STUDENT MATERIAL

Chemical Kinetics Equation 1 can be written as,

Chemical Kinetics → It is the branch of
chemistry which deals with the rates of
chemical reactions and the mechanism by
which they occur.
Δ [Α] signifies the change in concentration of A,
while 'Δt' is the time interval.
Similar to the above, with [B]2 as the
concentration of product B at time t2 and [B]1
as the concentration product B at a time t1,
then the average rate in terms of B is,

Rate of a chemical reaction → It can be

defined as the speed with which the reactants Equation 3 can be written as,
are converted into products.

Equations (2) and equation (4) represent the

It may be expressed either as the rate of
decrease in concentration of reactants or the
rate of increase in concentration of products.
average rate of a reaction. For the hypothetical
reaction , the rate of the reaction in
the terms of appearance and disappearance of
the product and reactant is given as,

For a reaction
A → B
Instantaneous Rate of Reaction
Δ [A] Δ [B]
Rate of reaction= − = Instantaneous rate of reaction is defined as the
Δt Δt rate of change of concentration of any one of
the reactants or products at a given time. To
Where Δ [A], Δ [B] → concentrations of A and measure the instantaneous rate the time
interval ' t' should be made as small as
B respectively possible so that there is the least possible
change in rate over that interval. Such rates
Δ t → Change in time may be represented in terms of infinitesimally
small change in concentration of reactant or
product (written as d[x]) in infinitesimally
Average and Instantaneous rate of a small interval of time, 'dt'. The rate of the
reaction:- reaction may be expressed as:

Average Rate of Reaction If the rate is expressed in terms of

The average rate of a reaction is defined as the
rate of change of concentration of a reactant or
a product over a specified measurable period
of time. This can be calculated by dividing the
concentration difference by the given time
interval. Considering the above
reaction , if [A] 2 is the
concentration of reactant A at time t2 while [A]
1 is the concentration reactant A at a time t1
then average rate (r) is
concentration of any one of the reactants,
which keeps on decreasing, the negative sign
is used. On the other hand, if the rate of the
reaction is expressed in terms of the
concentration of any one of the products which
goes on increasing, it is a positive value.
Mathematically, instantaneous rate (rinst) for
the reaction is given by,

The square brackets are used to express molar Instantaneous rate is the value of for the
concentration. tangent at a given time 't'. In terms of the
concentration versus time curves of the

CBSE 12 Chemistry 1

reactants and the products shown earlier, it is
actually the slope of the tangent.
rinst = -slope for the reactant = + slope for the
product
Example: Dehalogenation of trimethyl bromide
(CH3)3 CBr is given by the reaction.
The following data were obtained.
[(CH3)3 CBr] x
Time (hr)
10-2 M
0 10.39
3.15 8.96
6.20 7.76
10.00 6.39
18.30 3.53
30.80 2.07
Calculate the instantaneous rate by plotting
the data as concentration versus time and
taking the slope of the tangent drawn to the
curve at some point of time 't'.
Solution:
The plot of concentration versus time is shown
in figure below. The rate of the reaction at a
particular time is determined by drawing a
tangent to curve at a point corresponding to
that time. Then the slope of the tangent gives
the rate of the reaction at that time.
The instantaneous rates were calculated at
times 6.5 hours and 16.2 hours. The rates are,
At time 6.5 hours = 0.39 M / hr
At time 16.2 hours = 0.23 M / hr
From the above data it is observed that the
instantaneous rate appear to change with time.
Factors Affecting Rate of Reaction
CBSE 12 Chemistry
STUDENT MATERIAL
1. Concentration of the reactants: In most
cases, the rate of a reaction is accelerated with
increase in concentration of a reactant. A piece
of wood burns faster in oxygen than in air.
2. Temperature at which the reaction
occurs: A rise in temperature increases the
rate of a reaction. Cooking at sea level takes
less time than on the mountain top because
water boils at lower temperature at sea level
than at the mountain top.
3. Concentration of catalyst (in
homogenous reactions): A catalyst usually
speeds up the rate of reaction although it is
not consumed in the reaction. Oxidation of
sulphur dioxide (SO2) to sulphur trioxide (SO3)
is a very slow reaction. However, this reaction
accelerates in the presence of nitric oxide
(NO).
4. Surface area: In a heterogeneous reaction
an increase in surface area of a solid reactant
or catalyst leads to an increase in the rate of a
reaction. A reaction between a solid phase and
a gas or between a solid and a liquid occurs on
the surface area of the solid. For example,
when charcoal is crushed to powder it ignites
easily to produce a flame; solid charcoal has
been subdivided into many smaller particles
with larger surface area per volume and
therefore burns rapidly.
Rate Law
The representation of rate of reaction in terms
of concentration of the reactants is known as
rate law. It is also called the rate equation or
rate expression.
Rate Expression and Rate Constant
Let us consider a reaction of a simple type.
In this reaction, only a single substance
undergoes the reaction and, thus, the rate of
the reaction will depend only on the
concentration of A. Mathematically, it may be
expressed as:
Rate = k [A]
Where [A] represents the molar concentration
of ‘A’ while ‘k’ is a constant of proportionality
for this reaction and is known as rate constant.
The rate constant is also called velocity
constant or specific reaction rate.
If the concentration of the reactants involved
in the reaction is unity i.e., [A] = 1,
we get:
Rate of reaction = k x 1 = k
Thus, the rate constant of a reaction at a given
temperature may be defined as the rate of the
2

reaction when the molar concentration of each
of the reactants is unity.
For another hypothetical reaction,
The rate of reaction can depend on the
concentrations of A and B in the following
manners.
i)
ii)
The expressions, k[A][B] and k'[A]2[B] are the
rate law expressions for the rate of the
reaction and k is the rate coefficient or specific
rate constant of the reaction. There can be
other rate law expression for the same
hypothetical reaction given above such as,
Rate = k''[A][B]o
Rate = k'''[A]1/2[B]1
Rate Law
In general, for any hypothetical reaction,
The rate law expression can be written as,
Rate (r) = k [A]a[B]b.
It is an equation that relates the true rate of
reaction to the concentrations of the reactants
raised to some power.
Rate Constant
For the equation: a A + b B Æ c C + d D,
Rate = k [A]a [B ]b
Rate constant is defined as the rate of the
reaction when the concentration of each
reactant is taken as unity.
Characteristics of Rate Constant
The value of rate constant
• Gives an idea about speed of the reaction
• Is fixed for a reaction at a particular
temperature.
• Changes with temperature.
• Is independent of the concentration of the
reacting species
• Has units depending on the order of the
reaction
Order of a Reaction
CBSE 12 Chemistry
STUDENT MATERIAL
The order of a reaction is the sum of the
powers to which the concentration terms are
raised in a rate law expression. The order of
reaction is determined with respect to each
reactant in the reaction. For the reaction,
Where there are more than one reactants, the
order of the reaction is determined with A and
then with B.
For a general reaction,
The reaction rate is described by the
expression, Rate= k [A]p [B]q [C]r
Where, k is the rate constant of the reaction.
[A], [B] and [C] are the molar concentrations
of the reactants A, B and C.
Then,
Order of the reaction with respect to A = p
Order of the reaction with respect to B = q
Order of the reaction with respect to C = r
And,
Overall order of the reaction = p + q + r.
The total number of concentration variables
which determine the rate of any reaction, is
called the overall order of the reaction.
Characteristics of Order of Reaction
• The order of a reaction is generally a small
integer, half-integer or zero. It may have
any value such as, 1, 2, 3, 1/2, 3/2 or 0.
• Order of reaction is obtained from the
experimentally obtained rate concentration
data. So, order of reaction is an
experimental parameter.
• Generally, reaction order cannot be
deduced from the stoichiometry of the
reaction.
• Order of the reaction depends on the way a
reaction goes through to completion. This
could be either in one elementary step or a
series of complex steps. If the reaction
takes place in a single step then the
stoichiometric coefficient(s) of the
reactant(s) in the balanced chemical
equation gives the order of the reaction
with respect to the respective reactant.
The overall order then is given by the sum
of all the stoichiometric coefficients.
• In complex reactions the reaction order is
to be determined experimentally.
Zero Order Reactions
The reaction whose rate does not depend upon
the concentration of the reactant is called a
zero order reaction. Thus, for a zero order
reaction
3
 STUDENT MATERIAL
• The molecularity of any process can only
be a small positive integer and cannot be
zero, fractional or negative.
Units of Rate Constant for Reactions of
• Molecularity of a reaction depends upon
Different Orders:
the mechanism postulated for the reaction
Reaction and is not an experimental parameter.
Rate Law
Order • The molecularity of a reaction is not the
same as the order of reaction. However,
0 Rate = -k [A]° = k for an isolated, single step reaction, the
molecularity and the order of the reaction
1 Rate = -k [A] are equal to each other.
When a reaction proceeds through two or more
2 Rate= -k [A]2 elementary reactions, each elementary
3 Rate= -k [A]3 reaction has its own rate. Some elementary
reactions may be fast, while others may be
slow, the rate of formation of a product cannot
be faster than the rate of the slowest
Unit of Rate elementary reaction.
Rate Constant (k) The slowest elementary reaction in any
Constant (k)
mechanism is called the rate-determining
mol L-1 -s-1 reaction or rate determining step. The rate of
the overall reaction, i.e., the rate of formation
mol L-1 min-1 of the final products, is governed by the rate of
the slowest elementary reaction. For example,
s-1
in a reaction,
min-1

= time-1

Mol-1 L s-1
mol-1 L min-1 The overall rate of reaction is governed by the
rate of the slowest step,
= concentration-1 time-1

mol-2 L2 s-1 as its half-life is the longest (1s) in this

sequence of reactions.
mol-2 L2min-1 The rate of formation of G and H will be
governed by the slowest step.

= concentration-2 time-1
Comparison of Order and Molecularity of a
Reaction
Molecularity of a Reaction
Elementary reactions are classified according Molecularity Order
to their molecularity. The number of reacting Number of reacting Sum of the powers to
species, which are involved in simultaneous
collision to bring about a chemical reaction, is species undergoing which the
called the molecularity of the reaction. simultaneous concentration terms
1. Unimolecular reaction--Æ decomposition of
NH4NO2 to N2 and 2H2O, collision are raised in a rate
The molecularity is 1 law expression
Theoretical concept Experimentally
2. Bimolecular reaction ---Æ determined
Has integral values Can have fractional
values also
The molecularity is 2 Cannot be zero Can be zero
Provides no Helps in judging the
Characteristics of Molecularity

CBSE 12 Chemistry 4
 STUDENT MATERIAL
information on slowest step, hence (iii) K[SO2Cl2] Wrt SO2Cl2 1
reaction mechanism gives further =1
information about
the mechanism Integrated Rate equation
The rate of reaction in the differential form
Example: Express the relationship between cannot be used to determine rate law and
the rate of production of iodine and the rate of order of the reaction.
disappearance of hydrogen iodide in the So the differential equations are integrated
following reaction: over a meaningful range of limits to give the
integrated rate equation:

Solution:
Rate of production of iodine = 1/2 x Rate of
disappearance of HI
Zero Order Reactions
When a reaction has a rate which is
independent of the concentration of the
reactant(s) it is called a zero-order reaction.
Example: The rate of formation of a dimer in a
second order dimerisation reaction is 9.1 x 10-6
mol L-1 s-1 at 0.01 mol L-1 monomer In the above reaction increasing the
concentrations. Calculate the rate constant. concentration of the reacting species A will not
Solution: Let the second order dimerisation speed up the rate of the reaction.
reaction be, 2A → A2
Rate of formation of dimmer (r) = k
[Reactant]2 = k[A]2
d[A] = k dt
r = 9.1x10-6 mol L-1 s-1= k (0.01 mol L-1) 2
If this differential equation is integrated both
or,
sides
[A] = - kt + I
Where, I is the integration constant.
At t = 0, the concentration of the reactant A =
Example: With the help of the following rate [A]0, where [A]0 is initial concentration of the
expressions of the reactions, find out the reactant. Substituting in above equation
overall order of the reactions and the order [A]0 = -k x 0 + I
with respect to the following reactant: ∴ [A]0 = I
(a) For reaction: Substituting the value of I, gives an equation
which is often called the integrated zero-order
rate law.
(b) For reaction: [A] = - kt + [A]0
Where [A] represents the concentration of the
chemical of interest at a particular time and
(c) For reaction: [A]0 represents the initial concentration. Zero
order rate constant is given as,
Solution: The order with respect to each
reactant and the overall order of the reaction
are tabulated below:
The reaction is zero-order if it occurs in a
Reaction Rate Order Overall
closed system when there is no net build-up of
Order intermediates and there are no other reactions
occurring. For a zero order reaction the
(i) K wrt 3
concentration versus time profile is linear and
2
[NO] [O2] NO2=2,wrt the rate of reaction versus time has the profile
as shown in the graph. The slope of this
O2=1
resulting line is the zero order rate constant - k
(ii) K[N2O] wrt N2O=1 1 and intercept [A]0.

CBSE 12 Chemistry 5
 STUDENT MATERIAL

In terms of X the concentration of A at time t

in the rate law equation is given as:

The above equation can also be written as

This equation rearranges it to

Integrating this function with very small

First Order Reactions
changes in X and t, we have
For a first order reaction with rate constant
(k), at time (t) the initial concentration [A]0
will change to the new concentration at time t
[A]t.
The rate of formation of X from the chemical  ‐‐‐‐‐‐‐‐ Æ(i) 
reaction:
Where C is constant of integration which can

Where the initial concentration of A is [A]o. be evaluated as follows;

And the initial concentration of X is 0. The
concentration of X at time t is [X]t. The
concentration of A at time t is [A]t.
The rate of a reaction is:

The rate for a first order reaction is: Substituting this equation in equation (i)
Rate = k[A]t
These two may be combined as:

This rearranges to give

The concentration of A at time t may also be ln [A]o - ln ([A]o - [X]) = kt
written in terms of X (the amount that has
reacted) since the area under a plot of [A] vs
time is the amount that has reacted.

CBSE 12 Chemistry 6

Since [A]o - [X] at time t is also [A]t, this may
be rewritten as follows:
This is the integrated first order rate equation,
which rearranges in different ways for different
applications:
When the concentration of the reactant are
[A]1 and [A]2 at time t1 and t2 respectively
then the above equation can be written as,
Taking antilog on both sides, the equation
arranges to,
In the log form the first order rate equation is
written as,
A plot of ln [A]t against t gives a straight line
with slope = -k and intercept equal to ln [A]0.
If a graph is plotted between
CBSE 12 Chemistry
STUDENT MATERIAL
Half Life of a Reaction
The half-time (or half-life period) of a reaction
may be defined as the time period during
which the concentration of a reactant gets
reduced to one-half (50%) of its initial value or
the time required for the completion of 50% of
the reaction. Half-life time is denoted by t1/2
and its value depends upon the speed of the
reaction. Fast reactions have short half-life
time, while slow reactions have long half-life
time.
For a zero-order reaction the rate constant is
Substituting this in the above equation we
have,
∴ Half-life is given as,
It is clear that t1/2 is directly proportional to the
initial concentration of the reactants and
inversely proportional to the rate constant for a
zero order reaction.
The half life (t1/2) of the first order reaction can
be derived from the rate constant as follows:
When the reaction has proceeded half way
then [A]=[A]o/2. On substitution of this value
in the integrated equation the expression of
7
 STUDENT MATERIAL
t1/2 becomes,

Temperature coefficients for most of the

or
Only for the first order reaction t1/2 is
independent of the initial concentration of the
reactant. This relation can be used to
determine the order of a reaction.
In general, for a reaction of order n, t1/2 is
proportional to initial concentration of A raised
to power n - 1, that is,
Pseudo First Order Reaction
In some acid catalyzed reactions like the
inversion of cane sugar and hydrolysis of ethyl
acetate, the stoichiometric equations show
them to be bimolecular but they are found to
be first order by experiment.
For the inversion of cane sugar reaction the
rate of reaction is proportional to the
concentration of sucrose only.
So, in the rate equation,
Rate = k' [C12H22O11] [H2O]
The term [H2O] is constant. The equation,
thus, becomes
Rate = k [C12H22O11]
Where k = k' [H2O]
As the reaction behaves as first order reaction,
such reactions are called pseudo first order
reactions.
reactions lie between 2 and 3, i.e., the rate
constant can double (or even triple) when the
temperature is raised by ten degrees near the
normal room temperature.
The effect of temperature on the rate constant
is mathematically expressed by the Arrhenius
equation. Arrhenius studied gas phase
reactions and in 1897 arrived at an empirical
equation that described the temperature
dependence of reaction rate constant 'k' by the
equation,
The equation called Arrhenius equation
indicates exponential dependency of the rate
constant on temperature. Here 'A' is the
Arrhenius factor or the frequency factor also
called the pre exponential factor. It is a
constant specific to a particular reaction. Ea is
the energy of activation for the reaction
measured in joules/mole (Jmol-1), R is the gas
constant, T the temperature, and the
exponential factor (-Ea/RT) is a measure of the
probability for the occurrence of a molecule at
the top of the energy-barrier.
Threshold energy is the energy required by
the reacting molecules to overcome the
activation barrier.
Activation energy is the difference between the
threshold energy & the average energy of the
reacting molecules.
Ea = ET - ER
Where, Ea is the activation energy of the
reaction; ET is the threshold energy; ER is the
average energy of the reactant molecules.
Each reaction also has a typical energy of
activation value Ea. The concept of activation
can be easily visualized from the below figure.

Temperature Dependence of Reaction

Rate and Arrhenius Equation
The temperature coefficient of a reaction,
defined as a ratio of the rate constants at two
temperatures of a particular reaction differing
by 10 °C (usually measured from 25 °C to 35
°C), gives the dependence of reaction rates on
temperature It is given by,

CBSE 12 Chemistry 8

So, it is seen that,
• When the activation energy is small, then
larger number of the reactant molecules
will be able to cross over the top of the
energy-barrier, and the reaction will be
faster. Thus, if the activation energy is low,
then the reaction is fast.
• When the activation energy is high, then
only a few molecules would be able to
cross the top of the energy barrier, and the
reaction will be slow. Thus, if the activation
energy of a reaction is high, then the
reaction is slow.
• When the activation energy is zero,
then each molecule will be able to cross the
top of the energy barrier, and the reaction will
be instantaneous, and almost explosive. Thus,
if the activation energy of a reaction is zero,
then the reaction is instantaneous and very,
fast.
Arrhenius’ explanation of how temperature
increases the reaction rate
CBSE 12 Chemistry
STUDENT MATERIAL
At any temperature, the number of molecules
possessing energies equal to or greater than a
certain energy (say, 'E') is proportional to the
area under the curve beyond that energy (the
shaded area shown in the Figure (a). When the
temperature is increased, the distribution gets
broadened and the area under them curve
beyond 'E' increases, shown in Figure (b).
Thus, at higher temperature, more molecules
would possess energies equal to or greater
than certain energy i.e., threshold energy.
Therefore with a rise in temperature, more
molecules are able to take part in chemical
reaction. As a result, the reaction rate
increases with an increase in temperature.
According to Arrhenius, a rise in temperature,
increases in the rate of reaction mainly due to
the increase in the number of molecules
possessing energies equal to or greater than
the threshold energy for the reaction.
Graphical Method for Determination of
Activation Energy
Arrhenius equation for the rate constant of a
reaction is
Where, is the activation energy of the
reaction
Rewriting Arrhenius equation by taking
logarithm on both the sides,
9

Or,
Subtracting one equation from the other one
gets
Knowing k1, k2, T1,T2, Ea can be calculated from
the equation .
Effect of Catalyst on Reaction Rates
Catalyst provides an alternative pathway of
lower activation energy so the reacting
molecules can cross the energy barrier easily.
CBSE 12 Chemistry
STUDENT MATERIAL
Two types of catalytic reactions are usually
distinguished according to the number of
phases of a system.
• Homogenous catalysis and
• Heterogenous catalysis
Homogenous catalysts are of the same phase
of the reactants. Oxidation of sulphur dioxide
(SO2) to sulphur trioxide (SO3) in the presence
of nitric oxide (NO) is an example of
homogenous catalytic reaction.
In heterogenous reaction, the catalyst exists in
a different phase from the reactants. Usually a
solid catalyst is used and the reactants can be
either in the liquid or gaseous phase. Nitric
oxide can be replaced by platinum in the above
reaction to demonstrate heterogenous
catalysis.
Here, the surface area of the catalyst affects
the rate of the reaction, especially under low
reactant concentrations. Another example of
heterogenous catalytic reaction is
hydrogenation of unsaturated hydrocarbon.
Autocatalysis
The phenomenon where the reaction rate
increases as a product is formed is called
autocatalysis. An example of autocatalytic
reaction is the Belousov-Zhabotinskii (BZ)
reaction.
The product HBrO2 is the reactant in step I.
10
 STUDENT MATERIAL
• The effect of temperature on the rate 3. Define average rate and Instantaneous rate.
constant can be explained by Collision
(Outside Delhi 2003)
Theory, especially for gas phase reactions.
• A reaction can take place only when the
reacting molecules collide with energy
Answer: Average rate: It is defined as the
greater than the threshold energy and with
proper orientation. average charge in the concentration of
• In collision theory, the rate constant is
reactants or product during a definite time
related to three factors Z, f and p by the
equation k = Zfp interval
• The fraction of collisions that have energy
greater than the threshold value increase changeinconcentration
Averagerate =
rapidly with temperature and this explains time int erval
the exponential temperature dependence
of rate constant. Δx
=
• Transition state theory explains the rate of Δt
reaction in terms of formation of a
'transition state' of reacting molecules. The Average rate can be determined by taking the
formation of transition state requires change in concentration during a time interval.
energy of activation.
• The activated complex is an unstable
higher energy transition state soon breaks
and decomposes to transform into
products.
• The high and low activation energy values
explain the stability and reactivity of
reactants and products.
• Reversible reactions have different forward
activation energies and backward
activation energies. The overall activation
energy of a reaction in any direction
determines the rate of reaction in that Instantaneous rate: When the rate of
direction.
reaction is determined at a particular time, it is
called instantaneous rate.
Instantaneous rate = Slope of the tangent at a
particular time

Review Questions dx
=
dt
1. For the reaction 3H2(g)+N2(g) → 2 NH3(g),
Instantaneous rate can be determined by
how are the rate of reaction expression
drawing a tangent and determine the slope of
− d [H2 ] d [NH3]
and interrelated? (Delhi it at particular time.
dt dt
2006)
1 d [H2 ] 1 d [NH3]
Answer: − =+
3 dt 2 dt

2. Identify the reaction order if the unit of the

rate constant is sec-1. (Delhi 2006)
Answer: First order.

CBSE 12 Chemistry 11
 STUDENT MATERIAL
4. Distinguish between reaction rate and (iv) What does the slope of the above line
indicate?
reaction rate constant (Specific reaction rate)
(v) Draw the plot log [R]0/ [R] vs time t (s)
of a reaction. (Delhi 2004) Answer: (i) First order reaction
Answer: (ii) Per sec.
Reaction rate
Reaction rate
constant (iii) k =
1. The rate constant (iv) rate constant (k)
1. The rate of reaction
or specific reaction
is the rate of
rate is equal to the
disappearance of
rate of reaction
reactant or rate of the
when the
appearance of
concentration of the
product.
reactant is unity. (v)
2. Rate constant
can be calculated 6. State the role of activated complex in a
2. The rate of reaction
with the help of rate reaction and state its relation with activation
can be calculated by
law. energy. (Outside Delhi 2001)
calculating the
rate = k [A] Answer: Activated complex: In order that the
decrease in
where k = rate reactants many change into products, they
concentration of the
constant have to cross an energy barrier. When the
reactant in unit time.
[A] = concentration reactant molecules absorb energy, their bonds
For reaction A → B
of reactant are loosened and new bonds start forming
rate of reaction
The value of k between them. This highly unstable transition
d[A] d[B]
=− =+ depends upon the state between reactants and products is called
dt dt
order of reaction activated complex. It immediately dissociates
and temperature. to form the stable products.

5. For a certain chemical reaction variation in

the concentration in [R] vs. time (s) plot is
given below. Activation energy = energy of activated
complex – Average energy of reactants.

7. The rate of a reaction is given by

For this reaction write/draw
(i) what is the order of the reactions?
(ii) What are the units of rate constant k?
(iii) Give the relationship between k and t1/2
(half life period)
Rate=k [N2O5] In this equation what does k
stand for? (Outside Delhi 2000, 2002)
Answer: Here k is the rate constant for the
reaction and is equal to the rate of the reaction
when the concentration of the reactant is
unity.

CBSE 12 Chemistry 12
 STUDENT MATERIAL
-1 -1
8. Define activation energy of a reaction. (R=8.314 JK mol ). (Outside Delhi 2000,
(Outside Delhi 2000, 2002) 2002)
Answer: the minimum extra energy over and Ea
Answer: Slope of line = - =
above the average potential energy of the 2.303R
reactants which must be supplied to the
-6670K
reactants to enable them to cross over the
Ea =2.303 R x 6670 = 2.303 x 8.314 x 6670
energy barrier between reactants and products
=127711.43 J mol-1
is called activation energy.

11. The following experimental data was

9. A first order reaction is 20% complete in 10
collected for the reaction:
minutes. Calculate the time for 75%
Cl2(g) + 2NO (g) → 2NOCl (g)
completion of the reaction. (Outside Delhi
Initial Initial
2000, 2002)
cone. cone. Initial rate
Answer: Let a be the initial concentration of Trial
[Cl2] [No] Mol L-1 s-1
the reactant.
mol L-1 mol L-1
20 4a
Thus At t= 10 min, a – x = a - a= 1 0.010 0.010 1.20 x 10-4
100 5
2 0.010 0.030 10.8 x 10-4
75 a
t = ?, a – x = a - a = 3 0.020 0.030 21.6 x 10-4
100 4
for a first order reaction
Construct the rate equation for the reaction.
2.303 a 2.303 5
k= log = log (Outside Delhi 2001)
10 min 4a / 5 t 4
Answer: The rate law is
2.303 a 2.303 r = K [Cl2]x [NO]y
and k = log = log 4
10 min a/4 t
From trial 1, 1.20 x 10-4 = K [0.010]x [0.010]y
2.303 5 2.303 From trial 2, 10.8 x 10-4 = K [0.010]x [0.030]y
∴ log = log 4
10 min 4 t From trial 3, 21.6 x 10-4 = K [0.020]x [0.030]y
1.3865 Dividing (2) by (1), 9=3y ∴ y = 2
or 0.0223 min-1=
t
Dividing (3) by (2), 2=2x ∴ x = 1
t = 62.1749 mins
10. Rate constant k of a reaction varies with
12. The decomposition of a compound is found
temperature according to the equation:
to follow a first-order rate law. If it takes 15
Ea 1
log k = constant - x minutes for 20 per cent of original material to
2.303R T
react, calculate (i) the specific rate constant,
where Ea is the energy of activation for the
(ii) the time at which 10 per cent of the
reaction. When a graph is plotted for log K
original material remains unreacted, (iii) the
1 time it takes for the next 20 per cent of the
versus ,a straight line with a slope
T reactant left to react after the first 15 minutes.
-6670K is obtained? Calculate energy of (Delhi 2002)
activation for this reaction. State the units. Answer: (i) For a first order reaction

CBSE 12 Chemistry 13
 STUDENT MATERIAL
2No (g) + O2 (g) → 2NO2 (g)
2.303 [A ] [Fast]
K= log o
t A 2CO (g) + O2 (g) → CO2 (g)
2.303 [A o ] [Slow]
or K= log
15 [0.8 A o ] (ii) Concentration of reactants: Higher the
concentration of reactant, faster would be the
2.303 10 rate of reaction.
or K= log
15 8 (iii) Temperature: The rate of reaction
increases with increase in temperature.
or K=0.015 min-1 (iv) Surface area of reactant: Greater is the
surface area of reactant, faster will be the rate
of reaction.
2.303 [A o ] 2.303 (v) Presence of catalyst: The presence of
(ii) K= log = log 10
t1 [0.1A o ] t1 catalyst increases the rate of reaction.

From (1) and (2)

14. For the reaction 2A+B+C → A2 B+C, or the
rate law has been determined to be rate = k
2.303 10 2.303 log 1.25 log10
log = log 10 ⇒ = [A] [B]2.If the value of the k is 2.0 x 10-6 mol-2
15 8 t1 15 t1
L2 s-1 for the reaction, determine to be rate of
15 log 10
∴ t1 = the reaction with [A]=0.2 molL-1; [B] = 0.1
log 1.25
mol L-1; [C] = 0.5 mol L-1. (Outside Delhi
⇒ t1 = 154.78 min
2002)
∴ After 154.78 min., 10% of the original Answer: The rate law of the reaction:
material remains unreacted. 2A + B + C → A2B + C is
rate = k [A] [B]2
(iii) Also, k =
obviously the rate of the reaction does not
2.303 [0.8 A o ] depend upon the concentration of C
log
t2 [0.8 A o ] − 0.2 [0.8 A o ]
So, Rate = k [A] [B]2
2.303 [0.8 A o] 2.303 10 = (2.0 x 10-6 mol-2 L2 s-1) (0.2 mol L-1) (0.1
k= log = log
t2 [0.64 A o] t2 8 mol L-1)
From (1) and (3) = 9.0 x 10-9 mol L-1 s-1.

2.303 10 2.303 10
log = log
15 8 t2 8 15. The rate constant of a reaction is 3 x 10-4

∴ t2 = 15 min. L mol-1. what is the order of the reaction?

(Delhi 2003)

13. Mention the factors that affect the rate of Answer: Second order. Hint: Decide the

a chemical reaction. (Delhi 2002) order based on the unit of rate constant.

Answer: Factors that affect the rate of a 16. The rate constant of a reaction is 1.5 x 107

chemical reaction: Following factor affect the s-1 at 500C and 4.5 x 107 s-1 at 1000C.

rate of reaction. Calculate the value of activation energy. Ea for

-1
(i) Nature of reactants: Different reactants the reaction. [R = 8.314 J K mol-1] (Delhi
require different amount of energies for 2003)
breaking the old bonds and different amount of
energies for the formation of new bonds.

CBSE 12 Chemistry 14
 STUDENT MATERIAL

k2 Ea ⎡ T2 − T2 ⎤ Answer: In experiment 2 and 3 the

Answer: log = ⎢ ⎥
k1 2.303R ⎣ T1T2 ⎦ concentration of A in same. Therefore,
From the exp. 2,
4.5 x 107 Ea ⎡ 373 − 323 ⎤
log = ⎢ ⎥ Rate of formation of D ∞ [B]a
1.5 x 107 2.303 x 8.314 ⎣ 323 x 373 ⎦
9 x 10-2 mol L-1 min-1 ∞ [0.2]a
Ea 50 From the exp. 3,
log 3 = x
2.303 x 8.314 323 x 373
⇒ 3.6 x 10-1 mol L-1 min-1 ∞ [0.4]a
0.4771 x 2.303 x 8.314 x 323 x 373 a
Ea = 3.6 x 10−1 ⎡ 0.4 ⎤
50 ⇒ =⎢ ⎥
9 x 10−2 ⎣ 0.2 ⎦
= 22011.76 J mol-1 = 220.12 kJ mol-1.
⇒ (2)2 = (2)a

17. What is known as ‘activation energy’? How ⇒ a=2

is the activation energy affected by (i) the use Similarly from the experiment 1 and 4.

of a catalyst and (ii) a rise in temperature? b

3x 10−2 ⎡ 0.4 ⎤
⇒ =⎢ ⎥
(Outside Delhi 2003) 7.5x 10−3 ⎣ 0.2 ⎦
Answer: Activation energy: The minimum Or, 4 = (4)b
extra energy over and above the average Or, (4)1 = (b)b
potential energy of the reactants which must b=1
be supplied to the reactants to enable them to So, the rate law for the reaction is.
cross over the energy barrier between Rate of formation of D = k [A]2 [B]1
reactants and products is called activation Substituting the value of experiment 1, we get,
energy. 7.5 x10-3 mol L-1 min-1
Activation energy = Threshold energy – = k [0.1]2.[0] mol2 L-2 x mol L-1
Average energy of reactants.
7.5 x 10−3 mol L−1 min−1
(i) Activation energy of the reactants ⇒ k=
decreases by the use of a catalyst. 0.001mol3 L−3
(ii) Activation energy of the reactants
7.5x10-3 x 103
decreased by a rise in temperature. ⇒k= mol−2L2 min−1
1
18. The following rate data were obtained at
300 K for the reaction 2 A + B → C+D So, the required rate of formation of D,

Rate of = 7.5 mol-2 x L2 x min-1 [0.8 mol L-1]2 x [0.5

Experiment [A] [B] formation of mol L-1]

No. mol L-1 mol L-1 D = 7.5 x 0.64 x 0.5 mol L-1 min-1 = 2.4 mol L-1

mol L-1 min-1 min-1.

1. 0.1 0.1 7.5 x 10-3

2. 0.3 0.2 9.0 x 10-2 19. Define the order of a reaction. (Delhi

3 0.3 0.4 3.6 x 10-1 2004)

4. 0.4 0.1 3.0 x 10-2 Answer: The order of a reaction is equal to

Calculate the rate of formation of D when [A] the sum of the powers (exponents) to which

= 0.8 mol L-1 and [B] = 0.5 mol L-1 (Outside the various concentration terms are raised in

Delhi 2003) the rate law expression of the reaction.

CBSE 12 Chemistry 15
 STUDENT MATERIAL
24. Show that in a first order reaction, time
20. What is meant by an elementary reaction? required for completion of 99.9% is 10 times of
(Outside Delhi 2004) half-life (t1/2) of the reaction. (Delhi 2005)
Answer: A reaction which takes place in one Answer: When reaction is completed 99.9%
step is called elementary reaction. For example ∴ [R]o − 0.999 [R]o = 0.001 [R]o
reaction between H2 and I2 to form 2HI is an
2.303 [R]o
elementary reaction. ∴ K= log
t [R]n

2.303 [R]o
21. Give one example of pseudo first order K= log
tl 0.001 [R]o
reaction. (Outside Delhi 2004)
2.303
Answer: CH3COOC2H5 + H2O → CH3COOH + K= log 103
t
C2H5OH
2.303
rate = k [CH2 COOC2H5]1 [H2O]0 K= .3 log 10
t
6.909
22. A reaction: K=
t
Reactant → Product is represented by
6.909
∴ t =
t
For half-life of the reaction

0.693
t1 =
2 K
Dividing (1) by (2), we get

6.909
t K
Predict (i) the order of the reactions in this =
t1 0.693
case. 2
K
(ii) What does the slope of the graph t 6.909 K
= x
represent? (Delhi 2005) t1 K 0.693
2
Answer: (i) the reaction is of zero order.
(ii) Slope of the straight line graph = t
= 10 ⇒ t = 10 t 1
t1 2
d[R] 2
-k=
dt
23. Express the relation between the half-life 25. a) The following initial rate data were
period of a reactant and its initial concentration obtained at 300 K for the reactions:
th
for a reaction of n order. (Outside Delhi 2A + B → C + D
2005) [A] mol L-1 [B] mol L-1 Rate mol L-1 S-1
I 0.2 0.1 6.0 x 10-2
II 0.4 0.1 2.4 x 10-1
III 0.2 0.2 1.2 x 10-1
1
Answer: t /2 ∝
Deduce the rate law.

CBSE 12 Chemistry 16
 STUDENT MATERIAL
(b) If half-life of a reaction is inversely
proportional to initial concentration of the 2.303x8.314x300x310
Ea = log 2
reactant, what is the order of the reaction? 10
(Delhi 2005) = 2.303 x 8.314 x 30 + 310 x 0.3010
Answer: (a) Let the rate law for the reaction = 53598.6 J mol-1
be = 53.6 kJ mol-1
rate = k [A]x [B]y
29. For the reaction A → B, the rate of
reaction becomes twenty seven times when
Then
the concentration of A is increased three times.
or 4 = 2x
What is the order of the reaction?
∴ x=2
Answer: Let r= k [A]n
Then 27 r = k [3A]n [According to question]
−1 x y
rIII 1.2 x 10 k[0.2] x [0.2]
Again, = = 27r k[3A]n
rI 6.0 x 10−2 k[0.2]x x [0.1] y ∴ = or 33 = 3n
r k[A]n
or 2 = 2y
Order of reaction, n = 3.
∴ y=1
(Delhi 2006)
Hence the rate law is rate = k [A]2 [B].

30. (a) What is rate constant.

26. A substance with initial concentration ‘a’
(b) On what factors it depend. (Delhi 2006)
follows zero order kinetics. In how much time
Answer: (a) Rate constant or specific reaction
will the reaction go to completion? (Delhi
rate: Suppose A and B are two reactants in a
2005)
reaction. The rate depends on concentration of
Answer: If k is the rate constant of the
[A]x and [B]y. Then rate equations is
reaction, then the time for the completion of
x y
Rate α [A] [B]
the reaction will be a/k units of time.
Rate=k [A]x [B]y

27. The reaction A + B → C has zero order. Where k is called the rate constant or specific

What is the rate equation? (Outside Delhi reaction rate.

2005) (b) The value of rate constant k is independent

0
Answer: Rate = k [A] [B] = k. 0 of the concentration of the reactants but
depends upon

28. The rate of a particular reaction doubles (i) the temperature of the reaction

when temperature changes from 270C to 370C. (ii) the particular reaction considered.

Calculate the activation energy of such

reaction. (Outside Delhi 2005) 31. Nitric oxide reacts with hydrogen to give
nitrogen and water
k2 Ea ⎡ T2 − T1 ⎤
Answer: log = ⎢ ⎥ 2NO + 2H2 → N2 + 2H2O
k1 2.303R ⎣ T1T2 ⎦
The kinetics of this reaction is explained by the
Ea ⎡ 310 − 300 ⎤
log 2 = following steps:
2.303x8.314 ⎢⎣ 300x310 ⎥⎦

CBSE 12 Chemistry 17
 STUDENT MATERIAL
(i) 2NO + H2 → N2 + H2O2 (slow) there is only reactant and the reaction is of
(ii) H2O2 + H2 → 2H2O (fast) first order? (AI 1997C)
What is the predicted rate law? (Delhi 2007)
Answer: 2NO + 2H2 → N2 + 2H2O
6. A reaction is 50% complete in 2 hours and
Slow step of the reaction mechanism is
75% complete in a4 hours. What is the order
2NO + H2 → N2 + H2O2
of the reaction? (Outside Delhi 2006)
The rate law, therefore, is
Rate = k [NO]2 [H2]
7. A first order reaction is 15% complete in 20
minutes. How long will it take to be 60%
32. The rate constant for a first order reaction
complete? (Delhi 2007)
is 60 s-1. How much time will it take to reduce
the concentration of the reactant to 1/10th of
8. The first order rate constant for the
its initial value? (Delhi 2007)
decomposition of ethyl iodide by the reaction
2.303 [R]o
Answer: t = log C2H5 I (g) → C2 H4 (g) + HI (g)
K [R]
At 600K is 1.60 x 10-5 S-1. Its energy of
1 activation is 209 kJ/mol. Calculate the rate
Here k = 60 S-1. [R] = [R]o ⇒ [R]o = 10 [R]
10
constant of the reaction at 700 k.
2.303 10[R] (Delhi 2007)
t= log
60 [R]

2.303x1 9. A first order decomposition reaction takes

t= = 0.0384 S.
60 40 minutes for 30% decomposition. Calculate

its t 1 value. (Delhi 2008)

2
Additional Questions
1. How is rate of reaction experimentally
10. A reaction is believed to be either first or
determined?
second order, and has a half-life of 10 seconds
at the beginning of an experiment but a half-
2. For a reaction A + H2O → B
life of 20 seconds some time later. What is the
Rate ∝ [A] What is its (i) molecularity (ii)
order of the reaction?
Order of reaction (AI 1997)

11. A hydrogenation reaction is carried out at

3. A first order reaction is 30% completed in
500 K. If the same reaction is carried out in
50 minutes.Calculate the value of rate constant
the presence of a catalyst at the same rate,
(Foreign 1998)
the temperature required is 400K. Calculate
the activation energy of the uncatalyzed
4. Calculate the activation energy of a reaction
reaction if the catalyst lowers the activation
nwhose reaction rate at 310K gets doubled for
energy by 20 KJ / mol.
10K rise in temperature. (AI 1999c)

12. From collision theory, what is the factor

5. Show graphically, how the rate of reaction
that is responsible for increasing the rate of a
depends on the concentration of reactant when
reaction with temperature? Does the factor Z

CBSE 12 Chemistry 18
 STUDENT MATERIAL
-1 -1
increase with temperature? R = 8.314 JK mol ] (Delhi 2006)
 
13. The rate constant for the first order
decomposition of certain reaction is described
by the equation.

1.25 × 10 4
log (k) = 14.34 −
T
What is the activation energy?

14. What is the activation energy of a reaction

whose rate quadruples when the temperature
is raised from 293 K to 313 K.?

Homework Questions:
1. Define rate law. Give example.
(Outside Delhi 2006)

2. What is a first order reaction?

Give two examples of first order reaction.

3. Write units of rate constant K for zero order,

first order, second order and nth order
reaction. (Outside Delhi 2006)

4. Define the zero order reaction. Give is unit.

(Outside Delhi 2006)

5. N2O5 decomposes according to the equation,

2 N2O5 ⎯⎯
⎯→ 4 NO2 + O2
The reaction follows first order kinetics. After
30 minutes from the start of decomposition in
a closed vessel, the total pressure developed is
found to be 284.5 mm Hg and on complete
decomposition, the total pressure is 584.5 mm
Hg. What is the rate constant of the reaction?

6. The rate of a particular reaction triples when

temperature changes from 50oC to 100oC.
Calculate the activation energy of the reaction.
[Given log 3 = 0.4771;

CBSE 12 Chemistry 19