CH 6602 Chemical Reaction Engineering I

Dr. P. Senthil Kumar

Associate Professor
Department of Chemical Engineering
 Books
TEXT BOOKS:
1. Levenspiel O, Chemical Reaction Engineering, Wiley
Eastern Ltd., II Edition, 2000.
2. Smith, J.M, Chemical Engineering Kinetics, McGraw
Hill, III Edition, 1981.
3.Fogler.H.S., Elements of Chemical Reaction
Engineering, Prentice Hall of India Ltd., IIIrd Edition,
2000.
REFERENCE:
4. Froment. G.F. & K.B.Bischoff, Chemical Reactor
Analysis and Design, John Wiley and Sons, 1979.
 Chemical Reaction Engineering

Objectives
To impart knowledge on different types of chemical
reactors, the design of chemical reactors under
isothermal and non-isothermal conditions
 Unit I

Rate equation,

Elementary, non-elementary reactions,

Theories of reaction rate and prediction,

Design equations for constant and variable volume
batch reactors

Analysis of experimental kinetic data,

Integral and differential analysis.
 Unit II

Design for continuous reactors,

Stirred tank and Tubular flow reactor,

Recycle reactors

Combination of reactors

Size comparison of reactors.
 Unit III

Design of reactors for multiple reactions,

Consecutive, parallel and mixed reactions,

Factors affecting choice

optimum yield and conversion

Selectivity, reactivity and yield
 Unit IV

Non-isothermal homogeneous reactor systems,

Adiabatic reactors,

Rates of heat exchanges for different reactors,

Design for constant rate heat input and constant heat
transfer coefficient,

Operation of batch and continuous reactors,

Optimum temperature progression
 Unit V

The residence time distribution as a factor performance

Residence time functions and relationship between
them in reactor

Basic models for non-ideal flow

Conversion in non-ideal reactors
Chemical Process Industry
 Classification of reactions
1. Homogeneous and Heterogeneous reactions based on
number of phases involved.
2. Catalytic and Non-catalytic reactions based on catalyst
usage.
3. Unimolecular, bimolecular and termolecular reactions
based on molecularity of the reaction
4. Exothermic and endothermic reactions based on heat
effect
5. First , second, third order, etc., nth order of reaction
based on order of the reaction
6. Reversible and irreversible reactions based on reaction
proceed in one or both directions
 Law of mass action

The law of mass action is a mathematical model that

explains and predicts behaviors of solutions in dynamic
equilibrium.

It can be described with two aspects:

1) The equilibrium aspect, concerning the composition of a
reaction mixture at equilibrium and
2) The kinetic aspect, concerning the rate equations for
elementary reactions
 Rate of a chemical reaction
1. Based on unit volume of reacting fluid
1 dN A moles of A disappeared
rA = =
V dt ( volume of fluid ) (time)

2. Based on unit mass of solid in fluid-solid systems

1 dN A moles of A disappeared
rA' = =
W dt (mass of solid ) (time )

3. Based on unit interfacial area in a fluid-fluid systems or

based on unit surface area of solid in gas-solid systems
1 dN A moles of A disappeared
rA" = =
S dt (surface) (time)
4. Based on unit volume of solid in gas-solid systems
1 dN A moles of A disappeared
rA'" = =
VS dt ( volume of solid) (time)

Vs = Vp (volume of catalyst pellet)

5. Based on unit volume of reactor
1 dN A moles of A disappeared
rA"" = =
Vr dt ( volume of reactor) (time)

(-rA)V = (-rA)W = (-rA)S = (-rA)Vs = (-rA)Vr

Consider an irreversible reaction
aA + bB rR
1 dN A moles of A disappeared
rA = =
V dt ( volume of fluid ) (time)

For the constant volume systems,

d( N A / V ) dC A
rA = =
dt dt

Similarly, d( N B / V ) dC
rB = = B
dt dt

d(N R / V ) dC R
rR = =
dt dt
The relation b/w the rates of chemical reaction from the
stoichiometry of a reaction is

rA rB rR
= =
a b r

For example:
2A + B 3R

rA rB rR
= =
2 1 3
 Check your understanding

1. What do you meant by homogeneous reactions?

2. What do you meant by heterogeneous reactions?
3. Differentiate order and molecularity of the reaction.
4. Define reversible and irreversible reactions.
5. Define exothermic and endothermic reactions.
6. Discuss the importance of catalyst.
7. Define law of mass action.
Factors affecting the rate of reaction ???
 Factors affecting the rate of reaction

Nature of reactants and products

Concentration of reactants

Temperature of a system For homogeneous reaction

Pressure of a system

Nature of catalyst

Surface area of reactants

Rates of heat and mass transfer
For homogeneous systems

Temperature Concentration
rA = f
dependent term , dependent term

Consider reaction type, A R

rA = k C A

rA = k o exp(E a / RT) C A

Where, ko exp (-Ea/RT) = Temperature dependent term

CA = Concentration dependent term
Ea = activation energy
= order of reaction w.r.to A
 Concentration dependent term of a rate equation

Temperature of the system should be maintained as constant

Different types of reactions

1. Single and multiple reactions
2. Elementary and non-elementary reactions
3. Molecularity and order of the reactions
 Single and Multiple reactions

Single reactions
A Products

Multiple reactions
1. Series reactions ARS
2. Parallel reactions

3. More complicated form (parallel w.r.to B and series

with A, R and S)
 Elementary and Non-elementary reactions
Elementary reactions
Consider a single reaction with stoichiometric equation
A + B R
- rA = k CA CB
Non-Elementary reactions
 Molecularity and order of the reaction
Consider the reaction type,
aA + bB rR
Molecularity of the reaction = a+b
If the reaction is an elementary reaction
- rA = k CAa CBb

Over all order of the reaction, n = a+b

 Rate constant
For a homogeneous chemical reaction the dimensions of
the rate constant k for the nth-order reaction are
(time)-1(concentration)1-n
For 1st order reaction i.e., n =1,
(time)-1
For 2nd order reaction i.e., n =2
(time)-1(concentration)-1
 Kinetic models for non-elementary reactions
Kinetics of the reaction (non-elementary) A2 +B2 2 AB

Where * indicates unobserved intermediates

The type intermediates formed
1. Free radicals
2. Ions and polar substances
3. Molecules
4. Transition complexes
5. Non-chain reactions
6. Chain reactions
Free radicals
Free atoms or larger fragments of stable molecules that
contain one or more unpaired electrons are called free
radicals.
Example: triphenylmethyl (stable)

Unstable and highly reactive free radicals

Ions and polar substance
Electrically charged atoms, molecules, or fragments of molecules

Molecules
Consider the consecutive reactions A R S
R is highly reactive its mean lifetime will be very small and its
Concentration in the reacting mixture can become too small to measure
Transition Complexes
The numerous collisions between reactant molecules result in a
wide distribution of energies among the individual molecules. This
can result in strained bonds, unstable forms of molecules, or
unstable association of molecules which can then either decompose
to give products, or by further collisions return to molecules in the
normal state. Such unstable forms are called transition complexes.
Non-chain reactions

Chain reactions

In the propagation step intermediate is acting as a catalyst

Examples of reaction mechanisms
 Check your understanding

1. List out the factors affecting the rate of the chemical reactions?
2. Differentiate single and multiple reactions.
3. What is rate constant?
4. List out the different types of intermediates formed during the
reactions.
5. Differentiate chain and non-chain reactions.
 Temperature dependent term of a rate equation

The rate of reaction for an elementary reactions

According to Arrhenius law, (or) ln k = ln ko (E/R)(1/T)

At the same concentration, but at two different temperatures, Arrhenius
law indicates that

Where, ko is the frequency or pre-exponential factor

E is the activation energy
R is the gas constant = 8.314 J/(mol.K)
Temperature dependency of the reaction rate
 Arrhenius equation from thermodynamics
k1
A B
k 2

Variation of equilibrium constant with temperature is given by Vant Hoff

equation d ln K H R
=
dT RT 2

d ln(k 1 / k 2 ) H R
=
dT RT 2
Where K = (k1/k2)
d ln k 1 d ln k 2 H1 H 2
= 2

dT dT RT RT 2

d ln k 1 H1 d ln k 2 H 2
= 2
; =
dT RT dT RT 2
Integrate the above equation, it will gives the Arrhenius equation
Temperature dependency from collision theory
Collision theory
Before molecules react, there must be collision between the
reactant molecules and only these collisions in which the colliding
molecules possess a certain minimum amount of energy are
effective.
Consider the Bimolecular collisions of unlike molecules
A + B Products
According to collision theory the rate of the reaction is given by
-rA = (collision rate in mol/l.s) x (fraction of effective collisions)
Fraction of effective collisions = fraction of collisions releasing energy
equal to or greater than E
= e (-E/RT)
 For bimolecular collisions of unlike molecules in a mixture of A and
B from kinetic theory of gases,
2 1/ 2
A + B 1 1
Z AB = n A n B 8 k B T
+
2 M A M B

2 1/ 2
+ B N2 1 1
Z AB = A 8 k T
B + C A CB
2 10
6
M A M B
Where
A, B = molecular diameters of molecules A and B respectively in cm

+ B
AB = A = average molecular diameter (collision diamter ), cm
2
M = mass of a molecule (molecular weight/N), g
MA = mass of a molecule A (molecular weight of A/N), g
MB = mass of a molecule B (molecular weight of B/N), g
CA = concentration of A, mol/l
CB = concentration of B, mol/l
N = Avogadros Number (6.023 x 1023 molecules/mol)
nA = number of molecules of A/cm3 (NCA/103)
nB = number of molecules of B/cm3 (NCB/103)
kB = Boltzmann constant (R/N = 1.30 x 10 -16 erg/K)
number of collisions of A with B
Z AB =
(s) (cm 3 )

Z AB 103
Collision rate in mol /(l.s) =
N

Z AB 103 E / RT
Rate of reaction = .e
N
 1/ 2
103 E / RT
2
A + B N2 1 1
Rate of reaction= 8 k T
B + CA CB e
2 10
6
M A MB N
2 1/ 2
A + B N 1 1 E / RT
= 8 k B T + .e .CA CB
2 10
3
M A MB
Rate of bimolecular type reaction is given by rA = k CA CB
Compare the above two equations
2 1/ 2
A + B N 1 1 E / RT
k = 8 k B T + .e
2 10
3
M A MB

k = k 'o T1/ 2 .e E/RT (Collisions theory)

where 2 1/ 2
A + B N 1 1
ko =
'
8kB +
2 10
3
M A MB
Taking the logarithm
E
ln k = ln k 'o + 12 ln T
RT
Differentiating the above equation
d(ln k ) 1 E
= +
dT 2 T RT2
In most cases, the term (1/2T) is small compared to (E/RT2), so
neglecting (1/2T), we get

d(ln k ) E
=
dT RT2

The above equation is an equation originally proposed by Arrhenius.

For bimolecular collisions of like molecules/identical molecules
A + A Products -rA = kCA2
1/ 2
8 k B T
Z AA = 2A n 2A
MA
1/ 2
N 2
8 k T
Z AA = 2A 6 B
C 2
A
10 M A
-rA = (collision rate in mol/l.s) x (fraction of effective collisions)

Z AA 10 3 E / RT
Rate of reaction = .e
N
1/ 2
N 8 k T E / RT 2
rA = 2A 3 B
e .C A
10 M A 1/ 2
N 8 k B
2 N 8 k B T
1/ 2
where, k "o = 2A 3
k = A 3 e E / RT 10 M A
10 M A

k = k "o T1/ 2 e E / RT
The temperature dependency of the reaction rate constant is given by

k T1/ 2 e E / RT

Significance of Collision theory

1. This theory is satisfactory for number of bimolecular gas phase
reactions as well as for many reactions in solution involving simple
ions.
2. Not suitable for unimolecular reactions.

Probability Factor (Steric factor, P):

Actual rate of reactions Rate calculated from the theory

k observed
P=
k theory
Temperature dependency from Transition state theory

The fundamental postulate of the theory

1. The reacting molecules must form unstable intermediate called
activated complex before being converted to products.
2. There exists an equilibrium b/w the activated complex and
reactants at all times and that the rate of decomposition of complex
is the same for all reactions and is given by

kBT/h
Where
kB is the Boltzmann constant (1.380 x 10-16 erg/K)
h is the Planck constant (6.024 x 10-27 erg.s)
The bimolecular reaction b/w a molecules of A and B
A+B AB* Products
Rate = Concentration of activated Frequency of decomposition of
complex x activated complex
k BT
= C AB* (1)
h
The equilibrium constant K*C for formation of the activated complex
may be written as
C AB*
K *c = ( 2)
C A CB
C AB* = K *c .C A .C B
Then the rate becomes
k BT *
Rate = K c .C A .C B (3)
h
The equilibrium constant can be expressed from thermodynamic terms

G* = RT ln K *c = H * TS *

TS * H *
ln K *c =
RT
TS* H*

K *c = e RT

S* H*

K *c = e R RT
.e ( 4)

Equation (3) becomes

S* H*
k B T R RT
Rate = e .e .C A .C B (5)
h
Experimentally obtained rate equation, Rate = k CA CB (6)
Comparing equations (5) and (6)
S* H*
k B T R RT
k= e .e (7)
h
Equation (7) is the fundamental relation of the transition state theory
In the above equation, the term e(S*/R) is so much less temperature
sensitive that we may take it to be constant.
The relationship b/w H* and the Arrhenius activation energy E for
liquids and solids is
E = H * RT (8)
The relationship b/w H* and the E for gases is
E = H * (molecularity 1) RT (9)
The difference b/w H* and the E is small and of the order of RT;
hence transition state theory predicts approximately that

k T e E RT (10)
 Comparison of theories
Collision theory Transition state theory
Predicted reaction Does not agree Agree
rate with
experimental rate
Theory is based on Kinetic theory of Statistical mechanics
gases
Activated complex The decomposition Formation of AC is very
(AC) of AC is very rapid rapid
Activated complex Formation of AC is The decomposition of AC
(AC) slow and rate is slow and rate
controlling controlling
Temperature
dependency k T1/ 2 e E / RT k T e E RT
reaction rate
 Check your understanding

1. Define Arrhenius law.

2. Define activation energy.
3. Write the temperature dependency of a rate equation at two
different temperatures.
4. Derive the Arrhenius equation from Van't hoff equation.
5. List out the assumptions made in the Collision theory.
6. What is the relationship between rate constant and
Temperature from Collision theory?
7. What are the assumptions made in the Transition state theory?
8. Give the relationship between rate constant and temperature
fromTransition state theory.
 Problems
1. A rocket engine, burns a stoichiometric mixture of fuel (liquid
hydrogen) in oxidant (liquid oxygen). The combustion
chamber is cylindrical, 75 cm long and 60 cm in diameter, and
the combustion process produces 108 kg/s of exhaust gases.
If combustion is complete, find the rate of reaction of
hydrogen and of oxygen.
2. A reaction has the stoichiometric equation 2A + B 3R. What
is the order of the reaction.
3. An elementary reaction has the stoichiometric equation
2A + B 3R . What is the order of the reaction.
4. What is the relationship b/w the rate of disappearance and
rate formation for the following reaction.
2 NO 2 + 12 O 2 N 2 O 5
5. A certain reaction has a rate given by
rA = 0.5 C 2A , mol /(cm 3 . min)
if the concentration is expressed in mol/l and time in hours,
what would be the value and units of rate constant.
6. On doubling the concentration of reactant, the rate of reaction
triples. Find the order of the reaction.
7. Milk is pasteurized if it is heated to 63C for 30 min, but if it is
heated to 74C it only needs 15 s for the same result. Find the
activation energy of this sterilization process.
8. The pyrolysis of ethane proceeds with an activation energy of
about 75000 cal/mol. How much faster is the decomposition at
650 oC than at 500 oC.
9. At 500 K the rate of a bimolecular reaction is ten times the rate
at 400 K. Find the activation energy for this reaction
(i). From Arrhenius law
(ii). From Collision theory
(iii). What is the % difference in rate of reaction at 600 K
predicted by these two methods?
10. Show that the following scheme:
k1 Is consistent with, and can
N 2O 5 NO 2 + NO*3 explain, the observed first-
k2
order decomposition of N2O5
NO 2 + NO*3 NO 2 + O 2 + NO*
3k

NO* + NO*3 k
4 2 NO 2
11. A reaction 2 HI(g) H2 (g) + I2 (g) is studied over a range of
temperatures. The results obtained are tabulated below

Temperature K 633 666 697 715 781

Rate constant k, 1.7 x 1.07 x 5.01 x 1.05 x 1.5 x 10-3
l/ (mol. s) 10-5 10-4 10-4 10-3

(i). Find out the value of activation energy

(ii). Determine by what factor the rate increases when temperature
rises from 600 K to 700 K.
12. A common rule of temperature is that the rate of a reaction doubles
for each 10 oC rise in temperature. What activation energy would
this suggest at a temperature of 35 oC.
 Batch reactor
Symbolic representation of batch reactor system
For batch reactor
At constant volume (change in pressure)
At constant pressure (change in volume)
 Batch Reactor

Batch reactor (BR) liquid phase reactions

Batch reactor
Advantages
1. Simple in construction
2. Simple to operate
3. It has flexibility of operation
4. Cost is relatively low
5. Requires small instrumentation and less supporting equipment
6. Give high conversion for long periods of time in the reactor
Disadvantages
1. High labor cost per unit volume of production
2. Requires considerable time to empty, clean out and refill
3. Quality control of product is poor
4. Large scale production is difficult.
 Design of Ideal Batch Reactor

Material balance of A on mole basis at any time, t

Input of A= Output of A+ Disappearance of A + Accumulation of A
by chemical reaction within the reactor

Input = 0
Output = 0
Disappearance = - Accumulation
Where
Disappearance by
chemical reaction = (-rA)V

Accumulation = dNA /dt

 d[N Ao (1 X A )]
=
dt
dX A
= N Ao
dt
substitute the terms
dX A
( rA )V = N Ao
dt
Re arranging
dX A
dt = N Ao
(rA )V
Integrating with the lim its
X A = 0 at t = 0
X A = X A at t = t
t XA
dX A
dt = N Ao (rA )V
0 0
continue...
XA
dX A
t = N Ao
0 (rA )V
This is the general design equation for batch reactor

For a cons tan t volume system

A = 0 and V = Vo
XA
N dX A
t = Ao
Vo 0 (rA )
XA
dX A
t = C Ao
0 (rA )
CA
dC A
t= ( r )
C Ao A

This is the performance / design eqn for a batch reactor

for a cons tan t volume reactor system
For a change in volume / density system
XA
dX A
t = N Ao
0 (rA )V
XA
dX A
t = N Ao
0 (rA )Vo (1 + A X A )
XA
dX A
t = C Ao
0 (rA )(1 + A X A )
This is the performance / design eqn for a batch reactor
for a var ibale density / volume system

Q The above equations are applicable to both isothermal

and non isothermal operations.
 Problems
1. The saponification reaction
NaOH + CH3COOC2H5 CH3COONa + C2H5OH
follows second order kinetics. A laboratory well-stirred tank
reactor is charged with an aqueous solution containing NaOH
and ethyl acetate, both of 0.1 molar (mol/l). After 15 min, the
conversion of ethyl acetate is 18%.
For the initial charge containing NaOH and ethyl acetate in
equal concentration of 0.2 molar, what time is required to
obtain a conversion of 30 % in a commercial batch reactor?
 Analysis of experimental kinetic data
Batch reactor (homogeneous reactions)
Methods of analysis of kinetic data
1. Integral method of analysis
2. Differential method of analysis
3. Initial rate method
4. Half-life method
5. Ostwalds method
Difference b/w integral and differential methods of analysis
Integral method Differential method
This method is easy to use and is This method is useful in more
recommended when testing specific complicated situations but requires
mechanisms, or relatively simple rate more accurate or larger amounts of
expressions data
This method is used to test the This method is used to develop
particular mechanism only or build up a rate equation to fit
the data
 Constant-Volume batch reactor
Its also called as constant density reaction system
In constant volume system the measure of the reaction rate of
component i becomes
1 dN i d(N i / V ) dC i
ri = = =
V dt dt dt
p N
For ideal gases C = =
RT V
d(p i / RT)
ri =
dt
1 dp i
ri =
RT dt
 Relation b/w concentration and conversion for constant-volume
batch system

Material balance of A:
A initially = A reacted + A unreacted
A unreacted = A initially - A reacted where
N A = N Ao N Ao X A N Ao = initial moles A
N A = N Ao (1 X A ) N Ao X A = moles of A reacted
N N (1 X A ) moles of A reacted
C A = A = Ao XA =
V V initial moles A
In constant-volume system, V = Vo
N Ao (1 X A )
CA =
Vo
C A = C Ao (1 X A )
 Integral methods of analysis of rate data
General procedure
dC A
1. Assume a rate expression (i.e., order of the reaction) rA = = k. f (C)
dt
2. Rearrange the rate expression to get in the following form
dC A
= k. dt
f (C)
CA dC A t
= k dt
C A o f (C) 0
3. Plot the integral of equation against time.
The plot should yield a straight line with
slope equal to k.
4. If the above plot yields a straight line passing
through the origin then the assumed rate equation is correct . If not then
the assumed rate equation is incorrect and another rate equation is tried.
 Integrated approach to different order reactions

1. Irreversible unimolecular-type first-order reactions

Consider the reaction A Products
The rate equation is given by

dC A
rA = = k. C A
dt
dC A
= k. dt
CA
int egrating the above equation within the lim its
C A = C Ao at t = 0; C A = C A at t = t
CA dC A t
= k dt
C Ao C A 0

C 1 C
ln A = k.t; k = ln Ao
C Ao t CA
In terms of conversion
dC A
= k. C A
dt
d(C Ao (1 X A ))
= k. dt
C Ao (1 X A )
dX A
= k. dt
(1 X A )
int egrating the above equation
X A = 0 at t = 0; X A = X A at t = t
XA dX A t
= k dt
0 (1 X A ) 0

ln(1 X A ) = k.t
Characteristics of first order kinetics
Half life
The time required to reduce the concentration of the reactant to half
of its original value.

1 C
k = ln Ao
t CA
2.303 C Ao
t= log
k CA
apply the condition is C A = C Ao / 2 at t = t1/ 2
2.303 C Ao
t1 / 2 = log
k Ao
C / 2
0.693
t1 / 2 =
k
2. Irreversible Bimolecular-type second-order reactions
Consider the reaction type 2 A Products (or)
A +B Products
For the equal concentrations of A and B, the rate expression is,
dC A
rA = = k. C 2A
dt
dC
2A = k. dt
CA
int egrating the above equation within the lim its
C A = C Ao at t = 0; C A = C A at t = t
CA dC A t
2
= k dt
C Ao C A 0
C
1 A 1 1 1 1 1
= k.t; C C = k.t; k=

C A C Ao A Ao t C A C Ao
In terms of conversion
dC A
= k. C 2A continue...........
dt
1 X A dY
d(C Ao (1 X A )) = kC Ao t
= k. dt Y 2
C 2Ao (1 X A ) 2 1

dX A [1 / Y ]11 X A = kC Ao t
= kC Ao . dt
(1 X A ) 2 1
1 = kC Ao t
int egrating the above equation 1 XA
X A = 0 at t = 0; X A = X A at t = t XA
= kC Ao t
XA t
1 XA
dX A
= kC Ao dt 1 XA
0 (1 X A ) 2
0 kt = 1 X
take 1 XA = Y
C Ao A

dX A = dY
At X A = 0, Y = 1
XA = XA , Y = 1 XA
Test for bimolecular reactions
Characteristics of second order kinetics
Half life
Consider the reaction type 2 A Products

1 1 1
k=
t C A C Ao
1 1
kt1/ 2 =
Ao
(C / 2 ) C Ao
1
t1 / 2 =
k C Ao
1
t1 / 2
C Ao
Significance
The half life method cannot be used with reactions where the concentrations of
A and B are different, since A and B will have different times for half reaction.
Empirical rate equation for nth order
For the reaction A Products
The rate is given by
dC A
rA = = k. CnA
dt
dC
nA = k. dt
CA
int egrating the above equation
C A = C Ao at t = 0; C A = C A at t = t
CA dC A t The dim ensions of rate cons tan t (k )
n
= k dt
C Ao C A 0 for n th order reaction are
C
C An +1 A (time) 1 (concentration)1n
= k.t
n + 1 C Ao
1 1 1 1 1
n 1 n 1 = k.t; n 1 n 1 = (n 1)k.t , n 1
n 1 C A C Ao C A C Ao
 Assignments
1. Derive the integrated rate equation for bimolecular-second order
reactions
reaction type is A +B Products (i.e., A and B are not in equal
concentrations)
2. Derive the integrated rate equation for termolecular-third order
reactions
reaction type is A +B+C Products (i.e., A, B and C are equal
concentrations)
3. Derive the integrated rate equation for termolecular-third order
reactions
reaction type is 2A +B Products (i.e., A and B are not in equal
concentrations)
Half-life method
For the irreversible reactions aA + bB + Products
The rate equation is
dC A
rA = = k. C A CB ...
dt
For reac tan ts A and B at any time,
CB b
=
CA a

dC A b
rA = = k. C A C A ...
dt a
= k.(b / a) ....C A+ +...
rA = k ' CnA
int egrating with initial condition
C A = C Ao at t = 0
C1An C1Ao
n
= k ' (n 1)t, for n 1
According to half life concept
t = t1/ 2 when C A = C Ao / 2
(12 C Ao )1n C1Aon = k ' (n 1)t1/ 2
n
C1Ao n
C1Ao = k ' (n 1)t1/ 2
21n
n 1
C1Ao 21n = k ' (n 1)t1/ 2
1

[
n n 1
C1Ao ]
2 1 = k ' (n 1)t1/ 2

t1 / 2 =
[2 n 1
1 1n
C Ao
]
k ' (n 1)
taking natural log on both sides of equation
2n 1 1
ln(t1/ 2 ) = ln + (1 n) ln C Ao
k ' (n 1)
 Irreversible reactions in parallel
Consider the following elementary reactions in parallel
A
k1
R
A k
2 S
The rate of disappearance of A is given by
dC A
rA = = k1 CA + k 2 CA
dt
int egrate this eqn and apply the lim its
C
ln A = (k 1 + k 2 ) t
C Ao
rates of formation of R and S
dC R dC S
rR = = k 1C A ; rS = = k 2C A
dt dt
rR (dC R / dt ) k 1
= =
rS (dC S / dt ) k 2
dC R k 1
=
dC S k 2
int egrate the above equation
C R C Ro k 1
=
CS C So k 2
 Irreversible reactions in series
Consider a unimolecular-type first order series reaction of the type
A
k1
R k
2 S
Rate equations for A, R and S
dC A
rA = = k1 CA (1)
dt
dC R
rR = = k 1 C A k 2 C R (net rate of formation of R ) (2)
dt
dC S
rS = = k 2 CR (3)
dt
Assume initially no R and S present and
let C Ao be the initial concentration of A
dC A
= k1 CA ( 4)
dt
rearranging and int egrating,
C
ln A = k 1 t
C Ao
C A = C Ao e ( k1 t ) (5)
In order to find the var iation in concentration of R , put the value of C A to rR
dC R
+ k 2 C R = k 1 C Ao e ( k1 t ) (6)
dt
The above eqn is a first order linear differential eqn of the form
dy
+ Py = Q (7)
dx
comparing the eqns (6) and (7)
y = C R ; x = t; P = k 2 ; Q = k 1 C Ao e ( k1 t )
The solution of the linear differential eqn
y e pdx = Q. e pdx . dx + C
y = C R ; x = t; P = k 2 ; Q = k 1 C Ao e ( k1 t )
The solution of the linear differential eqn
y e pdx = Q. e pdx . dx + C
C R e k 2dt = k 1 C Ao e ( k1 t ) e k 2dt . dt + C
C R e k 2t = k 1 C Ao e (k 2 k1 ) t dt + C
e ( k 2 k1 ) t
CRe k 2t
= k 1 C Ao +C (8)
(k 2 k 1 )
Initial condition, C Ro = 0 at t = 0
k 1 C Ao
0= +C
(k 2 k 1 )
k 1 C Ao
C= (9)
(k 2 k 1 )
substituting C in eqn (8)
e ( k 2 k1 ) t k C
CRe k 2t
= k 1 C Ao 1 Ao
(k 2 k 1 ) (k 2 k 1 )
 e k1t e k 2t
C R = k 1 C Ao (10)
(k 2 k 1 ) (k 2 k 1 )
e k1t e k 2t
C R = k 1 C Ao + (11)
(
2k k 1 ) (k 1 k )
2

No change in total number of moles (cons tan t density system)

C Ao = C A + C R + CS
CS = C Ao C A C R
putting the C A value from eqn (5) and C R from eqn (10) in the above eqn
( k1 t ) e k1t e k 2t
CS = C Ao C Ao e k 1 C Ao
(k
2 k 1 ) (k 2 k )
1

( k1 t ) k 1 k 1e k 2t
CS = C Ao 1 e 1 + +
k 2 k 1 k 2 k 1

( k1 t ) k 2 k 1e k 2t
CS = C Ao 1 e + (12)
k 2 k1 k 2 k1
If k 2 is much l arg er than k 1 , the eqn (12) reduced to
[
CS = C Ao 1 e ( k1 t ) ] (13)
If k 1 is much l arg er than k 2 , the eqn (12) reduced to
[
CS = C Ao 1 e ( k 2 t ) ]
Maximum concentration of R
e k1t e k 2t
C R = k 1 C Ao
(
2 k k 1 ) (k 2 k )
1

k C
[
C R = 1 Ao e k1t e k 2t
(k 2 k 1 )
]
dC R
dt
k C
[
= 1 Ao k 1e k1t + k 2e k 2t
(k 2 k 1 )
]
dC R
At max imum R formation condition =0
dt
k 1 C Ao
[
(k 2 k 1 )
]
k 1e k1t + k 2 e k 2t = 0
 k 1 C Ao
can not be zero
(k 2 k 1 )
k 1e k1t + k 2 e k 2t = 0
Taking log arithm, we get
ln k 2 k 2 t ln k 1 + k 1t = 0
ln(k 2 / k 1 ) = k 2 t k 1t
t (k 2 k 1 ) = ln(k 2 / k 1 )
ln(k 2 / k 1 ) 1
t= = (14)
(k 2 k 1 ) k log mean
By combining eqns (10) and (14) the max imum concentration of R is given by
k 2 /(k 2 k1 )
C R max k 1
=
C Ao k2
 Autocatalytic reactions
A reaction in which one of the products of reaction acts as a
catalyst is called as an autocatalytic reactions.
Consider the following autocatalytic reaction A+RR+R
The rate of the reaction is
dC A
rA = = k CA CR
dt
at any time t
Co = C A + C R = C Ao + C Ro = cons tan t
dC A
rA = = k C A (Co C A )
dt
dC A
= k dt
C A (C o C A )
Braking int o partial fractions, we get
1 dC A dC A
+ = k dt
Co C A (Co C A )
 CA
dC A C A dC A
= kCo t
C Ao C A C Ao (C o C A )

C Ao Co C A
ln + ln = kCo t
CA Co C Ao
C Ao (Co C A )
ln = kCo t
C A (C o C Ao )
Co = C Ao + C Ro = C A + C R
C A = Co C R
C Ao = C o C Ro
C Ao (Co Co + C R )
ln = kCo t
C A (C o Co + C Ro )
C Ao .C R C R / C Ro
ln = ln = kCo t = (C Ao + C Ro ) kt (1)
C A .C Ro C A / C Ao
If M = C Ro / C Ao and X A is the fractional conversion A
C Ao (Co C A ) = C Ao [C Ao + C Ro C Ao (1 X A )]
= C Ao [C Ao + C Ro C Ao + C Ao X A ]
C Ro
= C Ao .C Ao + XA
C Ao
C Ao (Co C A ) = C 2Ao [M + X A ]

C A (C o C Ao ) = C Ao (1 X A )[C Ao + C Ro C Ao ]
= C Ao (1 X A ) C Ro
C Ro
= C 2Ao (1 X A )
C Ao
C A (C o C Ao ) = C 2Ao (1 X A ) M

Co kt = (C Ao + C Ro ) kt
= C Ao (1 + C Ro / C Ao ) kt
Co kt = C Ao (1 + M ) kt
Interms of M and X A , the eqn (1) becomes
C 2 (M + X A )
ln 2Ao = C (M + 1) kt
C (1 X A )M Ao
Ao
(M + X A )
ln = C Ao (M + 1) kt
(1 X A )M
 Reversible reactions
Reversible unimolecular type first order reaction

k1
Consider the reaction AR
k2

Where, k 1 = forward reaction rate cons tan t

k 2 = backward reaction rate cons tan t

The net rate of disappearance of A rA = k 1C A k 2CR

dC A dC R
= = k 1C A k 2CR
dt dt
C
Initial molar ratio, M = Ro
C Ao
Concentration of A at time t , C A = C Ao (1 X A )
dC A = C AodX A
Concentration of R at time t , C R = C Ro + C Ao X A
 dC A dX A
= C Ao = k 1C Ao (1 X A ) k 2 (C Ro + C Ao X A ) (1)
dt dt

At equilibriu m, net rate is zero

(i.e., the rate of forward reaction = the rate of backward reaction)

dC A
=0 and X A = X Ae (equilibrium conversion)
dt

0 = C Ao [k 1 (1 X Ae ) k 2 (M + X Ae )]
k 1 (1 X Ae ) = k 2 (M + X Ae )
k 1 (M + X Ae ) C Re
= = KC =
k2 (1 X Ae ) C Ae
k 1 (1 X Ae )
k2 =
(M + X Ae )
from equation (1)
dX A
= k 1 (1 X A ) k 2 (M + X A )
dt
Substitue the k 2 value to the above equation
dX A k (1 X Ae )
= k 1 (1 X A ) 1 (M + X A )
dt (M + X Ae )
dX A (1 X A )(M + X Ae ) (1 X Ae )(M + X A )
= k1
dt ( M + X Ae )
dX A X Ae (M + 1) X A (M + 1)
= k1
dt ( M + X Ae )
dX A k 1 (M + 1)
= ( X Ae X A )
dt (M + X Ae )
XA dX A k 1 (M + 1) t
= dt
0 ( X Ae X A ) ( M + X )
Ae 0
 X XA (M + 1)
ln Ae = k 1t
X Ae (M + X Ae )
X XA C C Ae (M + 1)
ln Ae = ln A = k 1t ( 2)
X Ae C Ao C Ae (M + X Ae )
The above eqn (2) is the desired int egrated rate eqn for
reversible first order reaction

X XA
plot ln Ae Vs t
X Ae
Comparison of reversible 1st order and irreversible 1st order

For a irreversible 1st order

ln (1 X A ) = ln (C A / C Ao ) = kt (1)
For a reversible 1st order with C Ro = 0
X XA C C Ae 1
ln Ae = ln A = k 1t
X Ae C Ao C Ae X Ae
If X Ae = 1 (or ) C Ae = 0 then the above eqn reduced to
ln (1 X A ) = ln (C A / C Ao ) = kt ( 2)

The irreversible 1st order reaction is simply a special case of

the reversible 1st order reaction
in which X Ae = 1 (or ) C Ae = 0 (or ) K C =
 Reversible bimolecular second order reaction
k1
(i ) 2A R + S
k2
k1
(ii ) A +BR +S
k2
k1
(iii ) 2 A 2R
k2
k1
(iv ) A + B 2R
k2

with C Ao = C Bo and C Ro = CSo = 0, the int egrated rate eqn

applicable to all the forms

X ( 2X Ae 1) X A 1
ln Ae = 2k 1 1C Ao t
X Ae X A X Ae
 Differential method of analysis of data

Procedure
1. Assume a rate equation -rA = - (dCA/dt) = k f (C)
2. Plot a graph of concentration v/s time (experimental studies)
3. Draw a smooth curve through these data.
4. Determine the slope of this curve by drawing tangents to the curve
at the suitably selected concentration values. dCA/dt are the rates
of reaction at the selected concentration.
5. Evaluate f (C) for each of the selected concentrations.
6. Plot a graph of - (dCA/dt) v/s f (C). If we get a straight line passing
through the origin then the rate eqn is consistent with the data (i.e.,
assumed rate eqn is correct). If we do not get a straight line then
another eqn should be tested.
Differential method of analysis of data
 Ostwalds isolation method
This method is used to determine the order of the reaction by taking
a number of reactants in large excess except one. The rate of the
reaction depends upon this isolated reactant which is present in the
least amount.
The rate is given by
dC A
= k C A CB C C
dt
If B and C are taken in a l arg e excess
dC A
= k C A C B0 C C0
dt
dC A
= k C A (use int egral / differential method)
dt
Similarly , and were det er min ed by assu min g the
rate of the reaxn is depends on one of the reac tan t
 Variable volume batch reactor (or)
constant pressure batch reactor
Example: Gas-phase reactions
N 2 O N 2 + 12 O 2
The rate of change of component ' i '
1 dN i
ri =
V dt
1 d(C i V )
ri =
V dt
1 dC i dV
= V + Ci
V dt dt
dC i C i dV
= +
dt V dt
dC i d ln V
= + Ci
dt dt
For the volume of reaction system var ying linearly with conversion
V = Vo (1 + A X A )
A is the fractional change in the volume of the reaction system b/w
no conversion and complete conversion of reactant A
VX A =1 VX A =0
A =
VX A =0
Change in total number of moles for complete conversion
A =
Total number of moles fed to the reactor

Example
A 4R
4 1
A = =3
1
Example :

50 mole % A + 50 mole % inerts

A 4R
no conversion complete conversion

50 mole of A 4 50 = 200 mole of R

50 mole of I 50 mole of I

100 mole 250 mole

250 100
A = = 1.5
100
Exercise :

1). 75 mole % A + 25 mole % inerts

A 3R

2). 40 mole % A + 60 mole % inerts

A 4R

3). 90 mole % A + 10 mole % inerts

A 2R

4). 55 mole % A + 45 mole % inerts

A 4R
 Zero-order reactions

1 dN A 1 d[N Ao (1 X A )]
rA = = =k
V dt Vo (1 + A X A ) dt
N Ao 1 d[(1 X A )]
=k
Vo (1 + A X A ) dt
C Ao dX A
=k
(1 + A X A ) dt
C Ao dX A
=k
(1 + A X A ) dt
C Ao dX A
= k dt
(1 + A X A )
int egrate the above eqn
t = 0; X A = 0
t = t; X A = X A
 XA dX A t
C Ao = k dt
0 (1 + X
A A ) 0
use substitution method
1+ A XA = Y
A dX A = dY
dY
dX A =
A
C Ao (1+ A X A ) dY
=k t
A 1 Y
C Ao
ln(1 + A X A ) = kt
A
C Ao V
ln = kt
A Vo
 First-order reactions
Consider the reaction type A Pr oducts
1 dN A 1 d[N Ao (1 X A )]
rA = = = k CA
V dt Vo (1 + A X A ) dt
C Ao dX A C Ao (1 X A )
= k
(1 + A X A ) dt (1 + A X A )
dX A
= k dt
(1 X A )
int egrate the above eqn
t = 0; X A = 0
t = t; X A = X A

ln(1 X A ) = k t
we know that
V = Vo (1 + A X A )
V Vo
XA =
A Vo
V
XA =
A Vo
V
ln (1 X A ) = ln1 = k t
A Vo
 Second-order reactions
Consider the reaction type 2 A Pr oducts
A + B Pr oducts with C Ao = C Bo
1 dN A C Ao dX A
rA = = = k C 2
(1 + A X A ) dt
A
V dt
2
C Ao dX A 2 1 XA
= k C Ao
(1 + A X A ) dt 1 + A A
X

Solve the above eqn then we will get

(1 + A ) X A
+ A ln(1 X A ) = k C Ao t
1 XA
(1 + A )V V
+ A ln1
= k C Ao t
Vo A V Vo A
 Problems
1. The half-life period of a reaction of the first order is 5 minutes.
Calculate its rate constant in seconds.
2. Show that the decomposition of N2O5 at 67oC is a first order reaction.
Calculate the value of the rate constant.

Time, min 0 1 2 3 4
CN2O5, mol/l 0.16 0.113 0.08 0.056 0.040

3. The half life of a first order reaction A B is 20 min. what percent of

A remains after 100 min?
4. The decomposition of a component is second order. When the initial
concentration of that component is 5x10-2 mol/L, it is 30 %
decomposed in 30 min. calculate the value of rate constant.
5. In case of a first order reaction, show that the time required for 75%
conversion is double the time required for 50 % conversion.
6. For the reaction A Products, the following data were obtained at
25oC, in which the concentration of A is given at different intervals of
time.

Time, min 0 10 20 30 40
CA, mol/l 0.860 0.740 0.635 0.546 0.405

find the order of reaction and calculate the rate constant and the half
life period.
7. The decomposition of NH3 on tungsten wire at 856 oC yielded the
following results

Time, s 200 400 600 1000

Total pressure, 228 250 273 318
(torr)
Find the order of the reaction and calculate the rate constant.
8. In a gaseous phase reaction, the time for half change (t1/2) for the
various initial partial pressures (p) of the reactant was given as
follows
t1/2, (min) 200 300 400
pAo, (torr) 150 99.8 75.3
Find the order of the reaction.
9. The first order reversible liquid phase reaction A R takes place in
a batch reactor. After 8 minutes, the conversion of A is 33.3 % while
equilibrium conversion is 66.7 %. Find the rate equation to represent
this reaction. Take CAo = 0.50 mol/l and CRo = 0
10. The liquid phase reaction A R+S with CAo = 0.1823 mol/l, CRo = 0
and CSo = 55 mol/l proceeds as follows.

Time, (min) 0 36 65 100 160

CA, (mol/l) 0.1823 0.1453 0.1216 0.1025 0.0795 0.0494

Find the rate expression for this reaction

11. Consider the reaction type A Products takes place in a batch
reactor and the results are tabulated.

Time, (min) 0 1 2 3 4 5 6
CA, (mol/l) 0.041 0.034 0.027 0.023 0.021 0.018 0.016

Time, (min) 7 8 9 10 15 20
CA, (mol/l) 0.015 0.0136 0.012 0.0014 0.0009 0.0007

Use the differential methods of analysis to determine the order of the

reaction and also the rate constant.

12. For the series reaction A

1 R
k 2 k
S with k1 = k2. Find the
maximum concentration of R and the time at which it is reached.