M.E.

S INDIAN SCHOOL, DOHA -QATAR

Notes 2026- 2027
Section: Boys & Girls Date: 03.04.2026
Class &Div : XII ( all divisions) Subject : Chemistry
Lesson /Topic: CH:3- CHEMICAL KINETICS
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The branch of Chemistry that deals with the rate of chemical reaction, factors affecting the rate
and the mechanism of a reaction is called Chemical Kinetics.

Rate of a chemical reaction

The rate of a chemical reaction is the change in concentration of any one of the reactant or product
in unit time. Or, it is the rate of decrease in concentration of any one of the reactant or the rate of
increase in concentration of any one of the product.
For a chemical reaction, if Δx is the change in concentration of a reactant or a product in a time
Δt, the rate of reaction (r) = Δx/Δt.
For a hypothetical reaction R → P, the rate of reaction can be expressed by decrease in
concentration of reactants or by increase in concentration of products. i.e., Rate of reaction = Rate
of disappearance of R
r = Decrease in concentration of R
Time taken
Or, r = –Δ[R] / Δt
[Since, Δ[R] is a negative quantity (as concentration of reactants is decreasing), it is multiplied
with –1 to make the rate of the reaction a positive quantity].
Or, Rate of reaction = Rate of appearance (formation) of P
= Increase in concentration of P
Time taken
i.e., r = Δ[P]/ Δt
The above rate expressions are also called Average rate.

Units of Rate of reaction

If concentration is expressed in moles/L and time is in second, the unit of rate of reaction is
mol/L/s. In general the dimension of rate of reaction is Concentration/Time. For gaseous reactions,
the concentration is replaced by partial pressure and so the unit of rate of reaction is atm/s.

Instantaneous Rate of a reaction

The rate of a reaction at a particular instant of time is called Instantaneous Rate of a reaction. Or,
it is the rate of a reaction when the time interval approaches zero.

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For the reaction, R→ P, the Instantaneous Rate is given by, Rate (inst)
= – d[R]/dt = d[P]/dt
For the reaction, 2N2O5 → 4NO2 + O2, rinst = – d[N2O5]/dt = - d[NO2]/dt = d[O2]/dt

Determination of Instantaneous Rate of a reaction

Instantaneous Rate of a reaction can be determined graphically. First conduct the chemical reaction
and find out the concentration of reactants or product at a regular interval of time. Then plot a
graph between concentration along y-axis and time along x-axis.
In order to determine the Instantaneous Rate at a particular time, mark the point on the graph at
that time and draw a tangent at the point. The slope of this tangent gives the instantaneous rate at
that time.

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 concentration

It is found experimentally that Rate of reaction is directly proportional to the concentration of
reactants.
Thus for a general reaction, aA + bB → cC + dD,
Rate α [A]x[B]y
Or, r = k [A]x[B]y (where x and y may or may not be equal to a and b)

This expression is known as rate law or rate equation. Thus rate law is a “mathematical equation
relating the rate of a chemical reaction and concentration of reactants, in which each concentration

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term is raised to a power which may or may not be equal to the stoichiometric coefficients in the
balanced chemical equation.”
In the above equation ‘k’ is a constant called rate constant or velocity constant or specific reaction
rate of the reaction. It is defined as the rate of the reaction when the concentration of each of the
reactants is unity.

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.
For a general reaction, aA + bB → cC + dD; r = k[A]x[B]y, Order of the reaction = x + y
If the order of a reaction is zero, it is called zero order reaction, if it is one, it is called first order
reaction, if it is two, it is called second order reaction and so on.

Molecularity of a reaction
It is the total number of reacting species collides simultaneously in a chemical reaction. It is a
theoretical quantity. It cannot be zero or fractional. It can have values 1,2,3 etc. it is applicable
only to elementary reactions.
If the molecularity of a reaction is 1, it is called unimolecular reaction. e.g.
Decomposition of ammonium nitrite
NH4NO2 → N2 + 2H2O
If the molecularity of a reaction is 2, it is called bimolecular reaction. e.g.
Decomposition of Hydrogen Iodide
2HI → H2 +I2
Differences between Order and Molecularity of a reaction
Order Molecularity
1. It is the sum of the powers of the concentration terms in the rate law expression It is the
total number of reactant species collide simultaneously in a chemical reaction
2. It is an experimental quantity It is a theoretical quantity
3. It can be zero or fractional It cannot be zero or fractional
4. It is applicable to both elementary and complex reactions It is applicable only to elementary
reactions
Elementary and complex reactions
A reaction that takes place in a single step is called elementary reaction. While a reaction that
occurs in more than one step is called a complex reaction. In a complex reaction one of the steps
is slower than the other steps and this step is called the Rate determining step. The overall rate of
the reaction is controlled by this slowest step. The sequence of steps by which a chemical reaction
occurs is called the mechanism of the reaction.

Consider the decomposition of hydrogen peroxide which is catalysed by iodide ion in alkaline
medium.

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The rate equation for this reaction is found to be r = – d/dt [H2O2][I-]
This reaction is first order with respect to both H2O2 and I–. This reaction takes place in two steps
(1) H2O2 + I– → H2O + IO– (2)
H2O2 + IO– → H2O + I– + O2
Here the first step is slower than the second. So it is the rate determining step (rds).

Unit of Rate constant

Different ordered reactions have different units for k.
⮚ For an nth order reaction, the unit of rate constant is given by the formula, mol1-n Ln-1 s-
1
where n=order of reaction
▪ For Zero order reaction (n=0) K= mol L-1 S-1
▪ For First order reaction (n=1) K= S-1
▪ For Second order reaction (n=3) k= mol-1 L s-1

Integrated Rate law Equations

These are equations relating the rate of a reaction and concentration of reactants. Different ordered
reactions have different integrated rate law equations.

1. Integrated Rate law Equation for a Zero Order Reaction

Zero order reactions are reactions in which the rate of reaction is independent of concentration of
the reactants. Consider a zero order
R → P----------- (1)
The rate expression for the above reaction is r= – d[R]/dt ............................ (2)
Rate law for the above reaction is
From equations (1) & (2), we can write
The above equation is known as differential rate equation
Or, d[R] = – [Link]
On integrating the above equation we get,
[R] = –kt +C............................... (3)
Where C is the constant of integration.
When t=0, [R]= [R]0
Substitute these values in eqn. (3)
[R]0 = – k x0 + C
Or, C = – [R]0

Substituting in equation (3), we get

[R] = – kt – [R]0 .................. (4)
Or, [R]0 - [R] = kt
Or, k= [R]0 - [R] t
…………………. (5) This equation is of the form of a
straight line, –k and intercept equal to [R]0.

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Example for zero order reaction
N2 + H2 →2 NH3
In this reaction, platinum metal acts as a catalyst. At high pressure, molecules. So, a further change
in reaction conditions order reaction. Another e.g. is the thermal decomposition of HI on gold
surface

2. Integrated Rate law Equation for a First order reaction

Here the rate of the reaction is proportional to the concentration of the reactant

Examples for 1st order reactions are:

1. Hydrogenation of ethene
2. All natural and artificial radioactive decay

Half life of a reaction (t 1/2)

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The half-life of a reaction is the time taken for concentration of a reactant is reduced to one half
of its initial concentration. Or, it is the time taken for half of a reaction to complete. It is represented
as t1/2.

1. Half life of a zero order reaction

For a zero order reaction, the integrated rate law is: k = [R]0 – [R]
t
When t = t1/2, [R] = . [R]0
On substituting these values in the above equation t1/2 =
[R]0
2k
i.e. half life of a zero order reaction is directly proportional to the initial concentration of the
reactants and inversely proportional to the rate constant.

2. Half life of a first order reaction

For a first order reaction, k = 2.303 log [R]0
t [R]
When t = t1/2, [R] = [R]0/2
Substitute these values in the above equation t1/2 =
0.693
k
Thus for a first order reaction, half-life period is constant. i.e., it is independent of initial
concentration of the reacting species.

Pseudo first order reaction

These are reactions which appear to follow higher order but actually follow first order kinetics. 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.

e.g. 1. Hydrolysis of ester (ethyl acetate)

CH3COOC2H5 + H2O → CH3COOH + C2H5OH; r = k [CH3COOC2H5]
Here the concentration of water does not change during the reaction.
2. Inversion of cane sugar
C12H22O11 + H2O → C6H12O6 + C6H12O6; r = k [C12H22O11]
Cane sugar Glucose Fructose

Rate of reaction and Temperature

Most of the chemical reactions are accelerated by increase in temperature. It has been found that
for a chemical reaction, when the temperature is increased by 10°, the rate of the reaction and the

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rate constant is nearly doubled. The ratio of the rate constants of a reaction at two temperatures
differing by 100 is called temperature coefficient.
i.e., Temperature coefficient = Rate constant of the reaction at (T + 10) K
Rate constant of the reaction at T K
The temperature dependence of the rate of a chemical reaction can be accurately explained by
Arrhenius equation. The equation is:
k = A e - Ea /RT.................................................... (1)
Where A is a constant called the Arrhenius parameter or the frequency factor or the pre exponential
factor. It is constant for a particular reaction. R is the universal gas constant and Ea is activation
energy measured in joules/mole (J mol –1).
According to Arrhenius, a chemical reaction occurs by the collision of reactant molecules. All the
molecular collisions are not effective. For effective collision, the colliding molecules should have
a minimum kinetic energy called activation energy. When such molecules collide, an unstable
intermediate called activated complex is formed, which decomposes to form products.

For e.g. the reaction between H2 and I2 to form HI takes place in the following steps.
H2 + I2 → 2HI

If we plot a graph between potential energy and the progress of reaction, we get the following
graph.

Reaction coordinate
Reaction coordinate represents the profile of energy change when reactants change into products.

In a chemical reaction, all the molecules in the reacting species do not have the same kinetic
energy. Ludwig Boltzmann and James Clark Maxwell calculated the distribution of kinetic energy
among molecules. They plotted a graph between the fraction of molecules with a given kinetic
energy against kinetic energy. This plot is known as Maxwell- Boltzmann distribution curve of
molecular energies

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The peak of the curve corresponds to the most probable kinetic energy. It is the kinetic energy
possessed by maximum fraction of [Link] the temperature is raised, the maximum of
the curve moves to the higher energy value and the curve spreads to the right. That is the fraction
of molecules with activation energy increases (almost doubled).

At normal temperature the fraction of molecules having energy equal to or greater than activation
energy is very low. As the temperature increases, the fraction of molecules having energy equal to
or greater than activation energy increases and hence the rate of reaction also increases. In the
Arrhenius equation the factor e -Ea /RT corresponds to the fraction of molecules that have kinetic
energy greater than Ea.

Taking logarithm on both sides of equation (1), we get ln k

= – Ea + ln A
RT
This equation is of the form y = mx + c, equation for a straight line. So if we plot a graph between
ln k against 1/T, we get a straight line with slope = – Ea/R and the y-intercept ln A

If k1 is the rate constant at temperature T1 and k2 is the rate constant at temperature T2, then

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 ln k2 – ln k1 = Ea – Ea
RT1 RT2

From this equation we can calculate the value of activation energy (Ea), by knowing all other
values.

Effect of Catalyst
A catalyst is a substance which alters the rate of a reaction without itself undergoing any permanent
chemical change. The action of the catalyst can be explained by intermediate complex theory.
According to this theory, a catalyst participates in a chemical reaction by forming an intermediate
complex. This is unstable and decomposes to yield products and the catalyst.

A catalyst increases the rate of a chemical reaction by providing an alternate pathway or reaction
mechanism by reducing the activation energy between reactants and products.

The important characteristics of a catalyst are:

1. A small amount of the catalyst can catalyse a large amount of reactants.
2. A catalyst does not alter Gibbs energy, ΔG of a reaction. It catalyses the spontaneous reactions
but does not catalyse non-spontaneous reactions.

3. 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.

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Collision Theory
This theory was developed by Max Trautz and William Lewis. It is based on kinetic theory of
gases. According to this theory, the reactant molecules are assumed to be hard spheres and reaction
is occurred when molecules collide with each other. The number of collisions per second per unit
volume of the reaction mixture is known as collision frequency (Z).
Another factor which affects the rate of chemical reactions is activation energy. For a bimolecular
elementary reaction
A + B → Products
Rate of reaction can be expressed as
Rate (r) = ZAB e –Ea/RT
Where ZAB represents the collision frequency of reactants, A and B and e – Ea /RT represents the
fraction of molecules with energies equal to or greater than Ea. Comparing with Arrhenius
equation, we can see that A is related to collision frequency.
A third factor which affects the rate of a chemical reaction is the proper orientation. To account
for this, a factor P called the probability or steric factor is introduced. So the above equation
becomes:
Rate (r) = PZAB e –Ea/RT
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.

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1. The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact
containing wood had only 80% of the 14C found in a living tree. Estimate
theageofthesample.
Sol: Radioactive decay follows first order kinetics.

2. The rate constant for a first order reaction is 60 s-1. How much time will it take to reduce the
initial concentration of the reactant to its 1/16 th value ?

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3. Show that for a first order reaction the time required for 99% completion of a reaction is twice
the time required to complete 90% of the reaction.

4. A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.

5. The following data were obtained during the first order thermal decomposition of SO2Cl2 at a

constant volume.
Calculate the rate of the reaction when total pressure is 0.65 atm.

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6. The rate of a reaction quadruples when the temperature changes from 293 K to 313 K. Calculate
the energy of activation of the reaction assuming that it does not change with temperature.

7. The following results have been obtained during the kinetic studies of the reaction.
2A+B ——–> C + D

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Determine the rate law and the rate constant for the reaction.

**************************************THE END**********************************************

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