend on time
• Differential Rate Law: how the rate of a reaction depends on
concentrations
• Determine the differential rate law for a given reaction, the
form of integrated rate law can be automatically known, and
vice versa
 Initial-Rate method
• To determine the instantaneous rate before the initial
concentration of reactants have changed significantly.
• Several experiments are carried out using different initial
concentrations.
• The initial rate is determined for each run.
 Exercise
2NO + 2H2  N2 + 2H2O is the reaction we’re studying, this is the data found during our
experimentation

Experiment Conc. of NO Conc. of H2 Rate of N2

Number (M) (M) forming (Ms-1)
1 0.210 0.122 0.0339
2 0.210 0.244 0.0678
0.420 0.122 0.1356
3

Exp #1 and #2, [NO] is unchanged, [H2] is doubled and this causes the rate to
double (0.0678/0.0339 =2), the H2’s rate order is 1.
Exp #1 and #3, [H2] is unchanged, [NO] is doubled and this causes the rate to
quadruple (0.1356/0.0339 =4), NO’s rate order is 2.
Rate = k [NO]2[H2]
The overall rate order for this reaction is 3 (1+2)
 Exercise
• Use the kinetics data to write the rate law for the reaction. What
overall reaction order is this? 2NO + O2 2NO2

Exp # [NO] [O2] Rate forming

NO2 (M/s)
1 0.015 0.015 0.048
2 0.030 0.015 0.192
3 0.015 0.030 0.096
4 0.030 0.030 0.384

• exp #1 and exp #2, [O2] remained constant, where [NO] is doubled. The rate
is quadrupled. The rate order for [NO] is 2.
• Exp #1 and exp #3, [NO] remained constant, where [O2] is doubled. The rate
is doubled. The rate order for [O2] is 1.
• Overall reaction order (1+2) = 3
  
NH  NO  N 2  2 H 2O
4 2

d [ NH ]
 4
 k[ NH 4 ]n [ NO2 ]m
dt
Experiments   Initial Rate
NH 4 NO 2

1 0.1M 0.005M 1.35X10-7

2 0.1M 0.01M 2.70X10-7

3 0.2M 0.01M 5.40X10-7

Rate 2 2.7 10 7 k (0.1) n (0.01) m
 7
  (2) m
 2  m 1
Rate 1 1.35 10 n
k (0.1) (0.005) m

Rate 3 5.4 10 7 k (0.2) n (0.01) m

 7
  (2) n
 2  n 1
Rate 2 2.7 10 n
k (0.1) (0.01) m

Rate  k [ NH 4 ][ NO2 ]

1.35 10 7  k (0.1)(0.005)

k  2.7 10 4 Lmol 1s 1
 k1
2 NO N2O2 fast
k-1
k2
N2O2+H2 N2O+H2O slow

Overall: 2NO+H2 N2O+H2O

R=[NO]2[H2]

Treatments
1. Rate-Determining Step Approximation
2. Steady-State Approximation
 Rate-Determining Step Approximation

k1
k1[ NO]  k 1[ N 2O2 ]  [ N 2O2 ] 
2
[ NO] 2

k 1
R  k 2 [ N 2O2 ][ H 2 ]
k1k 2
 2
[ NO] [ H 2 ]
k 1
 k[ NO] [ H 2 ]
2
 Steady-State Approximation
rate of production of N 2 O 2  rate of consumtion of N 2 O 2
d [ N 2O2 ]
0
dt
d [ N 2O2 ]
 k1[ NO]  k 1[ N 2O2 ]  k 2 [ N 2O2 ][ H 2 ]  0
2

dt
k1[ NO]2
 [ N 2O2 ] 
k 1  k 2 [ H 2 ]
k1k 2 [ NO]2 [ H 2 ]
R
k 1  k 2 [ H 2 ]
 2
k1k 2 [ NO] [ H 2 ]
R
k 1  k 2 [ H 2 ]
k1k 2 [ NO]2 [ H 2 ]
if k 1  k 2 [ H 2 ]  R   k1[ NO]2
k2[ H 2 ]
k1k 2
if k 1  k 2 [ H 2 ]  R  [ NO] [ H 2 ]  k[ NO] [ H 2 ]
2 2

k 1
Temperature Dependence of Rate
Constants
Temperature dependent term of the Rate
Equation
 Temperature and Rate
• The rates of most chemical reactions
increase with temperature.
• How is this temperature dependence
reflected in the rate expression?
• Rates increase with temperature
because rate constants increase with
temperature. An example is the 1st
order reaction:
CH3NC ---> CH3CN

𝒓𝒂𝒕𝒆=𝒌
  [𝑪 𝑯 𝟑 𝑵𝑪]

Variation in k with
temperature
 Activation Energy Needed to Reach Transition State

• Lets go back to the reaction Transition state

CH3NC ---> CH3CN
• The molecule passes through a
transition state, a high-energy
intermediate in which the CN
bond gets rotated 90o.

Enthalpy
• This is an unstable configuration
and requires an activation ΔH
energy to be reached.

nitrogen carbon

• Once this transition state is reached, the process is energetically downhill. The
transition state is always the highest energy point in the reaction pathway. As
drawn, this reaction is exothermic because the energy of the products is less
than the energy of the reactants.
 Temperature Dependence of Rate
Constants
• The order of 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.
 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 fraction of molecules that have an energy equal to or greater than the
activation energy is given by the expression:
𝑬𝒂
  −
𝑹𝑻
𝒇 =𝒆
• Arrhenius noted that reaction-rate data depended on three aspects
(1) the fraction of molecules possessing an energy Ea or greater
(2) the number of collisions per second
(3) the fraction of molecules oriented in the right way for a reaction to
occur
• These factors are incorporated into the Arrhenius Equation
• This equation relates k to temperature. A is the frequency factor, and is
related to aspects (2) and (3) listed above.
𝑬𝒂
  −
𝑹𝑻
𝐤=𝐀𝒆

  𝑬𝒂
𝐥𝐧 𝒌 =− +𝐥𝐧 𝑨
𝑹𝑻
 Ea

k  zpe RT
T(K) and k
z:the coll ision freq uency
p: steric factor
Ea

k  Ae RT

Ea 1
ln(k)   ( )  ln(A)
R T
Plot ln(k) vs. 1/T
The collision frequency is
Collision theory
Comparison
 Showing Changes in k Graphically

• From the data below, determine the activation energy of the 1st order reaction

Plot ln k vs 1/T to get the slope. We

Temperature, C K (s )
o -1
know R, so we can calculate Ea. T must
189.7 2.52 x 10-5 be in Kelvin.
198.9 5.25 x 10-5
0
230.3 6.30 x 10-4 -2
0 0 0 0 0 0 0 0

251.2 3.16 x 10-3 -4

ln k
-6
f(x) = − 19038.46 x + 30.52
-8

-10
1/T (oK-1) ln K
-12

0.002161 -10.5887 1/T

0.002119 -9.8547   𝐸𝑎 𝐸𝑎
𝑠𝑙𝑜𝑝𝑒=− 19038=− =−
0.001987 -7.36979 𝑅 𝐽
(8.314 )
𝑚𝑜𝑙 𝐾
0.001908 -5.75718  𝑬 =𝟏 .𝟓𝟖 𝒙 𝟏𝟎𝟓 𝑱
𝒂
𝒎𝒐𝒍
 • The reaction above has an activation energy of 43.5 kJ/mol. The
reaction occurs at 298 K with a rate constant of 110 s-1. What will the
rate constant be if we increase the temperature to 308 K?

  𝑘 2 𝐸𝑎 𝑇 2 − 𝑇 1
ln =
(
𝑘1 𝑅 𝑇1 𝑇 2 )
  𝑘2 43500 𝐽 𝑚𝑜𝑙 −1 308 −298
ln = (
110 8.314 𝐽 𝑚𝑜𝑙 − 1 𝐾 −1 91784 )
  𝑘2
ln =.57
110

𝑘
 ( 𝑙𝑛 ) 2

𝑒 110 =𝑒 .57

  𝑘2
=1.77
110

𝑘  2 =194.7 𝑠 −1
• 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

Desired rxn cannot

Cl .
Br H occur.

Cl . Br Desired rxn cannot

occur.
H
Desired rxn can
occur.
Cl . H Br
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 reaction-energy
diagram.
 Reaction Energy Diagrams
– a plot of potential energy changes that occur as
reactants are converted to products
• Given a reaction energy diagram for a chemical reaction, you
should be able to identify the reactants, products, transition
state, activation energy, the heat of reaction, and whether the
reaction is endothermic or exothermic.
Exothermic Reactions
Endothermic Reactions
Unstable intermediate Reactions
 Reaction Energy Diagrams
Example: For each reaction energy diagram below, mark the
location of the reactants, products and transition state. Identify the
magnitude of Ea and DHrxn. Is each reaction endothermic or
exothermic?
 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.
Transition state theory
 Catalysis
• A substance can speed up a reaction without
being consumed itself.

• The catalyst is to provide a new pathway for

the reaction and to decrease activation
energy.
Effect of a catalyst
 Heterogeneous Catalysis

• Adsorption and activation of the reactants

• Migration of the adsorbed reactants on the
surface
• Reaction among the adsorbed substances
• Escape, or desorption, of the products.
Hydrogenation of ethylene
Exhaust gases