DELHI PUBLIC SCHOOL PATNA

CHEMISTRY KINETICS
CLASS XII
MODULE- 2 (Factors effecting Rate Of Reaction)
Learning outcome:
Students will be able to;
 List the factors affecting the rate of reaction
 State Rate law
 Understand the meaning of the terms rate constant and order in the rate law.
 Derive units for rate constants for various order
 Differentiate between order and molecularity of a reaction.
 Differentiate between elementary and complex reaction
FACTORS EFFECTING RATE OF REACTION
1. Concentration
2. Temperature
3. Catalyst
DEPENDENCE OF RATE ON CONCENTRATION OF REACTANTS

RATE LAW
The actual dependence of rate on concentration of reactants is given by Rate law which is obtained
experimentally.
It is the expression in which reaction rate is given in terms of molar concentrations of reactants with each term raised to
some experimentally determined power, which may or may not be same as the stoichiometric coefficient of the reacting
species in a balanced chemical equation. It is also called rate equation.
How is rate law of a reaction obtained and expressed?
Consider a general reaction:
aA+bBcC+dD
The rate expression for’ this reaction determined through experiments may be written as:
Rate  [A]x [B]y
Rate = K [A]x [B]y
Here, k = Proportionality constant called “Rate Constant”.
x = Order of the reaction w.r.t the reactant ‘A’
y = Order of the reaction w.r.t the reactant ‘B’
x + y = n = ‘Order of the reaction’
Note: i) ‘x’ and ‘y’ are experimentally determined values
ii) They may or may not be equal to the stoichiometric coefficient of the respective reactants.
For e.g.
If the rate law for a reaction is given as
Rate = K [NO]2 [O2],
The overall order of this reaction = 2+1= 3, which is obtained experimentally.
ORDER OF A REACTION
The sum of powers, to which the concentration terms of the reactants are raised to in the experimentally
determined rate law is called the order of a reaction.
 Order of a reaction can be 0, 1, 2 or 3.
 Order of a reaction can be a fraction also.
 For zero order reaction, the rate is independent of the concentration of reactants.
Units of rate constant (K) :
For a general nth order reaction,
Rate = K [A]n
K = Rate/[A]n
= molL-1 S-1 / (molL-1)n
=(mol L-1)1-n S-1.
So,

Reaction Order (n) Unit of K

Zero order 0 mol L-1 s-1

First order 1 s-1

Second order 2 mol-1 L s-1

 Let us differentiate between rate of reaction and reaction rate constant.

Rate of reaction Rate constant

It is the change in concentration of reactants and It is defined as the rate of a reaction when the
products per unit time. concentration of each reactant appearing in the
experimentally derived rate equation is taken as unity.

It depends on the molar concentration of reactants at It is constant at a particular temperature and does not
that instant of time. depend on the concentration of reactants.

Its unit is mol litre-1 time-1. For nth order reaction, the units of k is given by (conc) 1-n
time-1.

MOLECULARITY OF A REACTION (https://www.youtube.com/watch?v=aBphM8FIafU)

It is the number of reacting species (atoms, ions or molecules) taking part in an elementary reaction (one step
reaction), which must collide simultaneously in order to bring about a chemical reaction.
For e.g

Reaction Molecularity

NH4NO2  N2 + 2H2O 1 ( Unimolecular )

2 HI  H2 + I2 2 ( Bimolecular )

2NO + O2  2NO2 3 ( Trimolecular )

Note: The probability that more than three molecules can collide and react simultaneously is very small. Hence, reactions
with molecularity greater than 3 are very rare and slow to proceed.
For e.g., consider the following reaction:
KClO3 + 6 FeSO4 + 3 H2SO4  KCl +3 FeSO4 + 3 H2O
The molecularity of this reaction seems to be 10. But it is not so. This reaction actually proceeds through many steps.
Elementary and Complex Reactions:
Elementary Reactions: These are reactions taking place in one step.
Complex Reactions: These are reaction which does not take place in a single step but in a sequence of elementary
reactions.
For elementary reactions, the order of reaction is the same as its molecularity and order with respect to each
reactant is equal to its stoichiometric coefficient. .

Eg: For the elementary reaction A + B-C,

The order and molecularity is same, which is equal to 2, which is obtained from the stoichiometric coefficient.
How are rate and order of a complex reaction determined?

 For a complex reaction molecularity makes no sense.

 Since a complex reaction is made of elementary reactions, each elementary reaction will have a molecularity’
which can be obtained from the stoichiometric coefficient of reactants.
 Order is obtained from the rate law, which can be written from the slowest step which is called the rate
determining step.

For e.g Consider the decomposition of H2O2 catalysed by I- in alkaline medium

2 H2O2 -- ----------- 2 H2O + O2
(I- in Alkaline medium)
Actually this reaction takes place in two elementary steps:
1.) H2O2 + I-  H2O + IO- (slow)
2.) H2O2 + IO-  H2O + I- + O2(fast)
Here each step will have molecularity but the order is obtained from the slowest step only.
Rate law is obtained from the slowest rate determining step and is found to be
Rate = K [H2O2][I-]
As the first step is the slow and rate determining step, we can write the rate law from this step. So, the reaction is second
order.
Solved Questions :
1. Differentiate between order and molecularity of reaction.

ORDER MOLECULARITY

It is defined as the sum of the exponents to which Molecularity of elementary reaction is defined as the
each concentration term is raised in the experimentally number of reactant molecules which collide
derived rate law equation. simultaneously before they are converted into products

It is an experimental quantity It is a theoretical quantity.

It can have any value (zero, fractional, It cannot be zero or fractional. It is always a whole
number.
and integral).

2. Predict the order of a reaction: 2 NO + Br2  2 NOBr, which has a rate law expressed as, Rate = K [NO]2
[Br2].
Ans: 3
3. For the reaction, A  B, the rate of a reaction becomes three times when the concentration of A is increased
by nine times. What is the order of the reaction?
Ans: Suppose order of the reaction is ‘n’. Then
Rate = K [A]n
Initially, Rate = r = K [A]n Equation (1)
When, concentration is increased 9 times,
Rate = 3r = K [9 A] n Equation (2)
Dividing equation (2) by equation (1):
3 = (9A)n/An = 9n = 32n
So, 2n = 1, or n =1/2 = 0.5
4. The rate constant of a reaction is 3 x 102 h-1. What is the order of this reaction?
Ans: First order.
5. A reaction is of second order with respect to a reactant A and first order w.r.t B. How is the rate of
reaction affected if the concentration of A and B is doubled?
Ans: Rate= K [A]2[B]
Rate1 =K [2A]2 [2B]
 Rate1= 8 times
Assignments:
1. For the reaction, A  B, the rate of a reaction becomes four times when the concentration of A is doubled. What is
the order of the reaction?
2. For the reaction, A  B, the rate of a reaction becomes 8 times when the concentration of A is doubled. What is the
order of the reaction?
3. For the reaction, A  B, the rate of a reaction becomes 27 times when the concentration of A is increased by three.
What is the order of the reaction?
4. A reaction is of second order with respect to a reactant A and B. How is the rate of reaction affected?
(i) if the concentration of A and B is doubled?
(ii) if the concentration of A is doubled and that of B is halved.
NCERT exercise
1. What are the units of rate constant for a zero order and second order reaction?
2. NCERT Exercise Q.No – 4.1
3. NCERT Exercise Q.No – 4.2
4. NCERT Exercise Q.No – 4.3
5. NCERT Exercise Q.No – 4.5
6. NCERT Exercise Q.No – 4.6