CHEMICAL KINETICS

Rate Of Reaction
Rate of a chemical reaction can simply be defined as rate of change of
concentration of reactant or product w.r.t. time

Rate =
 Types of Rate Of Reaction

Instantaneous rate Average rate

Rate of reaction defined at a Rate of reaction defined over a
certain instant . time interval.

# It is equal to the slope of

Concentration – time graph
Differential Rate Expression or rate Law
Q. In a catalytic experiment involving the Haber process, N2 + 3H2 
2NH3, the rate of reaction was measured in terms of NH3

If there were no sides reactions, what was the rate of reaction expressed in
terms of (a) N2, (b) H2?
Q. The instantaneous rate of disappearance of
the MnO4– ion in the following reaction is 4.56 × 10–3 Ms–1.

MnO4– + I– + H+  Mn2+ + I2 + H2O The rate of appearance of I2 is -

(A) 1.14 × 10–3 Ms–1 (B) 5.7 × 10–3 Ms–1

(C) 4.56 × 10–4 Ms–1 (D) 1.14 × 10–2 Ms–1
Q. In a catalytic experiment involving the Haber process
at 900K , N2 + 3H2  2NH3, if the
pressure of hydrogen changes from 10 atm to 4 atm
in 1 minutes than calculate-

(1) Rate of reaction in atm sec-1

(2) Rate of appearance of ammonia in atm sec-1
(3) Rate of reaction in mol L-1sec-1.
Q. For the reaction N2 (g) + 3H2 (g)  2NH3(g) under
certain conditions of temperature and partial
pressure of the reactants, the rate of formation of
NH3 is 3.4 g min-1. The rate of decomposition of H2 under
the same condition is ............ g min-1.

(A) 0. 1 g min-1 (B) 0.3 g min-1

(C) 0.2 g min-1 (D) 0.6 g min-1
 Rate Law & Rate Expression
It is an experimentally determined expression which relates the rate of a reaction
with the concentration of reactants.
 Elementary Reactions
# These are the reactions which are completed in a single
step . These are also called simple reactions.

# Rate law can be directly written for an elementary

reaction by the stoichiometry of the reaction.

Complex Reactions
# These are the reactions which are completed in more
than one steps .

# Each step of a complex reaction is an elementary

reaction .

# The slowest step is called rate Determining Step(R.D.S)

 Order & Molecularity
Molecularity
It is defined as the number of reacting
species(atoms/molecules/ions/free radicals etc.) which
collide together to form products in a single step reaction.
Characteristics of Molecularity
# Molecularity is a theoretical concept.

# Molecularity of a reaction cannot be zero, -ive

or fractional .

# Reactions with moleculairty greater than 3 are

rarely observed as probability of colliding of
more than three molecules to form products is very less
.
 Order
It is defined as the sum of powers of all the concentration
terms involved in the rate law for a given reaction.
Characteristics of Order
# Since rate law can only be written experimentally ,
order is an experimentally determined Quantity.

# Order of a reaction cann be zero and fractional but

cannot be infinite.

# Order with respect to a particular reactant may be –

ive but overall order cannot be –ive.
# For a complex reaction each step has its own individual
molecularity and there is no meaning of Overall
molecularity.

# For a complex reaction overall Order is defined which

can be calculated by RDS method & Steady State
Approximation.
Q. The reaction, X + 2Y + Z  N occurs by the
following mechanism
(i) X + Y ↔ M (very rapid equilibrium)
(ii) M + Z  O (slow)
(iii) O + Y  N (very fast)
What is the rate law for this reaction
(A) Rate = k[Z] (B) Rate = k[X] [Y]2 [Z]
(C) Rate = k[N] (D) Rate = k [X] [Y] [Z]
Q. The mechanism of the following reaction is:
2NO (g) + 2H2 (g)  N2 (g) + 2H2O (g)

Step 1 : 2NO (g) + H2 (g)  N2 + H2O2 (Slow)

Step 2 : H2O2 + H2 2H2O
Determine the rate law
Q.3 The rate of a reaction is expressed in different ways as follows :
Q. In the following reaction : xA  yB

log  d[ A ] 
  dt 
  = log  d[B] 
 dt 
  + 0.3

where –ve sign indicates rate of disappearance of the

reactant. Thus, x : y is :
(A) 1 : 2 (B) 2 : 1 (C) 3 : 1 (D) 3 : 10
 Significance of order of reaction
The order of a reaction signifies that how the rate of reaction changes by changing
the concentration of a particular reactant.
Q. The following data are for the reaction A + B  products:

Conc. A Conc. B Initial Rate

(M) (M) (mol L–1 s–1)
0.1 0.1 4.0 × 10–4
0.2 0.2 1.6 × 10–3
0.5 0.1 2.0 × 10–3
0.5 0.5 1.0 × 10–2
(i) What is the order with respect to A and B for the reaction?
(ii) Calculate the rate constant.
(iii) Determine the reaction rate when the concentrations of A and B
are 0.2M and 0.35M, respectively.
Relation between different Rate constants
Q. Dinitropentaoxide decomposes as follows :

N2O5(g)  2NO2(g) + ½ O2(g)

Given that –d [N2O5] / dt = k1[N2O5]

d [NO2] / dt = k2[N2O5]
d [O2] / dt = k3[N2O5]

What is the relation between k1, k2 and k3?

Unit of Rate Constant
Analysis of reactions of various order
Zero Order Reactions
Q. The reaction A(g) + 2B(g)  C(g) + D(g) is an elementary
process. In an experiment, the initial partial pressure of A &
B are PA = 0.6 and PB = 0.8 atm, if PC = 0.2 atm then
calculate the ratio of rate of reaction relative to initial rate.
Q. The rate constant of the reaction A  2B is 1.0 × 10–3 mol lit–1 min–1, if the
initial concentration of A is 1.0 mole lit–1 what would be the concentration
of B after 100 minutes.
(A) 0.1 mol lit–1 (B) 0.2 mol lit–1
(C) 0.9 mol lit–1 (D) 1.8 mol lit–1
Q. Graph between concentration of the product and time of the reaction
A  B is of the type

Hence graph between – d[A]/dt and time will be of the type :

(–d[A]/dt)
(A) (B)

Time

(C) (D)
Q. For the following data for the reaction A  products.
Calculate the value of k.
Time (min.) [A]
0.0 0.10 M
1.0 0.09 M
2.0 0.08 M
Q. The data for the reaction A + B  C is
Exp. [A]0 [B]0 initial rate
1 0.012 0.035 0.10
2 0.024 0.035 0.80
3 0.012 0.070 0.10
4 0.024 0.070 0.80

(A) r = k [B]3 (B) r = k [A]3

(C) r = k [A] [B]4 (D) r = k [A]2 [B]2 .
First Order Reactions
Q. For an elementary reaction
X (g)  Y (g) + Z (g)
the half life periods is 10 min. In what period of time would the
concentration of X be reduced to 10% of original concentration -
(A) 20 Min. (B) 33 Min (C) 15 Min (D) 25 Min
A and B are two different chemical species undergoing 1st
order decomposition with half lives equal to 5 sec. and 7.5 sec.
respectively. If the initial concentration of A and B are in the
ratio

3 : 2. Calculate after three half lives of A.

Report your answer after multiplying it with 100.