CHEMICAL KINETICS

Chemical reactions are classified in to

1)Fast reactions
Takes place very rapidly

2)Moderate reactions
Takes place in a moderate speed

3)Slow reactions
Takes place very slowly
 RATES OF CHEMICAL REACTIONS
Rate of a chemical reaction is defined as the change in
concentration of any one of the reactants or products
per unit time.
For a hypothetical reaction,
A—› B
Rate of reaction can be represented as
-[A]/ t = +[B]/  t
-[A] = Decrease in concentration of reactant with
time.
+[B] = Increase in concentration of product with
time.
t = Time interval.
 Instantaneous rate & Average rate
Instantaneous rate is defined as the rate of change in
concentration of any one of the reactants or products at
a particular time.
For the reaction aA—›bB
Instantaneous rate = - (1/a) (d[A]/dt) =+ (1/b) (d[B]/dt)
Average rate is defined as the rate of change in
concentration of any one of the reactants or products at
a particular time interval.
Average rate =- (1/a) ( [A]/  t ) = +(1/b)( [B]/  t)
Units of rates of reaction.
Concentration time -1
OR mol L-1 s-1
C4H9Cl(aq) + H2O(l) → C4H9OH(aq) + HCl(aq)
 Factors affecting rate of reactions
1) Concentration of reactants.
2) Temperature.
3) Nature of reactants and products
4) Exposure to light(Radiation)
5) Presence of catalyst
Effect of concentration on reaction rates

Rate of a chemical reaction increases with

increase in concentration of any one of the
reactants.
According to law of mass action the rate of a
chemical reaction is proportional to the molar
concentration of the reactants or products.
 Rate Equation
For the reaction aA + bB —› P
Rate ∞ [A]a[B]b
Rate = k [A]a[B]b
k = rate constant or specific reaction rate.
[A] = 1 and [B] = 1 ; Rate = k
Rate constant or specific reaction rate is the rate
of a reaction when the concentration of the
reactants is unity.
The above expression is called Rate equation.
 Order of a reaction
In the rate equation the exponents of the concentration
terms may not be equal to the stoichiometric coefficient in
the balanced chemical equation.
For the reaction aA + bB —› P
Rate = k [A]x[B]y
x & y may or may not be equal to a & b
Order of reaction is defined as the sum of the powers to
which the concentration terms are raised in the rate law
expression. Order = x + y
Order is an experimentally determined quantity. It may be
zero, whole number, fractional, or negative.
If the order of a reaction is one it is called a first order
reaction. If it is two it is called second order reaction.
 Reactions of different orders
1st order
N2O5 —› 2NO2 + 1/2O2 Rate = k[N2O5]
Decomposition of NH4NO2 in aqueous solution
NH4NO2 —› N2 + 2H2O Rate = k[NH4NO2]
IInd order
2NO2 —› 2NO + O2 Rate = k[NO2]2
H2 + I2 —› 2HI Rate = k [H2] [I2]
IIIrd order
2NO + O2 —› 2NO2 Rate = k[NO]2 [O2]
2NO2 + Cl2 —› NOCl + O2 Rate = k[NO2]2[Cl2]
Order 3/2
CH3CHO —› CH4 + CO Rate =k. [CH3CHO]3/2
Zero order
Decomposition of Ammonia on metal surface.
2NH3 —› N2 + 3H2 Rate = k[NH3]0
 Units of rate constant
For a zero order reaction Rate = k[A]0

k = rate/[A]0 = mol L-1 s-1 /1 = mol L-1 s-1

For a first order reaction Rate = k[A]
k = rate/[A] = mol L-1 s-1/ mol L-1 = s-1
For a Second order reaction Rate = k[A]2
k =rate/[A]2 = mol L-1 s-1/ ( mol L-1 )2 = mol-1 L s-1

In general mol1-n Ln-1s-1

 Molecularity of a reaction

Molecularity of a reaction can be defined as the

number of molecules, atoms or ions which
collide simultaneously to bring about the
chemical reaction.
For the reaction aA + bB —› P

Molecularity = a+ b
If the molecularity of a reaction is one the
reaction is a unimolecular reaction. If it is two
reaction is a bimolecular reaction.
Egs
O3 —› O2 + O Unimolecular.
2HI —› H2 + I2 Bimolecular
Molecularity of a reaction can also be defined as
the number of molecules of reactants which
appear in the equation when the reaction is
represented by a correct stoichiometric
equation.
 Elementary and complex reactions
Chemical reactions takes place in a single step are
called elementary reactions. Egs
NH4NO2 —› N2 + 2H2O Molecularity = 1
H2 + I2 —› 2HI Molecularity = 2
A reaction which takes place in a number of steps
is called a complex reaction. Egs. Decomposition
of H2O2 in presence of I-(Two step process)
H2O2 + I- —› H2O + IO- (Slow)
H2O2 + IO- —› H2O + I- + O2 (Fast)
The slowest step is called the rate determining
step.
Differences between Order and Molecularity

Order Molecularity
1. It is the sum of the 1. It is the number of
powers of the reacting species
concentration terms colliding simultaneously
2. It is determined 2. It is a theoretical
experimentally concept.
3. May be whole number, 3. It always a whole
Fraction or zero number
4. It gives some idea about 4. It does not gives some
the mechanism of the idea about the
reaction mechanism of the
reaction
 Integrated rate equation
Zero Order Reactions
Zero order reaction means that the rate of the
reaction is proportional to zero power of the
concentration of reactants.
Consider the reaction, R → P
Rate = - d[R]/dt =k[R]0.
- d[R]/dt =k
d[R]=-kdt
Integrating both sides
[R] = – k t + I ...................(1)
where, I is the constant of integration.
At t = 0, the concentration of the reactant R =
[R]0, where [R]0 is initial concentration of the
reactant.
Substituting in equation (1)
[R]0 = –k × 0 + I
[R]0 = I
Substituting the value of I in the equation (1)
[R] = -kt + [R]0
Further simplifying, we get the rate
constant, k as
k={[R]0 - [R]}/t
Zero order reactions are relatively uncommon
but they occur under special conditions.
Some enzyme catalysed reactions and
reactions which occur on metal surfaces are
a few examples of zero order reactions.
2NH3(g) ⎯⎯⎯⎯⎯→N2(g) +3H2(g)
Rate = k [NH3]0 = k
The equation for a straight line is y=mx+c,
where m is slope and c is the intercept.
[R] = -kt + [R]0
So on plotting [R] against t, we get a
straight line with slope –k and intercept [R]0
slope=- k

[R]

time
 First Order Reactions
In this class of reactions, the rate of the
reaction is proportional to the first power of
the concentration of the reactant R. For
example,
R → P
Rate = - d[R]/dt =k[R].
- d[R]/[R] =k.dt
d[R]/[R] = - k.dt
Integrating this equation, we get
ln [R] = – kt + I .............(1)
Again, I is the constant of integration.
When t = 0, R = [R]0, where [R]0 is the initial
concentration of the reactant.
Therefore, equation (1) can be written as
ln [R]0 = –k × 0 + I
ln [R]0 = I
Substituting the value of I in equation (1)
ln[R] = -kt + ln[R]0
Rearranging this equation,
ln[R]/[R]0 = -kt
k=(1/t)ln[R]0/[R]
k= (2.303/t) log{[R]0/[R]}
If we plot log[R]0/[R] against t, we get a
straight line with slope k/2.303

slope=k/2.303
log[R]o/[R]

time
Half-Life of a Reaction
The half-life of a reaction is the time in which
the concentration of a reactant is reduced to
one half of its initial concentration. It is
represented as t1/2.
For a zero order reaction, rate constant
is given by equation
k={[R]0 - [R]}/t
At t = t1/2, [R]=[R]0/2
The rate constant at t1/2 becomes
k={[R]0 -1/2 [R]0}/t1/2
t1/2 = [R]0/2k
It is clear that t1/2 for a zero order reaction is
directly proportional to the initial concentration
of the reactants and inversely proportional to
the rate constant.
Half-Life of a Reaction : first order
k= (2.303/t) log[R]0/[R]

 [ R ]0 
2.303 log   kt
 [ R]  At half-life [R]=[R]o/2
 [ R ]0 
2.303 log   kt1/ 2
 1 / 2.[ R ]0 
2.303 log 2  kt1/ 2
Half-Life of a first order
0.693  kt1/ 2
Reaction is independent of
0.693
t1/ 2 
k initial concentration.
 Pseudo first order reaction.
Reactions which appear to be higher order but
actually follow lower order kinetics is called
Pseudo order reactions.
1)Acid catalysed hydrolysis of Ethyl acetate.
CH3COOC2H5 + H2O —› CH3COOH + C2H5OH
Rate = k[CH3COOC2H5]
2) Inversion of cane sugar
C12H22O11 + H2O —› C6H12O6 + C6H12O6
Rate = k[C12H22O11]
Temperature dependence of the rate of a reaction
Rate of reactions increases with temperature.
With 100C rise in Temperature, rate get doubled.
Ratio between rate constant at two temperatures
differing by 100C is called temperature coefficient
of the reaction.
Arrhenius Equation (Relation between k and T)
k = A.e (-Ea/RT)
Ea – Activation energy.
T – Temperature.
R – Gas constant.
A – Arrhenius parameter
According to Arrhenius, a reaction can take
place only when reactant molecules collide
to form an unstable intermediate called
activated complex (C). It exists for a very
short time and then breaks up to form the
products. The energy required to form this
intermediate, is known as activation
energy (Ea).
 activated complex
e

n
Ea
e reactants

r
H = (-)
g products

Progress of reaction
Activation Energy
Energy is released when the complex
decomposes to form products. So, the final
heat of the reaction depends upon the
nature of reactants and products.
 Limitation of Arrhenius
All the molecules in the reacting species do
not have the same kinetic energy. To
overcome this problem, Ludwig Boltzmann
and James Clark Maxwell used statistics to
predict the behaviour of large number of
molecules. They plotted the fraction of
molecules (NE/NT) with a given kinetic
energy (E) vs kinetic energy
Fraction of molecules

most probable kinetic energy

Kinetic energy of molecules

The peak of the curve corresponds to the
most probable kinetic energy, i.e., kinetic
energy of maximum fraction of molecules.
Explanation of increase in reaction rate
with temperature
When the temperature is raised, the
maximum of the curve moves to the higher
energy value and the curve broadens out,
i.e., spreads to the right, as a result a large
number of molecules will have higher
energy.
 Maxwell-Boltzmann distribution curve

T2 > T1

Fraction of molecules
T2

T1

Ea
Kinetic Energy

(i) The total area under the curve is proportional to the total # molecules

present.
(ii) Total area is the same at T1 and T2.

(iii) The shaded areas represent the number of particles that exceed the energy of activation,

Ea. 37
Kinetic Energy
Effect of Catalyst on reaction rate
A catalyst is a substance which alters the
rate of a reaction without itself undergoing
any permanent chemical change.
 For example, MnO2 catalyses the following
reaction so as to increase its rate
considerably.
2KClO3 ⎯⎯Mn⎯O2⎯→2 KCl + 3O2
 Effect of Catalyst
Explanation by intermediate complex theory

According to this theory, a catalyst

participates in a chemical reaction by forming
temporary bonds with the reactants forming an
intermediate complex. This intermediate
complex has a transitory existence and
decomposes to yield products and the catalyst.
 Intermediate complex theory
(contd…)
It is believed that the catalyst provides an
alternate pathway or reaction mechanism by
reducing the activation energy between
reactants and products and hence lowering the
potential energy barrier
 Features of catalysis
Catalyst does not initiate a reaction. It only
catalyses a spontaneous reactions, which is
underway. It is also found that a catalyst does
not change the equilibrium constant of a
reaction. It only helps to attain the
equilibrium faster. It catalyses the forward as
well as the backward reactions to the same
extent so that the equilibrium state remains
same but is reached earlier.
COLLISION THEORY OF REACTION RATES
It was proposed by Max Trautz and William
Lewis in 1916 -18.
This theory assumes the reactant molecules as
hard spheres
 Collision theory: postulates
1)A reaction takes place when reactant molecules
collide each other.
2)The collisions which actually bring about the
chemical reaction are called effective collisions.
3)The minimum energy which the colliding
molecule must possess to make the collisions
effective is called threshold energy.
Threshold energy = Activation energy + Energy
possessed by reactant molecules.
4)The number of collisions per second per volume
of the reaction mixture is called collision
frequency (Z).
for the reaction, A + B → Products
Rate = ZAB.e-Ea/RT
ZAB is the collision frequency
e-Ea/RT is the fraction of molecules with energy
equal to or greater than Ea .
The collisions in which molecules collide
with sufficient kinetic energy and proper
orientation leads to breaking of bonds
between reacting species and formation of
new bonds to form products are called
effective collisions.
To account for effective collisions, another
factor P, called the probability or steric factor
is introduced. It takes into account the fact
that in a collision, molecules must be
properly oriented. So
Rate = P.ZAB.e-Ea/RT
Molecular Collisions
Collision Theory
Thus collision theory considers both
activation energy and proper orientation of
the molecules as the criteria for an effective
collision and hence the rate of a chemical
reaction.
The drawback of collision theory is that it
considers atoms/molecules as hard spheres
and ignores their structural aspects.
The End