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