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UNIT 4 Reading

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UNIT 4 Reading

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Bharat
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UNIT 4 : CHEMICAL KINETICS

Chemical Kinetics:- It deals with the study of reaction rates and their mechanisms.

Rate of a chemical reaction:It is defined as the rate of change in concentration of


either reactant or product per unit time.
(a) Average Rate of a reaction: Average rate of reaction can be obtained by
dividing the total change in concentration of reactant or product by the
elapsed time.
Average rate =

(b) Instantaneous rate of a reaction: It is the rate of any one of the species
involved in a reaction at particular instant of time.
Instantaneous rate= average rate as t approaches zero.
Instantaneous rate =

Factors affecting the rate of a reaction:-


1. Concentration of the reactants
2. Temperature of reactants
3. Presence of a catalyst

Effect of concentration: Rate of a reaction depends on concentration of reactants.

Rate law: Rate law is the expression in which reaction rate is given in terms of reactants
with each term raised to some power ,which may or may not be same as the stoichiometric
coefficient of the reacting species in a balanced chemical equation.

For a reaction: aA + bB → Product

The rate law is written as: Rate = k[A]x[B]y where, x and y may or may not be equal to
stoichiometric coefficients (a and b) of the reactants
Rate constant (K): It is equal to the rate of reaction when concentration of reactant(s)
is unity.

Order of a reaction: It is defined as the sum of the powers of the concentration of the
reactants terms in experimentally determined rate equation. It can have a value of
zero, integral values as well as fractional values.

Units of rate constant:

Depending on the order of the reaction unit of rate constant changes It can be generally
expressed as mol(1- n) L(n- 1) s-1 ,where n is the order of the reaction.

Examples of zero order reactions

The reaction of hydrogen with chlorine (Photochemical reaction)

Decomposition of nitrous oxide in the presence of hot Platinum catalyst

Decomposition of gaseous ammonia on a hot platinum surface

Examples of first order reaction

Hydrogenation of ethene is an example of first order reaction.

All natural and artificial radioactive decay of unstable nuclei take place by
first order kinetics.
.
Molecularity of a reaction: It is the number of reacting species (atoms, ions or
molecules) taking part in an elementary reaction, which must collide simultaneously in
order to bring about a chemical reaction. It can’t be zero.

Difference between order and molecularity


Order Molecularity

Experimental quantity theoretical

It can be zero and even a fraction but molecularity cannot be zero or a non
integer

Order is applicable to elementary as molecularity is applicable only for


well as complex reactions elementary reactions.

For complex reaction, order is given molecularity of the slowest step is


by the slowest step same as the order of the overall
reaction.

Integrated rate equation:


For a typical first order gas phase reaction

The integrated rate expression will be


Pseudo First Order Reaction : In a chemical reaction between two substances when one
reactant is present in large excess. The concentration of water does not get altered much during
the course of the reaction and the reaction behaves as first order reaction. e.g.

The term [H2O] may be taken as constant, therefore the rate becomes

2. Temperature dependence of the rate of reaction: It has been found that for a chemical
reaction with rise in temperature by 10°, the rate constant is nearly doubled. The temperature
dependence on the rate of a chemical reaction can be accurately explained by Arrhenius
equation

Where k is rate constant for the reaction, A is pre-exponential factor or frequency factor, R is
gas constant, T is temperature and Ea is activation energy of the reactant molecules.

According to Arhennius a reaction takes place only when reactant molecules collide to form
an unstable intermediate called activated complex,which exists for a short time and then
breaks up to form products.

It can be clearly explained using the example


Activation energy:- It is the extra energy which must be possessed by reactant molecules so
that collision between reactant molecules is effective and leads to formation of product
molecules. Activation energy can be calculated if we know the rate constants K1 and K2 at
temperatures T1 and T2 respectively, for the reaction.

Activation energy = threshold energy – energy normally possessed by molecules.

Distribution curve explaining temperature dependence of rate of reaction is given


below

3.Effect of catalyst on rate of reaction:


A catalyst is a substance which
increases the rate of a reaction without
itself undergoing any permanent
chemical change.

For example, MnO2 catalyses the following reaction.

catalyst provides an alternate pathway or reaction mechanism by reducing the activation energy
between reactants and products and hence lowering the potential energy barrier.

Collision theory of chemical reactions: According to this theory, the reactant molecules are
assumed to be hard spheres and reaction is postulated to occur when molecules collide with each
other
For a bimolecular elementary reaction A + B → Products

Rate of reaction can be expressed as Rate = ZAB e -Ea/RT where ZAB represents the collision
-Ea /RT
frequency of reactants, A and B and e represents the fraction of molecules with energies equal
to or greater than Ea.

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