BT 2352 Chemical Reaction Engineering

UNIT - 1

Chemical Reaction Engineering

Aim
To present reaction kinetic principles and
The different type of reactors to achieve the required
reaction.
Objectives
To gain knowledge on the selection of right type of
reactor for the required reaction.

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.

2.

3.

Based on unit volume of reacting fluid

1 dN A moles of A disappeared
rA

V dt
( volume of fluid ) (time )
Based on unit mass of solid in fluid-solid systems
1 dN A moles of A disappeared
rA'

W dt
(mass of solid ) (time )
Based on unit interfacial area in a fluid-fluid systems or based on
unit surface area of solid in gas-solid systems

rA"

1 dN A moles of A disappeared

S dt
(surface) (time )

4. Based on unit volume of solid in gas-solid systems

rA'"

1 dN A moles of A disappeared

VS dt
( volume of solid ) (time )

Vs = Vp (volume of catalyst pellet)

5. Based on unit volume of reactor
rA""

1 dN A
moles of A disappeared

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,

rA

d( N A / V )
dC A

dt
dt

Similarly,
rB

d( N B / V )
dC
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:
3A + B 4 R
rA rB rR

3
1
4

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

Concentration
Temperature
rA f

dependent term , dependent term

Consider reaction type, A R

rA k CA

rA k o exp(Ea / RT) CA
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
2. Parallel reactions

ARS

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 C A 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)

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

A2 +B2 2 AB

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

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

AB
k2

Variation of equilibrium constant with temperature is given by Vant Hoff

equation
d ln K H R

dT
RT 2

Where K = (k1/k2)

d ln( k 1 / k 2 ) H R

dT
RT 2
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
Integrate the above equation,
it will givesdT
the Arrhenius
dT
RT
RT 2 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,
Z AB

1
1
A B

n A n B 8 k B T
2
M
M

A
B

1/ 2

1/ 2

1
1
B

C A C B
Z AB A
8

k
T

6
2

10
M A M B
Where
A, B = molecular diameters of molecules A and B respectively in cm
2

N2

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)
Z AB

number of collisions of A with B

(s) (cm3 )

Z AB 10 3
Collision rate in mol /(l.s)
N
Z AB 10 3 E / RT
Rate of reaction
.e
N

2
1
1
A B N2

Rate of reaction
8

k
T

6
2

10
M A M B

1/ 2

103 E / RT
C A CB
e
N

1/ 2

1
1
A B N
.e E / RT .C A C B

8 k B T

103
M A M B
Rate of bimolecular type reaction is given by rA = k CA CB
Compare the above two equations
2

1
1
A B N

k
8 k B T

3
2

10
M A M B
2

where

1/ 2
.e

k k 'o T1/ 2 .e E/RT (Collision s theory)

2
A B N
'
ko
8kB

3
2

10

1
1

M A M B

1/ 2

E / RT

Taking the logarithm

ln k ln k 'o 12 ln T

E
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
RT 2
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
2
N 8 k B T
2
Z AA 2A 6
C
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 B T
E / RT 2
rA 2A 3
e
.C A

10 M A
where,
k 2A

N 8 k B T

10 3 M A

k k "o T1/ 2 e E / RT

1/ 2

e E / RT

N 8 k B
k "o 2A 3

10 M A

1/ 2

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
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

The equilibrium constant K*C for formation of the activated complex

may be written as

C AB*

k BT
h

Then the *rateCbecomes

Kc

AB*

C A CB

(1)

(2)

C AB* K *c .C A .CB

Rate

k BT *
K c .C A .C B
h

(3)

The equilibrium constant can be expressed from thermodynamic terms

G* RT ln K *c H * TS *
ln K *c
K *c
K *c
Equation (3) becomes

TS * H *
RT
TS* H*

RT

S* H*

R RT

e
.e

S*

( 4)

H*

k B T R RT
Rate
e
.e
.C A .CB
h
Experimentally obtained rate equation, Rate = k CA CB

(5)
(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 rate

with experimental rate

Does not agree

Agree

Theory is based on

Kinetic theory of gases

Statistical mechanics

Activated complex (AC)

The decomposition of AC
is very rapid

Formation of AC is very rapid

Activated complex (AC)

Formation of AC is slow
and rate controlling

The decomposition of AC is slow

and rate controlling

Temperature
dependency reaction
rate

k T1/ 2 e E / RT

k T e E RT

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.
3.
4.

5.

6.
7.

A reaction has the stoichiometric equation 2A + B 3R. What

is the order of the reaction.
An elementary reaction has the stoichiometric equation
2A + B 3R . What is the order of the reaction.
What is the relationship b/w the rate of disappearance and
rate formation for the following reaction.
2 NO2 12 O 2 N 2O5
A certain reaction has a rate given by
rA 0.5 C2A , mol /(cm3 . min)
if the concentration is expressed in mol/l and time in hours,
what would be the value and units of rate constant.
On doubling the concentration of reactant, the rate of reaction
triples. Find the order of the reaction.
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:
Is consistent with, and can explain, the observed firstorder decomposition of N2O5
k1

N 2 O 5 NO 2 NO*3
k2

3
NO 2 NO*3
NO 2 O 2 NO*
k

4
NO* NO*3 k
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, l/
(mol. s)

1.7 x 10-5

1.07 x
10-4

5.01 x
10-4

1.05 x 10-3

1.5 x 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.

Analysis of experimental reactor data

Types of reactors
1. Batch reactor (homogeneous reactions)
2. Flow reactor (heterogeneous 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

recommended when testing specific
mechanisms, or relatively simple rate
expressions

This method is useful in more

complicated situations but requires
more accurate or larger amounts of
data

This method is used to test the This method is used to develop or build
particular mechanism only
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 ) dCi

V dt
dt
dt
p
N
For ideal gases
C

RT V
ri

ri

d(p i / RT)
dt

ri

1 dp i
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
N A N Ao N Ao X A
N A N Ao (1 X A )
N (1 X A )
N
C A A Ao
V
V
In constant-volume system, V = Vo

CA

N Ao (1 X A )
Vo

C A C Ao (1 X A )

where
N Ao initial moles A
N Ao X A moles of A reacted
XA

moles of A reacted
initial moles A

Integral methods of analysis of rate data

General procedure
1.
2.

Assume a rate expression (i.e., order of the reaction) rA

Rearrange the rate expression to get in the following form

dC A
k. f (C)
dt

dC A

k. dt
f (C)
CA

t
dC A

k dt
C A o f (C)
0

3.

4.

Plot the integral of equation against time.

The plot should yield a straight line with
slope equal to k.
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

t
dC A
k dt

C Ao C A
0

C
ln A k.t;
C Ao

1 C
k ln 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

t
dX A
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
t1/ 2

2.303 C Ao
log

k
C
/
2
Ao

t1/ 2

0.693
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

t
dC A
k dt

2
C Ao C A
0
CA

k.t;

C A C Ao

1
1
C C k.t;
A
Ao

1 1
1
k

t C A C Ao

In terms of conversion

dC A
k. C 2A
dt
d(C Ao (1 X A ))
C 2Ao (1 X A ) 2

continue...........
1 X A

k. dt

dX A
kC Ao . dt
2
(1 X A )
int egrating the above equation
X A 0 at t 0; X A X A at t t
XA

t
dX A
kC Ao dt

2
0 (1 X A )
0

take 1 X A Y
dX A dY
At X A 0, Y 1
XA XA , Y 1 XA

dY

kC Ao t
2
1 Y
[1 / Y ]11 X A kC Ao t
1
1 kC Ao t
1 XA
XA
kC Ao t
1 XA
1
kt
C Ao

XA
1 X

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

(
C
/
2
)
C
Ao
Ao
t1/ 2

1
k C Ao

t1/ 2

1
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
rA

dC A
k. C nA
dt

dC A
n k. dt
CA
int egrating the above equation
C A C Ao at t 0; C A C A at t t
CA

t
dC A
k dt

n
C Ao C A
0
C

C An 1 A

k.t

n 1 C Ao
1 1
1
n 1 n 1 k.t;
n 1 C A C Ao

The dim ensions of rate cons tan t (k )

for n th order reaction are
(time ) 1 (concentration )1n

1
1
n 1 n 1 (n 1)k.t , n 1
C A C Ao

Assignments
1.

2.

3.

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)
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)
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
The rate equation is

aA + bB + Products

dC A
k. C A CB ...
dt
For reac tan ts A and B at any time ,
rA
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

n
C1An C1Ao
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

21n

n
C1Ao
k ' (n 1)t1/ 2

n 1
C1Ao

1
21n k ' (n 1)t1/ 2

n n 1
C1Ao
2 1 k ' (n 1)t1/ 2

n 1

1 1n
C Ao
k ' (n 1)
taking natural log on both sides of equation
t1 / 2

2 n 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
k1
A
R
2
A k
S
The rate of disappearance of A is given by

dC A
k1 C A k 2 C A
dt
int egrate this eqn and apply the lim its
rA

C
ln A (k 1 k 2 ) t
C Ao
rates of formation of R and S
rR

dC R
k 1C A ;
dt

rS

dCS
k 2C A
dt

rR (dC R / dt ) k 1

rS (dCS / dt ) k 2
dC R k 1

dCS k 2
int egrate the above equation
C R C Ro k 1

CS CSo k 2

Irreversible reactions in series

Consider a unimolecular-type first order series reaction of the type
k1
2
A
R k
S
Rate equations for A, R and S

dC A
rA
k1 C A
(1)
dt
dC R
rR
k 1 C A k 2 C R (net rate of formation of R ) (2)
dt
dCS
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 C A
dt

(4)

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
CRe

k 2t

k 1 C Ao

e ( k 2 k1 ) t
C
(k 2 k 1 )

(8)

Initial condition, C Ro 0 at t 0
0

k 1 C Ao
C
(k 2 k 1 )

k 1 C Ao
(k 2 k 1 )

(9)

substituting C in eqn (8)

CRe

k 2t

k 1 C Ao

k C
e ( k 2 k1 ) t
1 Ao
(k 2 k 1 ) (k 2 k 1 )

 e k1t
e k 2t
C R k 1 C Ao

(
k

k
)
(
k

k
)
1
2
1
2

(10)

e k1t
e k 2t
C R k 1 C Ao

(11)

(k 2 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
CS C Ao C Ao e

( k1 t )

e k1t
e k 2t
k 1 C Ao

(
k

k
)
(
k

k
)
1
2
1
2

k 1 k 1e k 2t
( k1 t )
1

CS C Ao 1 e

k
k

2
1
2
1

k 2 k 1e k 2t
( k1 t )

CS C Ao 1 e

k
k

k
2
1
2
1

(12)

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

(
k

k
)
(
k

k
)
1
2
1
2
k C
C R 1 Ao e k1t e k 2t
(k 2 k 1 )

k C
dC R
1 Ao k 1e k1t k 2 e k 2t
dt
(k 2 k 1 )

At max imum R formation condition

k 1 C Ao
k 1e k1t k 2 e k 2t 0
(k 2 k 1 )

dC R
0
dt

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 )
t

ln(k 2 / k 1 )
1

(k 2 k 1 ) k log mean

(14)

By combining eqns (10) and (14) the max imum concentration of R is given by
C R max k 1

C Ao
k2

k 2 /( k 2 k1 )

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
rA A k C A C R
dt
at any time t
Co C A C R C Ao C Ro cons tan t
dC A
k C A (Co C A )
dt
dC A

k dt
C A (Co C A )

rA

Braking int o partial fractions, we get

dC A
1 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 CA
C
kCo t
ln Ao ln o
CA
Co C Ao
C (C C A )
ln Ao o
kCo t
C A (Co C Ao )
Co C Ao C Ro C A C R
C A Co C R
C Ao Co C Ro
ln

C Ao (Co Co C R )
kCo t
C A (Co Co C Ro )

C .C
C /C
ln Ao R ln R Ro 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 (C o 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

C Ao .C Ao Ro X A
C Ao

C Ao (C o 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 2Ao (1 X A )

C Ro
C Ao

C A (C o C Ao ) C 2Ao (1 X A ) M
C o kt

(C Ao C Ro ) kt
C Ao (1 C Ro / C Ao ) kt
C o kt C Ao (1 M ) kt

Interms of M and X A , the eqn (1) becomes

C 2 (M X A )
C (M 1) kt
ln 2Ao
Ao
C (1 X A )M
Ao

(M X A )
C Ao (M 1) kt
ln
(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 forward reaction rate cons tan t

The net rate of disappearance of A

rA k 1C A k 2 C R

dC A dC R

k 1C A k 2 C R
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 Ao dX 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 )
dt
dt

(1)

At equilibriu m, net rate is zero

(i.e., the rate of forward reaction the rate of backward reaction)
dC A
0
dt

and

X A X Ae (equilibriu m conversion)

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 )

k2
(1 X Ae )
k 1 (1 X Ae )
k2
(M X Ae )

KC

C Re
C 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
k (1 X Ae )
dX A
k 1 (1 X A ) 1
(M X A )
dt
(M X Ae )
(1 X A )(M X Ae ) (1 X Ae )(M X A )
dX A
k1

dt
(M X Ae )

X Ae (M 1) X A (M 1)
dX A
k1

dt
(
M

X
)

Ae
dX A k 1 (M 1)

( X Ae X A )
dt
(M X Ae )
dX A
k 1 (M 1) t

dt
(M X Ae ) 0
0 ( X Ae X A )

XA

 X XA
(M 1)

ln Ae
k 1t
X Ae (M X Ae )
X XA
C C Ae
(M 1)
ln A

ln Ae
k 1t
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 Ae X A
Vs t
plot ln
X Ae

( 2)

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 A

ln Ae
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 C So 0, the int egrated rate eqn

applicable to all the forms
X (2 X Ae 1) X A
1

2k 1
ln Ae
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 CC
dt
If B and C are taken in a l arg e excess
dC A

k C A C 0B CC0
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
V dt
1 d(C i V )
ri
V dt
1 dCi
dV
V
Ci
V dt
dt
dCi C i dV

dt
V dt
dCi
d ln V

Ci
dt
dt
ri

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
A
A

VX A 1 VX A 0
VX A 0
Change in total number of moles for complete conversion
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
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
dN Ao (1 X A )
1 dN A
1
rA

k
V dt
Vo (1 A X A )
dt

N Ao
d(1 X A )
1
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

C Ao

XA

t
dX A
k dt

(
1

X
)
0
0
A A

use substitution method

1 AXA Y
A dX A dY
dX A

dY
A

C Ao 1 A X A dY
k t

A
Y
1
C Ao
ln 1 A X A kt
A
C Ao
V
ln
kt
A
Vo

First-order reactions
A Pr oducts
dN Ao (1 X A )
1 dN A
1
rA

k CA
V dt
Vo (1 A X A )
dt

Consider the reaction type

C Ao
C Ao (1 X A )
dX 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 )
XA

V Vo
A Vo

XA

V
A Vo

V
k t
ln 1 X A ln 1
A Vo

Second-order reactions
Consider the reaction type

2 A Pr oducts
A B Pr oducts with C Ao C Bo

rA

C Ao
1 dN A
dX A
2

k
C
A
V dt
(1 A X A ) dt

C Ao
dX A
2 1 XA

k
C
Ao

(1 A X A ) dt
1

A A

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
k C Ao t
A ln 1
Vo A V
Vo A

Problems
1.

2.

The half-life period of a reaction of the first order is 5 minutes.

Calculate its rate constant in seconds.
Show that the decomposition of N2O5 at 67oC is a first order reaction.
Calculate the value of the rate constant.
Time, min

3.
4.

CN2O5, mol/l
0.16
0.113
0.08
0.056
0.040
The half life of a first order reaction A B is 20 min. what percent of
A remains after 100 min?
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

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
Find the order
(torr)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)

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)

CA, (mol/l)

0.041

0.034

0.027

0.023

0.021

0.018

0.016

Time, (min)

10

15

20

CA, (mol/l)

0.015

0.0136

0.012

0.0014

0.0089

0.0067

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

reaction and also the rate constant.
k1
2
12. For the series reaction A
R k
S
with k1 = k2. Find the maximum concentration of R and the time at
which it is reached.