Molecularity of a Reaction

Q.Why the reactions having molecularity

greater than three is rare ?

Ans:- Since the chances of collision and

reaction of more than three molecules at a
time are very less, the molecularity greater
than three is rare.
 Molecularity of a Reaction
Molecularity in case of complex reactions?

Molecularity of a complex reaction has no meaning.

Actually a complex reaction is the series of two or
more elementary reactions and thus, it completes in
several steps. The slowest step or slowest reaction
determines the rate of the reaction. Hence we find
out the molecularity of the slowest elementary
reaction of a complex reaction which is, in general,
similar to the overall order of the complex reaction.
 Molecularity vs. Order
Molecularity of Reaction Order of Reaction
It is the number of atoms, ions or It is the sum of the power of
molecules that must collide with one concentration terms on which the rate
another simultaneously so as to of reaction actually depends or it is
result into a chemical the sum of powers of the
reaction. concentration terms in the rate law
equation.
Molecularity of reaction Order of reaction can be zero.
Cannot be zero.
It is a theoretical concept. It is determined experimentally.

It is always a whole number. It can even have fractional values.

The overall molecularity of complex Order of reaction is for overall
reaction has no significance. reaction.
Individual step has its own
molecularity.
 Integrated Rate Equations
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
 Integrated Rate Equations

Integrating both sides between proper limits

[R] ̶ [Ro] = ̶ kt
Or
[Ro ] ̶ [R] = kt
Or
k=
Integrated Rate Equations
 Integrated Rate Equations
First Order Reactions
First order reaction means that the rate of the reaction is
proportional to first power of the concentration of reactants.
Consider the reaction,
R→P
 Integrated Rate Equations
Integrating both sides between proper limits

ln[R] ̶ ln [Ro ] = ̶ kt
Or
ln [Ro ] ̶ ln[R] = kt
Or
[Ro]
kt = ln [R]
𝟏 [Ro]
Or k= ln
[R]
𝐭

𝟐.𝟑𝟎𝟑 [Ro]
Ork= log10
𝐭 [R]
 Integrated Rate Equations

𝟐.𝟑𝟎𝟑 [Ro]
k= log10
[R]
𝐭
 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
t1/2 for a Zero Order Reactions
 Half-Life of a Reaction
t1/2 for a First Order Reactions

Thus for a first order

reaction, half-life
period is constant, i.e.,
it is independent of
initial concentration
of the reacting species.
 Pseudo - first order reaction
Reactions which are not truly of the first order but under
certain conditions reactions become that of first order are
called pseudo unimolecular reaction.
For example: Hydrolysis of ester in presence of acid
CH3COOC2H5 + H2O → CH3COOH + C2H5OH
From this reaction, the rate expression should be
r = k [ester] [H2O]
Since, hydrolysis takes place in the excess of H2O and
concentration change of H2O is negligible practically.
therefore, r = k’ [ester]
Where k’ = k[H2O].
Methods of determining the order of a reaction

Integrated method
The equation which gives a constant value of k decides the order
of reaction
Graphical method
The data are plotted acc to different integrated rate equations
so as to yield a straight line .Slope gives the value of rate
constant
Initial rate method
Concentration of one of the reactant is varied

Half life method

In this method we plot half life of the reactant versus conc. of
the reactant.
Methods of determining the order of a reaction

Reaction Differential Integrated rate Characteristic Slope Units of rate

Order rate law law kinetics Plot of constant
kinetic
s plot

Zero −d[A] [A]=[Ao]-kt [A] vs t -k Mole l-1 sec-1

=k
dt

First −d[A] [A]=[Ao]e-kt In[A] vs t -k sec-1

= k [A]
dt

Second −d[A] [Ao] 1/[A] vs t k L mole-1 sec-1

= k [A] 2 A =
dt 1 + k + [A]
 Graphical Representation

dx dx dx
dt dt dt

Conc. Conc. (Conc.)

2

zero order first order second order

Graphical representation of rate versus concentrations
 Graphical Representation

Conc. [A] log [A] 1/ [A]

t t t
zero order first order second order

Graphical representation for concentration of integrated rate equation versus time

 Initial rate method
• This method involves the determination of the order
of each reactant separately.

• To determine the order of a particular reactant, its

concentration is varied keeping the concentrations of
other reactants constant.

• In every experiment, we determine the initial rate of

the reaction and observe the dependence of rate on
that particular reactant.

r  [A]m[B]n Keeping [B] constant

m
m
r1 [A1] [B] n
r1  [A1] 
= m n
; = 
r2 [A2 ] [B] r2 [A2 ] 
 Half life method

1
t1 / 2 
[A] 0n− 1

t1/2 t1/2 t1/2

a a 1/a
zero order first order second order
Graphical representation for half lives versus concentration
Integrated method

In this method, we put the data into the integrated

form of the rate laws and calculate the values of the
rate constants for different kinetics of the reaction.

The order of the reaction is that one for which the value
of rate constant is constant.
 Some first order reactions
Decomposition of H2O2
1
H2O2 → H2O + O2
2

Let Vo & Vt be volume of KMnO4 used during zero & time

t respectively

V  a
Vt  a − x
2.303 Vo
k = log
t Vt
Some first order reactions
Hydrolysis of ester
+
CH3COOC2H5 + H2O →
H
CH3COOH + C2H5OH
a 0 0
a−x x x
0 a a
Let V0 , Vt V be the volume of alkali required for titration

during 0 ,t & infinite time
VO  HCl
Vt  HCl + x
V  HCl + a

V − Vt  a −x 2.303 V − Vo
k = log 
V  a t V − Vt
 Theories of chemical kinetics

1. Collision theory

2. Transition state theory

 Collision theory
Reaction occurs when reacting species have sufficient energy
to collide and proper orientation in space.

Energy barrier:
The minimum energy which the colliding particles possess in
order to bring about the chemical reaction is called threshold
energy
The energy difference between threshold energy & average
energy of reacting molecules is called activation energy

Orientation barrier:
Colliding molecules should be in their proper orientation at
the time of collision.
 Transition State Theory
In the activated complex theory, we consider two reactants
approaching and their potential energy rising and reaching a
maximum.

H = Ea − Ea`

Activation energy - the energy needed to form activated

complex is called energy of activation. It is very low for some
reactions and very high for others.
 Some Points about Ea

1. Ea is always positive.

2. The larger the value of Ea, the slower the

rate of a reaction at a given temperature.

3. The larger the value of Ea, the steeper the

slope of (ln k) vs (1/T). A high activation
energy corresponds to a reaction rate that
is very sensitive to temperature.
 Effect of temperature on rate of chemical reaction

For a chemical reaction with rise in temperature by 10°,

the rate constant is nearly doubled

k(T+10)
The ratio kT is called the temperature
coefficient and its value is 2 or 3
 Effect of temperature on rate of chemical reaction

Arrhenius equation

The temperature dependence of the rate of a chemical reaction

can be accurately explained by Arrhenius equation

k = A.e-Ea/RT
A is frequency factor or Arhenius constant, Ea is activation
energy

or

Plot of log k vs 1/T is a straight line & slope = ̶ Ea/2.303R

Effect of temperature on rate of chemical reaction

Plot of ln k vs 1/T is a straight line & slope =-Ea/R

Effect of temperature on rate of chemical reaction

At temperature T1 Eqn.1

At temperature Eqn.2
T2
k1 and k2 are the values of rate constants at temperatures T1 and T2
respectively. Subtracting equation (2) from (1), we obtain
Effect of temperature on rate of chemical reaction

k = A.e-Ea/RT

k2 Ea 1 1
or log =  - 
k1 2.303 R  T1 T2 
 Catalysis

Catalyst: A substance that changes the rate of a reaction

without being consumed in the reaction.

• Provides an easier way to react.

• Lower activation energy.
• Still make the same products.
• Enzymes are biological catalysts.

Inhibitor: A substance that decreases the rate of reaction (a

negative catalyst).
How catalyst change reaction rate

• Catalysts are
the one way to
lower the
energy of
activation
for a particular
reaction by
altering the
path of the
reaction.

• The lower
activation
energy allows
the reaction to
proceed
faster.
 Rate Law and Mechanism
A mechanism is a collection of elementary steps devised to
explain the reaction in view of the observed rate law.
For the reaction, 2 NO2 (g) + F2 (g) → 2 NO2F (g), the rate
law is,
rate = k [NO2] [F2] .
Can the elementary reaction be the same as the overall
reaction?
If they were the same the rate law would have been
rate = k [NO2]2 [F2],
Therefore, the overall reaction is not an elementary
reaction.
 Rate-determining Step in a Mechanism

Slowest step:
The rate determining step is the slowest elementary step
in a mechanism, and the rate law for this step is the rate
law for the overall reaction.

Steady-state approximation:
The steady-state approximation is a general method for
deriving rate laws when the relative speed cannot be
identified. It is based on the assumption that the
concentration of the intermediate is constant.