PLUS TWOES

SHORT NOT

CHEMISTRY

CHEMICAL KINETICS
ONAM EXAM SPECIAL
 CHEMICAL KINETICS FACTORS AFFECTING RATE OF A
REACTION
The important factors which affect the rate of
a chemical reaction are :

1. Nature of the reactants

2. Concentration of the reactants
3. Temperature
4. Pressure (for gaseous reaction only)
5. Effect of catalyst
6. Influence of radiation

DEPENDENCE OF RATE OF REACTION ON

RATE OF A CHEMICAL REACTION CONCENTRATION – RATE LAW

The rate of a chemical reaction is the change aA + bB → cC + dD

in concentration of any one of the reactant or
product in unit time. Rate α [Α]a [Β]b
Decrease in concentration of any one of the Rate α [Α]x [Β]y
reactant in unit time
Increase in concentration of any one of the Rate = k [Α]x [Β]y
product in unit time.

aA + bB → cC + dD order = x+y
Avg.Rate = .......................

Inst.Rate = .......................
ORDER OF REACTION
Order is the sum of the powers of the
concentration terms of the reactants in the
rate law.
It is an experimental quantity.

It can have the values 0,1,2,3,...... or a fraction.

It is applicable to both elementary and
complex reactions

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MOLECULARITY OF A REACTION INTEGRATED RATE LAW EQUATION FOR
It is the total number of reacting species
A ZERO ORDER REACTION
collides simultaneously in a chemical reaction.
It is a theoretical quantity. For a first order reaction,
It cannot be zero or fractional. The rate of the reaction is proportional to the
concentration of the reactant.
It can have values 1,2,3 etc.
Consider a first order reaction, R → P
It is applicable only to elementary reactions

aA + bB → cC + dD

DIFFERENCES BETWEEN ORDER AND

MOLECULARITY
Order Molecularity

It is the sum of the powers of the It is the total number of reactant

concentration terms in the rate species collide simultaneously in
law expression a chemical reaction

It is an experimental quantity It is a theoretical quantity

It can be zero or fractional It cannot be zero or fractional

It is applicable to both elementary It is applicable only to elementary

INTEGRATED RATE LAW EQUATION FOR
and complex reactions reactions
A FIRST ORDER REACTION

UNIT OF RATE CONSTANT For a first order reaction,

The rate of the reaction is proportional to the
concentration of the reactant.
Different ordered reactions have different units
for k
Consider a first order reaction, R → P
For an nth order reaction, unit of k =

Zero order reaction; n=0 ....................................

1st order reaction; n=1 ....................................

2nd order reaction; n=2 ....................................

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HALF LIFE OF A REACTION (t1/2) PSEUDO FIRST ORDER REACTION
The half-life of a reaction is the time taken for These are reactions which appear to follow
the concentration of a reactant is reduced to higher order, but actually follow first order
one half of its initial concentration. It is kinetics.
represented as tl/2. In these reactions the concentration of one of
the reactants is large excess and so its change
in concentration does not affect the rate of the
reaction.
1. Hydrolysis of ester (ethyl acetate)

2. Inversion of cane sugar

HALF LIFE OF A ZERO ORDER REACTION
(t1/2)

RATE OF REACTION AND TEMPERATURE

Most of the chemical reactions are accelerated
by increase in temperature.
It is found that for a chemical reaction,
When the temperature is increased by 10°, the
rate of the reaction and the rate constant is
nearly doubled.
The temperature dependence of the rate of a
HALF LIFE OF A 1ST ORDER REACTION chemical reaction can be explained by
Arrhenius equation
(t1/2) The equation is:

k = rate constant
A = Arrhenius factor
Ea = Activation energy
R = Universal gas constant
T = Temperature

For a first order reaction, half-life period is

constant. It is independent of initial
concentration of the reacting species.

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ACTIVATION ENERGY EFFECT OF CATALYST
According to Arrhenius, A catalyst is a substance which alters the rate
of a reaction without itself undergoing any
a chemical reaction occurs by the collision of
permanent chemical change.
reactant molecules.
A catalyst increases the rate of a chemical
All the molecular collisions are not effective. reaction by reducing the activation energy
For effective collision, the colliding molecules between reactants and products.
should have a minimum kinetic energy called
activation energy.

THE IMPORTANT CHARACTERISTICS OF

A CATALYST ARE
1) A small amount of the catalyst can catalyse
a large amount of reactants.
2) It catalyses the spontaneous reactions but
does not catalyse non spontaneous
reactions.
2) A catalyst does not change the equilibrium
constant of a reaction, but it helps to attain
the equilibrium faster by increasing the rate
of both forward as well as the backward
reactions.

ADMISSION STARTED 6009 100 300 6

COLLISION THEORY
The collision in which collide with sufficient K.E
and proper orientation so as to facilitate
breaking of bonds between reactants and
formation of new bond to form products are
called effective collisions.
The number of collisions per second per unit
volume of the reaction mixture is known as
collision frequency (Z).

A + B → Products

Rate of reaction can be expressed as,

Rate(r) = (r) = ZAB e−Ea /RT

COLLISION THEORY
Thus, in collision theory activation energy and
proper orientation of the molecules together
determine the criteria for an effective
collision and hence the rate of a chemical
reaction.

ADMISSION STARTED 6009 100 300 7