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UNIT : CHEMICAL KINETICS

02. 10. 2023

RATE OF A CHEMICAL REACTION

( Refer NCERT XII Chemistry Part – I text book. Page – 96 , 97 , 98 )

―The rate of a chemical reaction is the change in the molar concentration of the species taking
part in a reaction per unit time‖

Reaction rate = Change in molar concentration

Time taken for the change

Consider a general reaction, R P

( Reactant ) ( Product )

Reaction rate with respect to R = Decrease in molar concentration of R = − ∆[R]

Time taken for the decrease ∆t

Reaction rate with respect to P = Increase in molar concentration of P = + ∆[P]

Time taken for the increase ∆t

It may be noted that negative sign is given to the reaction rate when expressed with respect to
reactants.

Significance of negative sign : As the reaction progresses, the molar concentration of the reactants
decreases. This means that at any stage in the reaction, the concentration of the reactants is less than
their initial concentration.

∆[R] = [R]Final − [R]Initial ( [R]Final < [R]Initial )

Therefore, ∆[R] is Negative

But as the rate of reaction is always positive therefore, negative sign is placed before the expression of
the reaction rate to make it positive.

 But it is not needed in case of products since the change in concentration is always positive.
This is because as the reaction progresses, more of products are formed.

∆[P] = [P]Final − [P]Initial ( [P]Final > [P]Initial )

Therefore, ∆[P] is Positive

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In the given example, the rate of decrease in concentration of R ( reactant ) is same as the rate of
increase in concentration of P( product ).

Therefore, rate of reaction = − ∆[R] = + ∆[P]

∆t ∆t

Consider another example : A + B 2C

Here,

2 x Rate of disappearance of A = 2 x Rate of disappearance of B = Rate of appearance of C

Rate of reaction = − ∆[A] = − ∆[B] = 1 ∆[C]

∆t ∆t 2 ∆t

The co-efficients of the reactant and product species involved in the reaction are called stoichiometric
coefficients.

These are the coefficients of the species involved in the balanced chemical equation.

Rate of a reaction is equal to the rate of disappearance or formation of a substance in a chemical

reaction divided by its stoichiometric coefficient.

UNIT OF RATE OF REACTION

If concentration is expressed in moles / litre and time in seconds. Therefore, the unit of the reaction
rate is expressed as mol L—1 s—1

In gaseous reactions, when the concentration of gases is expressed in terms of their partial pressures,
then the units of the rate equation will be atm s –1 .

REACTION RATE AS THE AVERAGE RATE

The rate of reaction is the change in molar concentration of the species divided by the time
taken for the change. This is infact the average rate of reaction.

The average rate of a reaction can also be determined graphically.

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Change in molar concentration = C2 − C1

Change in time = t 2 − t1

Reaction rate ( rav ) = ∆ [C] = C2 − C1

∆t t2 − t1

Limitations of Average rate :

Average reaction rate obtained by dividing the change in molar concentration by the time taken
for the change does not give the true picture of the reaction rate.

Actually, the change in molar concentration at a particular instant of time depends upon the actual
concentration at this point of time. As the actual molar concentration of the species keeps on changing
with time, so is the change in molar concentration or the reaction rate.

Therefore, the molar concentration does not change at a uniform rate and average rate of reaction fails
to give the true picture of the reaction rate.
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INSTANTANEOUS REACTION RATE

In order to get a true picture of the reaction rate, we should know the rate of reaction at any
particular instant during the course of the reaction. Such a rate is known as instantaneous rate of
reaction.

It may be defined as : the average reaction rate at the smallest interval of time which means

d t ( when ∆t approaches zero )

‗The average rate of reaction becomes equal to instantaneous rate if time interval ∆t is very small or
approaches zero‘.

Consider a general reaction, R P

( Reactant ) ( Product )

Average rate of reaction ( rav ) = − ∆[R] = ∆[P]

∆t ∆t

As ∆t approaches zero ( ∆t → 0 )

Instaneous rate of reaction ( rinst ) = − d[R] = d[P]

dt dt

( Instantaneous rate of a reaction can be found from the slope of the tangent to the curve obtained by
plotting time versus concentration of the reactant ( or product) at the point which corresponds to that
instant of time )
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DIFFERENCE BETWEEN AVERAGE RATE OF REACTION AND

INSTANTANEOUS RATE OF REACTION

Instantaneous Rate of Reaction Average Rate of Reaction

Instantaneous Rate of Reaction at any It is the appearance of product or disappearance
instant of time is defined as the rate of of reactants over a long time interval
change in concentration of any one of
the reactants or products at that
particular instant of time.
For a reaction :A+2B C
𝑑𝑥 −𝑑 𝐴 1𝑑 𝐵 𝑑 𝐶 −Δ 𝐴 1Δ 𝐵 Δ𝐶
= =- = = 𝑟𝑖𝑛𝑠𝑡 𝑟𝑎𝑣 = =- =
𝑑𝑡 𝑑𝑡 2 𝑑𝑡 𝑑𝑡 Δ𝑡 2 Δ𝑡 Δ𝑡

Example :

Question :

1. For the reaction N2 (g) + 3H2 (g) → 2 NH3 (g)

If d[NH3] = 4 x 10—8 mol L—1 s—1 , what is the value of d[H2] ?

dt dt

Answer :

Rate of reaction = − d[N2] = − 1 d[H2] = 1 d[NH3]

dt 3 dt 2 dt

d[H2] = − 3 d[NH3]
dt 2 dt

= − 3 x (4 x 10—8 mol L—1 s—1 )

2

= − 6 x 10—4 mol L—1 s—1

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FACTORS INFLUENCING THE RATES OF CHEMICAL REACTIONS

The rates of chemical reactions are influenced by a number of factors. These are

i. Concentration of reactants
ii. Temperature
iii. Presence of catalyst
iv. Nature of reactants
v. Surface area
vi. Exposure to radiations

DEPENDENCE OF RATE ON CONCENTRATION

At a given temperature, the rate of a chemical reaction is directly proportional to the product of
molar concentrations of the reacting species raised to the power their numerical coefficients also called
stoichiometric coefficients. ( a form of Law of mass action )

Let us consider a general reaction :

(1). A → Products
Reaction rate α [A] ( According to Law of mass action )
Reaction rate = k [A]

(2). A + B → Products
Reaction rate α [A][B] ( According to Law of mass action )
Reaction rate = k [A][B]

(3). aA → Products
a
Reaction rate α [A] ( According to Law of mass action )
a
Reaction rate = k [A]

(4). aA + bB → Products
a b
Reaction rate α [A] [B] ( According to Law of mass action )
a b
Reaction rate = k [A] [B]

Here ‗ k ‘ is known as rate constant or velocity constant

In case the concentration of each reactant is taken as 1 mol L—1 , then
Reaction rate ( r ) = k

The rate constant for a reaction at a given temperature is

-the rate of reaction when the molar concentration of each reactant is unity or 1 mol L —1 .
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CHARACTERISTICS OF RATE CONSTANT

The main characteristics of the rate constant ( k ) are

 The rate of any reaction depends upon the value of the rate constant and increases as the rate
constant increases
 Every reaction has a definite value of the rate constant at a particular temperature
 For the same reaction, the value of the rate constant changes with the change in temperature.
 The value of the rate constant is quite independent of the concentration of the reacting species,
pressure and also volume.
 The units of the rate constant depend upon the nature of the reaction or upon the order of the
reaction.

DIFFERENCE BETWEEN REACTION RATE AND REACTION RATE CONSTANT

REACTION RATE REACTION RATE CONSTANT

1. Rate of a reaction is the change in the 1. It is a constant of proportionality and is equal to
molar concentration of species taking part the rate of reaction when the molar concentration
in a reaction per unit time. of each reactant is unity.
2. Its value at any instant of time depends 2. Its value is independent of the molar
upon the molar concentration of the concentration of reactants and depends upon the
reactants or products at that time. temperature.
3. Its unit is always mol L—1 time—1 3. The units of rate constant depends upon the
nature of the reaction and also upon the order of
reaction.

RATE LAW FOR A CHEMICAL REACTION

( Refer NCERT XII Chemistry Part – I text book. Page- 101 )

In some cases, the experimentally determined reaction rate comes out to be different from the
rate predicted from Law of mass action.
For example, consider the reaction

(1). aA + bB → cC + dD

Reaction rate according to Law of mass action is

a b
Rate = k [A] [B]

The experimentally determined reaction rate is :

x y
Rate = k [A] [B]

( Note : Here a , b may be equal to x , y or may be different from them ).

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(2). CH3COOC2H5 + H2O → CH3COOH + C2H5OH

The reaction rate according to Law of mass action is :

Rate = k [CH3COOC2H5]1 [H2O]1

The experimentally determined reaction rate is :

0
Rate = k [CH3COOC2H5]1 [H2O]
The experimentally determined reaction rate represents the actual rate of reaction.

The expression which describes the reaction rate in terms of molar concentration of the reactants as
determined experimentally is called rate law.

Thus ,

Rate law is the expression in which reaction rate is given in terms of molar concentration of
reactants with each term raised to some power, which may or may not be same as the stoichiometric
coefficient of the reacting species in a balanced chemical equation.

ORDER OF A REACTION
( Refer NCERT XII Chemistry Part – I text book. Page- 102 )

Consider a general reaction aA + bB → cC + dD

Reaction rate according to Law of mass action is

a b
Rate = k [A] [B]

Reaction rate according to Rate Law or Rate equation is

x y
Rate = k [A] [B]

Here a , b ( stoichiometric coefficients ) may be equal to x , y ( actual coefficients ) or may be

different from them.

Order of a chemical reaction is : the sum of the coefficients ( or powers ) of the reacting species that
are involved in the rate law equation for the reaction.
OR
The sum of powers of the concentration of the reactants in the rate law expression is called the order of
that chemical reaction.

For the general reaction given above, Order of reaction = x + y

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 Order of a reaction can be 0, 1, 2, 3 and even a fraction. A zero order reaction means that the
rate of reaction is independent of the concentration of reactants.

Example of the reactions of different orders :

 First order reactions : ( Refer NCERT XII Chemistry Part – I text book. Page- 104 )
The reaction rate depends upon the concentration of one reacting species.

Consider the reaction (1). H2O2 → H2O + 1 O2

2
Rate law for the reaction is given as
Rate = k[H2O2]

(2). NH4NO2 → N2 + 2H2O ( NH4NO2 - Ammonium nitrite )

Rate law for the reaction is given as

Rate = k[NH4NO2]

 Second order reactions :

The reaction rate depends upon the concentration of two reacting species ( same or different )

Consider the reaction : 2 HI → H2 + I2

Rate law for the reaction is given as

2
Rate = k[HI]

 Third order reactions :

The reaction rate depends upon the concentration of three reacting species ( same or different )

Consider the reaction : 2 NO + O2 → 2 NO2 ( NO – Nitric oxide

NO2 – Nitrogen dioxide )
Rate law for the reaction is given as
2
Rate = k[NO] [O2]

 Zero order reactions : ( Refer NCERT XII Chemistry Part – I text book. Page- 106 )

A zero order reaction implies that the reaction rate is independent of the concentration of the
reacting species.
These reactions are mostly of heterogeneous nature carried out on the catalyst surface.
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Example (1).
The thermal decomposition of ammonia on the surface of platinum catalyst under high pressure.

1130 K / Pressure
2 NH3 (g) N2 (g) + 3 H2 (g)
Pt - catalyst

Rate law for the reaction is given as

0
Rate = k[NH3]

Rate = k

Under high pressure, the surface of the metal catalyst gets saturated with ammonia molecules.
This means that any further change in reaction conditions will not change or alter the amount of
ammonia on the surface of the catalyst. The reaction rate is independent of the molar concentration of
the reactant.

Example (2).

The photochemical reactions carried by ultraviolet radiations and proceeding by free radical
mechanism are also of zero order reactions
hƲ
H2 (g) + Cl2 (g) 2 HCl (g)

Rate law for the reaction is given as

0 0
Rate = k[H2] [Cl2]

 Fractional order reactions : ( Refer NCERT XII Chemistry Part – I text book. Page- 102 )

Consider the reaction : CHCl3 + Cl2 → CCl4 + HCl

Rate law for the reaction is given as

Rate = k [CHCl3 ] [Cl2]1/2

Order = 1 + 1 = 1 1 = 3
2 2 2
The reactions of fractional order involve more than one elementary steps.
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Order for Multi-step and Complex reactions :

Certain chemical reactions may proceed in more than one step In such cases, the order is
expressed with respect to the slowest step also called rate determining step.

Example (1).
Refer UNIT 10 : HALOALKANES AND HALOARENES
Topic : Nucleophilic substitution reactions of Haloalkanes.
Sub-topic : Substitution nucleophilic unimolecular reaction
Example :Mechanism of nucleophilic substitution reaction
- Reaction between tertiary alkyl halide and nucleophile.

Example (2).

Consider the reaction : 2 NO2 (g) + F2 (g) → 2 NO2F (g) ( NO2F – Nitryl fluoride )

The possible mechanism for the reaction is :

( slow )
Step – I : NO2 + F2 NO2F + F

( fast )
Step – II : NO2 + F NO2F

The rate equation for the reaction as determined experimentally is :

Rate = k[NO2][F2]

The order of reaction is 2 .

UNITS OF RATE CONSTANTS FOR REACTIONS OF DIFFERENT ORDERS

Let us consider a general reaction : n A → Products

n
Rate = k[A] , where n = order of the reaction.

Now, Unit of Rate = mol L—1 s—1 and [A] = mol L—1
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Rate constant , k = Rate

n
[A]

= mol L—1 s—1

n
( mol L—1 )

1− n n – 1 —1
= mol L s

( Refer NCERT XII Chemistry Part – I text book. Page- 103 )

ELEMENTARY AND COMPLEX REACTIONS

( Refer NCERT XII Chemistry Part – I text book. Page- 102 )

MOLECULARITY OF A REACTION
( Refer NCERT XII Chemistry Part – I text book. Page- 103 , 104 )

The basic condition for a chemical reaction is the simultaneous collisions among
the reacting species.

Molecularity of reaction may be defined as : the number of reacting species which

collide simultaneously.

OR
The number of reacting species (atoms, ions or molecules) taking part in an elementary reaction,
which must collide simultaneously in order to bring about a chemical reaction is called molecularity of
a reaction.
In chemical reactions, the reacting species which collide simultaneously are only count
towards molecularity.

Example :

(1). NH4NO2 → N2 + 2H2O ; Molecularity = 1

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(2). 2 HI → H2 + I2 ; Molecularity = 2

(3). 2 NO + O2 → 2 NO2 ; Molecularity = 3

(4). 2 FeCl3 + SnCl2 → 2 FeCl2 + SnCl4 ; Molecularity = 3

As the number of reacting molecules taking part in a reaction increases, the chances of their
simultaneous collisions go on decreasing. This means that the number of the reacting molecules which
are colliding simultaneously is less than the number of the molecules actually present. Therefore, the
reactions of high molecularity are less in number.

As a result, the chemical reactions with molecularities one or two are very common while those with
molecularities three or higher are comparatively less.

Example : Refer NCERT XII Chemistry Part – I text book. Page- 104 )

DISTINCTION BETWEEN ORDER AND MOLECULARITY OF A REACTION

( Refer NCERT XII Chemistry Part – I text book. Page- 104 , 105 )

ORDER MOLECULARITY
1. Order of a reaction is the sum of the 1. Molecularity is the number of reacting
coefficients of the reacting species species involved in simultaneous collisions
involved in the rate law or rate equation in an elementary or simplest reaction.
2. Order of a reaction is determined 2. The concept of molecularity is theoretical in
experimentally nature.
3. It is derived from the rate law or rate 3. It is derived from mechanism of reaction.
equation
4. It depends upon pressure and temperature 4. It is independent of pressure and temperature
5. Order of a reaction may be fractional in 5. Molecularity of reaction is always a whole
some cases number
6. Order of a reaction can be zero 6. Molecularity of a reaction cannot be zero
7. In a multistep reaction, order is determined 7. In a multistep reaction, the molecularities of all
for the slowest step only. the steps are determined
8. The overall order of the multistep reaction 8. A multistep reaction has no overall
is given by the slowest step only. molecularity.
Only the steps have the molecularity.