TOPICS TO BE COVERED

• Rate of a reaction (Average and instantaneous)

• Factors affecting rate of reaction: concentration,
temperature, catalyst
• Order and molecularity of a reaction
• Rate law and specific rate constant
• Integrated rate equations and half‐life (only for zero and
first order reactions).
CHEMICAL KINETICS

OR
It is the branch of chemistry that deals
with the study of reaction rates and their
mechanisms.
OR
Chemical kinetics also called reaction kinetics helps us
understand the rates of reactions and how it is
influenced by certain conditions. It further helps to
gather and analyze the information about the
mechanism of the reaction and define the
characteristics of a chemical reaction
Application of Chemical Kinetics
1. In determination of rates of reactions and factors governing
rates.
2. In predicting the conditions for maintaining the reaction rates
3. In determination of yield of reaction in certain period of time
4. In calculating the time required for completion of a reaction
5. In deciding the mechanism of a reaction.
 Classification of Reactions ( In terms of rate)

• Rate of Reaction can be calculated for limited type of

reactions:
• A) Very Slow Reaction: Rusting of Iron: Rusting of
Iron
• Rate of reaction cannot be determined for such reactions
B) Very fast Reactions (Ionic Reactions) Ex: BaCl2+
Na2SO4 →BaSO4 + 2NaCl
• Rate of reaction cannot be determined for such reactions
• C) Moderate Reactions: Neither very slow nor very
fast
• For Ex:(Molecular Reactions) H2 + Cl2 → 2HCl
• Rate of reaction can be determined for such reactions
 Rate of Reaction
• Rate of reaction: It is the change in concentration of
reactant (or product) w.r.t time.

• The unit of rate of reaction is mol L-1s-1.

•A+B→C+D
• ROR= Decrease in the concentration of Reactants/time
• ROR= Increase in the concentration of Reactants/time
 Rate of Reaction
Rate of disappearance of A
where d[A] is small change in conc. of ‘A’ and dt is
small interval of time

Rate of disappearance of B
Where d[B] is small change in conc. of ‘B’ and dt is
small interval of time
Rate of appearance of C

Where d[C] is small change in conc. of ‘C’ and dt is

small interval of time
Rate of reaction can be calculated with respect to reactant as well as with respect to
product
INITIAL RATE
• The initial rate of a reaction is the instantaneous rate at the
start of the reaction (i.e., when t = 0). The initial rate is equal
to the negative of the slope of the curve of reactant
concentration versus time at t = 0.

[dc/dt]t=0
If the stoichiometric coefficients of reactants and products are not same then?
2A +3B→ 2C
Example: Hg(I) + Cl2(g) →
HgCl2(s)
Example :2HI(g) → H2(g) + I2(g)
Question : For the reaction R ® P, the concentration of a reactant changes
from 0.03M
to 0.02M in 25 minutes. Calculate the average rate of reaction using units
of time both in minutes and seconds.

Solution:
Question : In a reaction, 2A ® Products, the concentration of A decreases from 0.5
mol L–1 to 0.4 mol L–1 in 10 minutes. Calculate the rate during this interval?

Solution:
The decomposition of N2O5 in CCl4 at 318K has been studied by monitoring the concentration of N2O5 in
the solution. Initially the concentration of N2O5 is 2.33 mol L–1 and after 184 minutes, it is reduced to
2.08 mol L–1. The reaction takes place according to the equation
2 N2O5 (g) ® 4 NO2 (g) + O2 (g)
Calculate the average rate of this reaction in terms of hours, minutes and seconds. What is the rate of
production of NO2 during this period?

Solution:
N2 + 3H2 → 2NH3 .During the formation of Ammonia, 2 moles of N2
disaapear in 1 min. Find the a) ROR b)ROD of H2 c) ROA of NH3. The vol
of vessel is 1 Litre.
Factors affecting the Rate of Reaction

1. Nature of Reactants:
2. Physical state of Reactants
3.Surface area of reactants
4. Intensity of light
5. Catalyst
6.Effect Of Solvent
7. Temperature
8. Concentration of reactants
Factors affecting the Rate of Reaction
Factors affecting the Rate of Reaction

• 1. Nature of Reactants: i) ROR for Covalent compounds is low so

measurable
ii)ROR for homogenous reactants is faster
iii) ROR is inversely proportional to stability of reactant and directly
proportional to stability of product.
For eg CH3COOH → CH3COO- + H+
HCOOH → HCOO- + H+ As HCOO- is more stable than
CH3COO- due to lower –I effect so ROR of HCOOH is > than CH3COOH
Factors affecting the Rate of Reaction

2. Physical state of Reactants : ROR of gases > than ROR of liquids> ROR
of solids due to more no of effective collisions.
3. Surface area of reactants:ROR is greater when thereis greater
Surface area of reactants.
4. Intensity of light : Some reaction are photosensitive . For such
reactions ROR increases on increasing intensity of light due to increase
in no of photons.
5. Catalyst: Catalyst accelerates a reaction by participating in it without
being consumed. Catalysts provide an alternate reaction pathway to
obtain products. They are critical to many biochemical reactions.
Factors affecting the Rate of Reaction

• 6. Temperature:If the temperature is increased, the number of collisions

between reactant molecules per second (frequency of collision). Increases,
thereby increasing the rate of the reaction. But depending on whether the
reaction is an endothermic or exothermic increase in temperature increases
the rate of forward or backward reactions respectively. In a system where
more than one reaction is possible, the same reactants can produce
different products under different temperature condition.
At 100 0C in the presence of dilute sulphuric acid, diethyl ether is formed from
ethanol. 2CH3CH2OH → CH3CH2OCH2CH3+H2O
At 180 0C in the presence of dilute sulphuric acid, ethylene is the major
product. CH3CH2OH → C2H4+H2O
Note: On 100 rise in temperature , the ROR increases by two or three times,
 Factors affecting the Rate of Reaction
7. Concentration of Reactants :According to collision theory,
which is discussed later, reactant molecules collide with each
other to form products. So Generally If the concentration of
reactants is increased, the number of colliding particles will
increase thereby, increasing the rate of reaction.
But it is not so always .
a)Sometimes the ROR may decrease by increasing the
concentration
b) Sometimes the ROR may remain unaffected by increasing the
concentration
c) Sometimes the ROR may depend on one or all or none of the
concentrations of reactants.
d) Sometimes the ROR may depend upon concentration of
products.
 Factors affecting the Rate of Reaction
8.Effect Of Solvent: The nature of the solvent also
depends on the reaction rate of the solute particles.
• Example:
• When sodium acetates react with methyl iodide it
gives methyl acetate and sodium iodide.
• CH3COONa(sol)+CH3I(liq)→CH3COOCH3(sol)+NaI(sol)
• The above reaction occurs more faster in organic
solvents such as DMF (dimethylformamide) than in
CH3OH (methanol), because methanol is able to form
a hydrogen bond with CH3CO2 – but DMF is not
possible.
 RATE LAW
• Rate law explains the dependence of ROR on concentration of species
in reaction.
• The dependence is very complex as it changes with the conc
of species.
• Here we will study the simplest form.
• The only method to find the Rate law is through
experiments.
Difference between Law of Mass Action and Rate law
The law of mass action states that the rate of a reaction is
proportional to the product of the concentrations of each
reactant , each term raised to the power equal to their
respective stoichiometric coefficient. Law of Mass action is
purely theoretical
2A + B → C
Acc to Law of Mass action: Rate of reaction =k[A]2[B]
Rate law: Rate of a reaction is directly proportional to the
product of concentration of reactants raised to the power of
their respective exponents which may or may not be equal to
their stoichiometric coefficient.
2A+B →C [ We cannot write its rate of reaction by simply observing its balanced
chemical equation . Rather we will need its experimental data]
Rate law is purely experimental
Rate Law
• 2A + B → C
• : Rate of reaction =k[A]a[B]b
Where a = order of reaction wrt A b= order of reaction wrt B

Suppose experimerntally it is determined that order of reation wrt A is 3 and order of

reaction wrt B is 1 then

ROR= k[A]3[B]1
total order of reaction= 4

Law of mass action cannot always be applied to write ROR . Law of mass action can be
applied for single step reaction but not for reaction which take place in multiple steps
and for reaction taking in multiple steps rate of reaction depends on slowest step which
becomes the rate deteremining step.
RATE LAW EXPRESSION

Rate law expression : ROR = k [A]x[B] y

K= Rate Constant/Velocity Constant/Specific reaction rate

If concentration of all the species in rate law expression is unity then ROR=k
Or Rate constant becomes equal to the rate of reaction whwn concentration of all
species is unity(1)

Unit of k
ROR/ [A]x[B] y
moleL -1s -1/[moleL -1]x[moleL -1] y
[mole L -1]1-n s -1
 Order of a Reaction
• The sum of power of the concentration of reactant in a
rate law expression gives the order of reaction.
• Let A + 2B → C + D be a chemical reaction.
• From rate law R = k [A]x [B]y
• Now Order of reaction is defined as addition of the
order of all the reactants participating in a chemical
reaction.
• order w.r.t. A = x
• Order w.r.t. B = y
• Overall order of the given reaction = (x + y).
RATE LAW
THIS IS A DIFFERENTIAL EQWUATION WHICH IS CALLED RATE LAW EXPRESSION
 • From rate law we come to know that we can write the rate of
reaction as a function of initial concentrations

We can do this fixing the concentration of one reactanmt and keep varying the concentration of the
other reactant.
RATE LAW EXPRESSION
• 2A + B→ Products

• ROR(r)α [A]x
• ROR(r) α [B] y

• Rate law expression : ROR = k [A]x[B] y

• [A]: Concentration of A
• [B]: Concentration of B
• x= order of reaction wrt A
• y= order of reaction wrt B
• x+y = n (n= Order of Reaction) n= integer ( +ve , -ve or even fraction )
Rate Law Expressions
According to the law of mass action,
For a chemical reaction,
aA + bB → Products
Rate α [A]a [B]b = k[A]a [B]b
But experimentally, it is observed that the rate of
reaction is found to depend upon ‘p’ concentration
terms of A and ‘q’ concentration terms of B Then,
Rate α [A]p [B]q = k[A]p [B]q
where, [A] and [B] molar concentrations of A and B
respectively and k is the velocity constant or rate
constant. The above expression is known as rate
law.
 RATE LAW EXPRESSION
• For eg: 2A + B→ Products
• From experiments suppose :
• A)if Conc of A is doubled then ROR doubles Then ROR α [A]1
• B) if Conc of B is doubled then ROR becomes 4 times Then ROR α [B]2

• Then Rate Law Expression for the reaction is written as

• ROR =k α [A]1 [B]2 k= rate constant
• Order of reaction wrt A=1
• Order of reaction wrt B=2
• Overall order of reaction = 3
ORDER OF REACTION

From the rate law expression we come to know that the power of concentration term does not depends
on stoichiometric coefficient but shows the sensitivity of reaction towards a specific reactant
Rate Constant k
• Rate constant may be defined as the specific rate of
reaction when the molar concentrations of the
reactants is taken to be unity, i.e.,
• Rate = k, if [A] = [B] = 1
• Units of rate constant or specific reaction rate for a
nth order reaction is given as
• K = (1/Time) x (1/[Conc.]n – 1)
Characteristics of rate constant
1.Greater the value of rate constant, faster is the
reaction.
2.Each reaction has a particular value of rate
constant at a particular temperature.
3.The value of rate constant for the same reaction
changes with temperature.
4.The value of rate constant for a reaction does’t
depend upon the concentration of the reactants.
5.Unit of rate constant directly depends on order of
reaction
Units of Rate Constant
• k = rate / [A]n = (mol.L-1s-1/molL-1) n or

• For zero order reaction , n=0

• For 1st order reaction , n=1

•k= rate / [A]1 = (mol.L-1s-1/molL-1) 1= s-1
•
• For 2nd order reaction, n=2
•k= rate / [A]2 = (mol.L-1s-1/molL-1) 2= L.mol-1s-1
•
Units of Rate Constant
• R=k[A]p[B]q
• K= R/ [A]p[B]q
• K= molL-1 s-1/[molL-1]p[molL-1]q
• K= molL-1 s-1/[molL-1]p+q where p+q=n

• K= molL-1 s-1/[molL-1]n
• K= [molL-1]1-n s-1
For the reaction:
2A + B ® A2B
the rate = k[A][B]2 with k = 2.0 × 10–6 mol–2 L2 s–1. Calculate the initial
rate of the reaction when [A] = 0.1 mol L–1, [B] = 0.2 mol L–1. Calculate
the rate of reaction after [A] is reduced to 0.06 mol L–1.

• The initial rate of the reaction is Rate = k [A][B]2

• = (2.0 × 10 - 6mol - 2L2s - 1) (0.1 mol L - 1) (0.2 mol L - 1)2

• = 8.0 × 10 - 9mol - 2L2s - 1
• When [A] is reduced from 0.1 mol L - 1to 0.06 mol - 1,
• the concentration of A reacted = (0.1 - 0.06) mol L - 1 = 0.04 mol L - 1
• Therefore, concentration of B reacted= 1/2 x 0.04 mol L -1 = 0.02 mol L - 1
• Then, concentration of B available, [B] = (0.2 - 0.02) mol L - 1= 0.18 mol L - 1
• After [A] is reduced to 0.06 mol L - 1, the rate of the reaction is given by,
• Rate = k [A][B]2
• = (2.0 × 10 - 6mol - 2L2s - 1) (0.06 mol L - 1) (0.18 mol L - 1)2
• = 3.89 mol L - 1s - 1
• The initial rate of the reaction is Rate = k [A][B]2

• = (2.0 × 10 - 6mol - 2L2s - 1) (0.1 mol L - 1) (0.2 mol L - 1)2

• = 8.0 × 10 - 9mol - 2L2s - 1
• When [A] is reduced from 0.1 mol L - 1to 0.06 mol - 1,
• the concentration of A reacted = (0.1 - 0.06) mol L - 1 = 0.04 mol L - 1
• Therefore, concentration of B reacted= 1/2 x 0.04 mol L-1 = 0.02 mol L - 1
• Then, concentration of B available, [B] = (0.2 - 0.02) mol L - 1= 0.18 mol L - 1
• After [A] is reduced to 0.06 mol L - 1, the rate of the reaction is given by,
• Rate = k [A][B]2
• = (2.0 × 10 - 6mol - 2L2s - 1) (0.06 mol L - 1) (0.18 mol L - 1)2
• = 3.89 mol L - 1s - 1
Units of Rate Constant k for different
Order of Reaction
Question : Identify the reaction order from each of the
following rate constants.
Question : Identify the reaction order from each of the
following rate constants.
(i) k = 2.3 × 10–5 L mol–1s–1
(ii) k = 3 × 10–4 s–1

Answer:(i) The unit of second order rate constant is L

mol s , therefore
–1 –1

k = 2.3 × 10 –5 mol–1s–1represents a second

–

order reaction.

(ii) The unit of a first order rate constant is s –

1
therefore
PROBLEM. From the rate expression for the following reactions, determine
their order of reaction and the dimensions of the rate constants.
(i) 3 NO(g) → N2O(g) Rate = k[NO]2
(ii) H2O2 (aq) + 3 I - (aq) + 2 H+→ 2 H2O (l) + I3- Rate = k[H2O2][I - ]

SOLUTION. (i) Rate = k[NO]2

Order of the reaction = 2
Dimension of k = Rate / [NO]2 = mol L-1 s-1 / (mol L-
)
1 2

= mol L-1 s-1 / mol2 L-2 = L mol-1 s-1

ii) Rate = k[H2O2][I - ]

Order of the reaction = 2
Dimension of k = Rate / [H2O2][I - ]
= mol L-1 s-1 / (mol L-1) (mol L-1)
= L mol-1 s-1
PROBLEM. From the rate expression for the following
reactions, determine their order of reaction and the
dimensions of the rate constants.
(i)CH3CHO(g) → CH4(g) + CO(g) Rate = k [CH3CHO]3/2
(ii)C2H5Cl(g) → C2H4(g) + HCl(g) Rate = k [C2H5Cl]

Solution: (i) Rate =k [CH3CHO]3/2 Order of reaction = 3/2

Dimension of k = Rate / [CH3CHO]3/2 = mol L-1 s-1 / (mol L-
)
1 3/2

= mol L-1 s-1 / mol3/2 L-3/2 = L½ mol-½ s-1

(ii) Rate = k [C2H5Cl]

Order of the reaction = 1
Dimension of k = Rate / [C2H5Cl]
= mol L-1 s-1 / mol L-1
• PROBLEM. For a reaction, A + B → Product; the
rate law is given by, r = k [A]½ [B]2. What is the
order of the reaction?
• SOLUTION. The order of the reaction = 1/2 + 2
• = 2 1/2
• = 2.5
A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three times?
(iii) How is the rate affected when the concentrations of both A and B are doubled?
• PROBLEM: Conversion 0f molecules X →Y follows second
order kinetics . If the concentration of X is increased three times, how
will it affect the rate of formation of Y?
• SOLUTION: r = k[X]2 …………..i
• If the concentration is increased three times then
• R’ = k[3X]2…………..ii
• Divide ii by I
• R’/R = k[3X]2/ k[X]2
= 9 times
Thus the rate of formation of Y increases by 9 times
Sample Question 2020

• Question :For a reaction the rate law expression is represented as follows:

• Rate = k [A][B]1/2
• i. Interpret whether the reaction is elementary or complex. Give reason to support your answer.
• ii. Write the units of rate constant for this reaction if concentration of A and B is expressed in
moles/L

Answer:Reaction is a complex reaction. And Order of reaction is 1.5.

Molecularity cannot be 1.5, it has no meaning for this reaction. The reaction occurs in
steps, so it is a complex reaction.

(ii)units of k are mol-1/2L1/2s-1

Question : Write down the rate Expression for
the reaction :
SO2 + 1/2O2 → SO3

Question : Write down the rate Expression for

the reaction :
½ N2 + 3/2H2 → NH3
Initial rate Method to calculate Rate Law
and Order of reaction

• By using the experimental data , we try to find the rate law and
Order of Reaction.
• Let A + 2B → C + D be a chemical reaction.
• From rate law R = k [A]x [B]y
• Now Order of reaction is defined as addition of
the order of all the reactants participating in a
chemical reaction.
• order w.r.t. A = x
• Order w.r.t. B = y
• Overall order of the given reaction = (x + y).
Numerical
• For the reaction A+B→products, the following initial rates were
obtained at various given initial concentrations. Write down the rate
law for this reaction and Determine the half life period.
S.No [A] mol/L [B]mol/L Initial rate

1 0.1 0.1 0.05

2 0.2 0.1 0.10

3 0.1 0.2 0.05

Sample Question 2020 –
Question
• The following results have been obtained during the kinetic studies of the reaction:
• P + 2Q  R + 2S Exp. Initial P(mol/L) Initial Q (mol/L) Init. Rate of Formation of R (M min-1)

1 0.10 0.10 3.0 x 10-4

2 0.30 0.30 9.0 x 10-4
3 0.10 0.30 3.0 x 10-4
4 0.20 0.40 6.0 x 10-4
• Determine the rate law expression for the reaction.
Sample Question 2020 -Solution
The rate for the decomposition of NH3​on platinum surface is zero order. What
are the rate of production of N2​and H2 if K=2.5×10−4 mol litre−1s−1.
Question 4.
Dividing Eq 2by 3
 Molecularity of a Reaction
• Another property of a reaction called molecularity helps in
understanding its mechanism.
• The number of reacting species (atoms, ions or molecules)
taking part in an elementary reaction, which must collide
simultaneously and effectively in order to bring about a
chemical reaction is called molecularity of a reaction.

OR
• Molecularity can be defined as no of particles colliding at a
specific point.
 Molecularity of a Reaction
• Molecularity of a reaction is defined as the number of reactant molecules (or
atoms or ions) taking part in an elementary reaction.
(a) Molecularity of a reaction is always a positive integer.
(b) It doesn't change with experimental conditions as it is a theoretical value.
(c) The molecularity of a reaction cannot have a fractional or zero values.
(d) The minimum value of the molecularity is one and maximum is 3.
(e) Molecularity is defined only for elementary reaction which takes place in
single step.
(f) For an elementary reaction the order and molecularity remain same.
Molecularity of a Reaction
• The molecularity of a reaction can be explained by considering the
following example :
Consider a reaction, i.e.,
N2​O5​(g)⟶2NO2 (g)+1/2​O2​(g)
In this reaction, only one molecule is taking part in the reaction,
therefore the rate law expression for this reaction is :
Rate =k[N2​O5​]
Hence, the reaction is unimolecular and first order.
Similarly, a reaction can be bimolecular or trimolecular depending
on the number of molecule taking part in the reaction.
 Molecularity of a Reaction
• The molecularity of a reaction can be explained by considering the
following example :
Consider a reaction, i.e.,
2HI​(g)⟶H2 (g)+I2​(g)
In this reaction, two molecules are taking part in the reaction,
therefore the rate law expression for this reaction is :
Rate =k[HI]2 Hence, the reaction is bimolecular and second order.
Similarly 2NO + O2 ⟶ 2NO2
• Rate =k[NO]2[O2]
• Hence, the reaction is trimolecular and third order.
• So in an elementary reaction the order and molecularity are always
same except in Psuedo Order Reactions.
 Molecularity of a Reaction
• A reaction with molecularity=1 is called Unimolecular
• Example : NH4NO2 → N2 + 2H2O
• A reaction with molecularity =2 is called bimolecular.
• Example : Cl + CH4 → HCl + CH3
• A reaction with molecularity =3 is called trimolecular.
Example : a) 2FeCl3 + SnCl2 → 2FeCl2 + SnCl4
b) 2NO + O2 → 2NO2
c) 2SO2 + O2 → 2SO3
• It is theoretical value and does not determine the rate of reaction. Nor
does it depend upon external factors like temperature or pressure, etc.
• It helps in understanding the mechanism of reaction .
• More than 3 molecules make complex reaction.
• Maximum molecularity can be 3 or <3 but cannot be zero or in fractions .
• Molecularity for a complex reaction cannot be explained bcoz it depends
on Rate determining step.
Molecularity is not defined for Complex Reactions
1. NO2 + CO→NO + CO2 (complex)
Rate = k[NO2]2 found experimentally
So order=2 but molecularity not defined

2. CH3CHO → CH4 + CO (complex)

Rate = k[CH3CHO]3/2 found experimentally
So order=3/2 but molecularity not defined
Difference between Order and Molecularity
A Pseudo first order reaction
• Hydrolysis of Cane Sugar –
• C12H22O11 + H2O → C6H12O6 + C6H12O6
Cane sugar(l) glucose(l) fructose(d)

The overall product is dextrorotatory

Molecularity =2

Order=1

As H2O is in excess so conc of H2O is taken to be constant.

A Pseudo first order reaction
• A Pseudo first order reaction can be defined as a
second order or bimolecular reaction that is made to
behave like a first order reaction. This reaction occurs when
one reacting material is present in great excess or is
maintained at a constant concentration compared with the
other substance.
• In this section, we will learn about the pseudo-first-order
reaction and their rate equations. To begin with, reactions
that appear to be second order in nature but are
approximated as a first-order of reaction on close analysis.
For example, a second – order of the reaction is given by
the equation,
• A + B —-> C + D
 A Pseudo first order reaction
• A + B —-> C + D
• This reaction is dependent upon the concentrations of both A
and B but one of the components is present in large excess and
thus its concentration hardly changes as the reaction proceeds.
• So, if component B is in large excess and the concentration of
B is very high as compared to that of A, the reaction is
considered to be pseudo-first order reaction with respect to A
and if component A is in large excess and the concentration of
A is very high as compared to that of B, the reaction is
considered to be pseudo first order with respect to B.
• For Ex: CH3COOC2H5 + H2O —–> CH3COOH + C2H5OH
 Integrated Rate Equations
• We have already noted that the concentration dependence of
rate is called differential rate equation. It is not always
convenient to determine the instantaneous rate, as it is
measured by determination of slope of the tangent at point
‘t’ in concentration vs time plot. This makes it difficult to
determine the rate law and hence the order of the reaction.
In order to avoid this difficulty, we can integrate the
differential rate equation to give a relation between directly
measured experimental data, i.e., concentrations at different
times and rate constant. The integrated rate equations are
different for the reactions of different reaction orders.
• We shall determine these equations only for
• A) zero order chemical reactions. and
• B) first order chemical reactions.
Zero Order Reaction
• A→ Product
• For Zero Order [A]0

In a zero order reaction as the time passes, concentration of A decreases

and concentration of product increases , but the rate of reaction remains
constant throughout the reaction
Thus in a zero Order reaction , the rate of reaction is inhdependant of the
concentration of reactants.
Thus ROR=k[A] 0 [A]0 =1
So ROR=k
All Possible graphs for zero
order Reaction
 Half life of a reaction

Definition :Half life of a reaction is the time taken by the reaction to reduce the concentration of
reactants to half of its initial concentration .

A → Products
At t=0 Initial concentration = A0
At= A0-kt
kt = A0-At
Now putting the above values In zero order reaction when the concentration becomes 50% , then At
t =t1/2 and Remaining concentration = A0/2
kt1/2= A0 - A0 /2

So t1/2 = [A0 ]/2k

Half life of a Zero Order
Reaction
For a reaction ,time required for 20% completion is
4o minutes and 40% completion is 80 minutes .
Find the order of reaction and rate constant.
 → Rate does not depend on concentration of HI
but depends on catalyst and pressure

→ Rate does not depend on concentration of

NH3 but depends on catalyst and pressure

→ Rate does not depend on concentration of

N2O but depends on Temperature

→ Rate does not depend on concentration of

H2 and Cl2 but depends on intensity of light

5) Enzyme catalysed reactions are also zero oder reaction

Half life of First Order Reaction
6) C2H4 + H2 → C2H6
7) Acidic hydrolysis of ester.
8) Inversion of cane sugar in acidic medium
9) Growth and decay of bacteria
• NCERT Question:The initial concentration of N2O5 in the following first
order reaction
N2O5(g) ® 2 NO2(g) + 1/2O2 (g) was 1.24 × 10–2 mol L–1 at 318 K.
The concentration of N2O5 after 60 minutes was 0.20 × 10 –2 mol L –1.
Calculate the rate constant of the reaction at 318 K.
AnS:
Prove that in first order reaction Time
required for 75% completion is equal to twice
of 50% completion
 Prove that In a first Order reaction, Time taken
for 99.9% completion of reaction is 10 times the
time taken for 50% completion of reaction .
Show that it follows a pseudo first order reaction, as the concentration of water remains nearly
constant (55 mol L–1), during the course of thereaction. What is the value of k¢ in this equation?
Rate = k¢ [CH3COOCH3][H2O]
For pseudo first order reaction, the reaction should be first order with respect to ester when
[H2O] is constant. The rate constant k for pseudo
first order reaction is k= 2.303/t log C0/C, where k = k’[H2O]
 Question :1 A first order reaction has a rate constant 1.15 10-3s-1. How
long will 5 g of this reactant take to reduce to 3 g?
From the question, we can write down the following information:
Initial amount = 5 g
Final concentration = 3 g
Rate constant = 1.15 10 - 3s - 1
We know that for a 1st order reaction,

= 444.38 s
= 444 s (approx)
• NCERT QUESTION: Time required to decompose SO2Cl2 to
half of its initial amount is 60 minutes. If the decomposition
is a first order reaction, calculate the rate constant of the
reaction.
 Question 2: For a reaction, A + B → Product; the
rate law is given by, r = k [A]½ [B]2. What is the
order of the reaction?
• The order of the reaction = 1/2 + 2
• = 2 1/2
• = 2.5
 Question3. A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three times?
(iii) How is the rate affected when the concentrations of both A and B are
doubled?
Question 5

Solution
A reaction is 50% complete in 2h and 75%
complete in 4 h . What is the order of
reaction?
 Sample Question 2020
• Question 21. The C-14 content of an ancient piece of wood was found to have three tenths of
that in living trees. How old is that piece of wood? (log 3= 0.4771, log 7 = 0.8540 , Half-life of C-
14 = 5730 years )
• Answer:
 Collision Theory
• According to the collision theory, “the molecules of reactants
are assumed to be hard spheres and the reactions are
assumed to occur only when these spheres (molecules)
collide with each other”. So it was important to quantify the
number of collisions occurring in order to form products so that we
can have a clear picture of the reaction, and hence came the term
collision frequency.
• Collision Frequency can be understood as the number of
collisions per second per unit volume of the reacting mixture. It is
generally denoted by Z.
 Collision Theory
• Let’s consider the following bimolecular elementary reaction:
• P + Q → Product
• Now as per the collision theory, the rate of the above reaction can be given by:

Rate=ZPQe−EaRT………………………….(1)

• Where: ZPQ = collision frequency of reactants P and Q

• Ea = Activation Energy R = Universal Gas Constant
• T = Temperature in absolute scale
• One more parameter that affected the rates of chemical reactions significantly is
activation energy (Ea). The term activation energy was given by Arrhenius, it is the
minimum amount of energy that the reactants must possess in order to form a
product during a chemical reaction.
Activation Energy

• The activation energy is the minimum amount of energy needed by the reacting
particles in any particular reaction for that reaction to take place. Unless
particles collide with sufficient energy to supply the activation energy they
simply don’t react. The activation energy must be supplied before a reaction
can take place.
• To start a chemical reaction chemical bonds need to be broken in the reactants,
which requires energy. The energy needed to start the reaction is known as
activation energy. Sometimes the activation energy is low so that the reaction
can start at room temperature without heating.
Arrhenius Equation

• As per the Arrhenius Equation, all the molecules that have energy
greater than or equal to activation energy will collide to form
products. But this postulate was not true for all the reactions. A
significant amount of deviation was observed in reactions involving
complex molecules.
• Some molecules having sufficient energy (activation energy) did not
collide to form the product. Only a few of them made effective
collisions, collisions that led to the formation of products. The
scientists found that the kinetic energy of the molecules is not the
only parameter that governs the reaction.
• They concluded that only those molecules that have the threshold
energy (activation energy) and proper orientation during the collision
will form products. They introduced a probability factor P to account
for the effective collisions.
Activation Energy
Dependance of rate/rate constant on temperature

• When we increase temperature, the no of effective collisions increase as a result rate orf
reaction and rate constant increases . Mathematically it is expressed as

…………………..Arrhenius Equation

Taking log on both sides

lnK =lnA + lne−EaRT
lnK = lnA -Ea/RT lne [lne=1]
lnK = lnA –Ea/RT another form of Arrhennius Equation
• lnK = lnA –Ea/RT
• If you increase temp Ea/RT decreases but-Ea/Rt increases so k also
increases
When temp of a reaction is increased from 27o C to
47 oC , rate constant becomes 10 times . Find
activation energy?
 Temperature Coefficient of a reaction α
α is the ratio of rate constant at two different temp which differ by 100C.For
most of reactions the value of α lies between 2 and 3.
When temperature of a reaction is increased from 100 C to 1000 C ,then
what will be its change in its rate constant
Arrhenius factor is equal to rate
constant at infinite temperature
 Arrhenius Equation
• The Arrhenius equation is an expression that provides a
relationship between the rate constant (of a chemical
reaction), the absolute temperature, and the A factor (also
known as the pre-exponential factor; can be visualized as
the frequency of correctly oriented collisions between
reactant particles). It provides insight into the dependence
of reaction rates on the absolute temperature. The
expression of the Arrhenius equation is:

•k denotes the rate constant of the reaction

•A denotes the pre-exponential factor which, in terms of the collision theory, is the frequency of
correctly oriented collisions between the reacting species
•e is the base of the natural logarithm (Euler’s number)
•Ea denotes the activation energy of the chemical reaction (in terms of energy per mole)
•R denotes the universal gas constant
•T denotes the absolute temperature associated with the reaction (in Kelvin)
Arrhenius equation relates activation energy and rate constant
∆H=-ve ∆H=+ve
Ep<Er Ep>Er
Note: It has been observed that for every 100 rise in temperature, the rate of
reaction becomes double
2.303log10k = 2.303log10A - Ea/RT
OR
log10k = log10A - Ea/2.303RT
Effect of catalyst on rate and rate constant
• In chemistry, a catalyst is any substance that increases a reaction rate without being
consumed on its own. In other words it’s a substance that increases the rate of a chemical
reaction without being changed in identity.
• In the presence of catalyst, an alternative pathway with lower activation energy is made
available. More collisions are successful because less energy is required for success. After
the reaction, the catalyst can be recovered after the reaction is over and used again and
again.
Effect of catalyst on rate and rate constant
• A small amount of the catalyst can catalyse a large
amount of reactants. A catalyst does not alter Gibbs
energy, DG of a reaction. It catalyses the spontaneous
reactions but does not catalyse nonspontaneous
reactions. It is also found that a catalyst does not change
the equilibrium constant of a reaction rather, it helps in
attaining the equilibrium faster, that is, it catalyses the
forward as well as the backward reactions to the same
extent so that the equilibrium state remains same but is
reached earlier.
 At 270C , when a catalyst is added , then
its activation energy is decreased by 2
Kilo calories, calculate the change in rate
constant ?
Arrhenius equation is

k=Ae−Ea/RTk=Ae−Ea/RT

In the presence of catalyst rate constant k' = Ae−Ea/RTAe−Ea/RT

Eq. (ii ) /Eq. (i), we get

k/′k=e(Ea/Ea′)/RT
k′k=e(20002×300)=e3.33

(∵Ea−Ea′=2000cal(given)]

∵∵ On taking log both sides,

logk/′k=3.33/2.303

k′/k= antilog 1.446 = 27.92 = 28

We know that, rate (R) ∝ k

∴kR′/R=k′/k=28

or R' =28 R
• The hall-life period of a radioactive substance is 140 days. After, how much time, 15 g will
decay from a 16 g sample of the substance ?
• A
• 140 days
• B
• 280 days
• C
• 420 days
• D
• 560 days
•
Ans: 560 days
• The half-life period of a radioactive substance is 70 days. One gram of
the same substance will become 0.25 gm after
1. 140 days
2. 70 days
3. 210 days
4. 280 days
Ans : 140 days