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Class 12th
Notes
Topic – Chemistry Kinetics

 Chemical kinetics
The branch of chemistry which deals with the rate of
chemical Reaction and the factors which effect the
rate is called as chemical kinetics.

Rate of Reaction

Average Rate Instantaneous Rate

The change in concentration of The change in concentration

reactant or product divided by of Reactant or product at
the time interval over which the different time interval, is
change occurs, is called as called as Instantaneous Rate
Average Rate of Reaction of Reaction
A→B It is obtained by drawing
Average −∆[𝐴] +∆[𝐵] tangent to the curve
= =
Rate of reaction ∆𝑡 ∆𝑡
A→B
Instantaneous −𝑑[𝐴] +𝑑[𝐵]
= =
Rate of reaction 𝑑𝑡 𝑑𝑡

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Important points.
Average Rate for reactant = -ve
Rate of reaction and
Instantaneous for product= +ve
Rate

 xA + yB → zC

1 𝑑[𝐴] 1 𝑑[𝐵] +1 𝑑[𝐶]

Instantaneous = - =- =
𝑥 𝑑𝑡 𝑦 𝑑𝑡 𝑧 𝑑𝑡
Rate of Reaction

 Rate law:-
The rate of reaction at a given time is proportional
to the molar concentration of reactants, raised to
the simple powers.
aA + bB → cC + dD

Rate of reaction α [A]x [B]y

Rate of reaction = K [A]x [B]y

 Imp point
Rate = K [A]x [B]y

The reaction is x order with respect to A and the

reaction is of y order with respect to B

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 Order of reaction:-
aA + bB → cC + dD

Rate of reaction = [Reactant]

Rate of reaction = [A]x [B]y

Overall order of reaction = (x+y)

Overall of reaction with respect to A = x
Overall of reaction with respect to B = y

 Overall order
The overall order of a reaction is defined as the sum
of concentration terms in the rate law expression.

 Elementary reaction:-
The reaction that occur in a single step and cannot
be broken down further into simpler reactions are
called as elementary reactions.

 Molecularity of Reaction:-
The number of reactant molecules taking part in a
chemical reaction, is called molecularity of reaction.

 Rate determining step(R.D.S)

The slowest step in the reaction, is called as Rate
determining step (R.D.S).

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 Reaction intermediate
The chemical species that is formed in one step and
consumed in the next step is called as reaction
intermediate
The reaction intermediate does not appear in the
rate law.

 Difference between order and molecularity

Points of Order Molecularity
difference
Experimental/ Order is Molecularity is
theoretical experimental theoretical
property property
Definition The order is the The
sum of the molecularity is
powers of the the number of
concentration reactant
terms of molecules
reactant in rate taking part in a
law. chemical
reaction
Nature of values It may be integer It is an integer
fraction or zero

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 Intergrated Rate Law for the first order Reaction

Consider a first order Reaction

1
A P ∫ . 𝑑𝑥 = 𝑙𝑛𝑥
𝑥
Reactant product 1
∫ ∫ . 𝑑 [𝐴] = 𝑙𝑛[𝐴]
−𝑑[𝐴] 𝐴
Rate = = + k [A]
𝑑𝑡 ∫ dx = x
𝑑[𝐴]
So = - k.dt
[𝐴] ∫ dt = t
Integrating both sides 𝑚
ln (m) – ln (n) = ln( )
𝑛
𝐴𝑡 𝑑 [𝐴 ] −𝑥 +𝑦
∫𝐴𝑜 1 [𝐴 ]
= −𝑘. 𝑑𝑡 =
𝑦 𝑥

− [𝐴 ] [𝐴 ]
In 𝐴𝑡
[𝐴]𝐴𝑜 = - k.t + 0 𝑡 𝑜
[𝐴 ] = [𝐴 ]
𝑜 𝑡
In [At] –ln [Ao] = -kt
Also
In [𝐴] 𝑡
[𝐴] 𝑜
= -k.t ln x = 2.303 x log10 x
1
k=- ln [𝐴]𝑡
𝑡 [𝐴]𝑜
1 𝐴𝑜
k= ln [ ]
𝑡 𝐴𝑡

2.303 𝐴𝑜
k= log10[ ]……… …….(for first order reaction)
𝑡 𝐴𝑡

Where, [Ao] = Initial concentration = (a)

[At] = concentration after time t = (a-x)
t = time
k = rate constant
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 2.303 𝑎
So k = log10( )
𝑡 𝑎−𝑥

[𝐴 ]
1
k= ln 𝑜
[𝐴 ]
𝑡
𝑡

So
[𝐴 ]
kt = ln 𝑜
[𝐴 ]
𝑡

[𝐴 ]
𝑜
[𝐴 ] e+kt
𝑡

[𝐴 ]
𝑡
[𝐴 ] = e-kt
𝑜

 Half life
The time required for the reactant concentration to
fall one half of its initial value is called as half life of
a chemical reaction.

 Expression for half life of a first order reaction.

The integrated rate law for the first order reaction is
given as

[𝐴 ]
2.303
K= log10 [𝐴𝑜] ………………………………….(1)
𝑡
𝑡

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 So now substitute
t= t1/2
[𝐴 ]
and [A]t = 𝑜
2

so eqn (1) becomes

[𝐴 ]
2.303
k= log10 𝑜
[𝐴]/2
t𝟏/𝟐
𝑜

2.303
k= log10 (2)
t𝟏/𝟐

2.303 𝑥 0.3010
k=
t𝟏/𝟐
0.693 𝑘
k= or t𝟏/𝟐 = 0.693…………………….(for first order reaction)
t𝟏/𝟐
 Graphical representation of the first order reactions.
i) Graph of rate versus initial concentration
y

Rate

x
initial concentration
−𝑑[𝐴]
rate = = k[A]t + o
𝑑𝑡

y m x c
(slope)
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ii) Graph of concentration versus time (t) :-

[𝐴 ]
iii) Graph of log [𝐴]0 versus time(t) :-
𝑡
[𝐴 ]
2.303
k= = log10 [𝐴]0
𝑡
𝑡
[𝐴 ]
𝑘
So log [𝐴]0 =( )𝑡 + 0
2.303
𝑡

X y-interept ©

y m(slope)

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 [𝐴 ]
Log 0
[𝐴 ] 𝑘
𝑡 Slope =
2.303

Time (t)→

iv) Graph of log [A]t versus time (t):-

[𝐴 ]
2.303
k= log10 0
[𝐴 ]
𝑡
𝑡
𝑘𝑡
So = log10[A]0 – log10 [A]t
2.303
−𝑘
log10[A]t = ( ) 𝑡 + log10[A] 0
2.303

y m x
c
y

−𝑘
Slope =
2.303
log[A]t

log[A]o

x
t (time)

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 Examples of first order reaction
i) 2H2O2(l) → 2H2O(l) + O2(g)
ii) 2N2O5(g) →4NO2(g) + O2(g)

 Integrated rate law for the gaseous phase(f) reaction

2.303 𝑃𝑖
k= log10
𝑡 2𝑃𝑖−𝑃

Where, k= rate constant

t = time in sec
Pi = Initial pressure
P = final pressure (pressure after time t)

 Zero order Reaction

The reaction which is independent of the
concentration of reactant is called as zero order
reaction.

 Integrated rate law for zero order Reaction

A → P
−𝑑[𝐴]
Rate = = k[A]0 = k
𝑑𝑡
𝑑[𝐴]
= -k…………………………………….[A]0 = 1
𝑑𝑡
Integrating both sides,…………………..(anything)0 = 1
We get
[𝐴]𝑡 𝑡
∫[𝐴] 𝑑[𝐴] = - ∫0 𝑑𝑡
𝑜
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[A]t – [A]o = -k.t
kt = [A]o – [A]t……………………………………….(for zero order reaction)

 Half life of zero order Reaction

So, substitute
kt = [A]0 – [A]t
[𝐴]
[𝐴] 𝑜
[𝐴] − [𝐴]
=
𝑜 𝑡
𝑡 2
t=
𝑘 t–t 1/2

[𝐴] − [𝐴]
𝑜 𝑡 2 [𝐴]− [𝐴] [𝐴]
t1/2= 2
= 𝑜 𝑜
= 𝑜
𝑘 2𝑘 2𝑘

[𝐴]
so t =1/2
𝑜
………….(for zero order reaction)
2𝑘

 Examples of zero order Reaction

a) Decomposition of ammonia (NH3) on Platinum

metal surface
2NH3(g) → N2(g) + 3H2(g)

b)Decomposition of Nitrous oxide in the presence of

Platinum(Pt) catalyst
2N2O(g) → 2N2(g) + O2(g)

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 Graphical representation of zero order reaction:-
i) Graph of [A]t versus time(t)

[A]t

 Pseudo-first order reaction

The reaction which are expected to be of higher order, but
follow first order kinetics, are called as pseudo first order
reaction.
Consider a reaction.

CH3COOCH3 (aq) + H2O(l) → CH3COOH(aq) + CH3OH(aq)

methyl acetate

Rate Law
Rate α [Reactant]
= k [Reactant]
Rate = k [CH3COOCH3][H2O]

 As here solvent water is present in large excess, so

there is negligible change (almost no change) in the
concentration of water(H2O).

Rate = k[CH3COOCH3] [H2O] = constant

Hence, pseudo first order reaction is of first order.

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 Units
 General formula of calculation unit

𝑚𝑜𝑙 1-n
Unit = ( ) sec-1
𝑙𝑖𝑡𝑟𝑒
Where n = order of reaction

a) Zero order Reaction

(n=o)

𝑚𝑜𝑙
Units of zero order reaction = (𝑙𝑖𝑡𝑟𝑒)1-0sec-1
𝑚𝑜𝑙
= (𝑙𝑖𝑡𝑟𝑒)1sec-1

b)First order Reaction

(n=1)
𝑚𝑜𝑙 1-1
Unit of first order reaction = ( ) sec-1
𝑙𝑖𝑡𝑟𝑒
𝑚𝑜𝑙 0
=( ) sec-1
𝑙𝑖𝑡𝑟𝑒
= sec-1

c) Second order Reaction

(n=2)

𝑚𝑜𝑙 1-2
Unit of second order reaction = ( ) sec-1
𝑙𝑖𝑡𝑟𝑒
𝑚𝑜𝑙 -1
=( ) sec-1
𝑙𝑖𝑡𝑟𝑒
= mol-1 litre1 sec-1

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d) Third order reaction
(n=3)
𝑚𝑜𝑙 1-3
Unit of third order reaction = ( ) sec-1
𝑙𝑖𝑡𝑟𝑒
𝑚𝑜𝑙 -2
=( ) sec-1
𝑙𝑖𝑡𝑟𝑒
= mol-2 litre2 sec-1

 Collision theory of bimolecular reactions

i) Collision between reactant molecules

1) Chemical reaction occurs as a result of collision
between the reactant species.
2) So, Rate of reaction = Rate of collision

ii) Activation Energy:- (Ea):-

The minimum kinetic energy, that the colliding
reactant molecules must possess (have) for the
reaction to occur, is called as Activation Energy
It is represented by(Ea).

iii) Orientation of reactant molecules

The colliding reactant molecules must have
proper orientations, for the reaction to be
successful or to occur.

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 Consider a reaction
A + BC → A – B + C

1) 1st way
O + O-O → O + O-O
A C B A C B

(no reaction, as the reactant molecules are not

properly oriented)

2) 2nd way
O + O-O → O-O + O
A BC AB C

(Reaction occurs, as the reactant molecules are

properly oriented)

 Activated Complex
The configuration in which, all the three atoms are
weakly connected together, is called as Activated
Complex.

A + B + C → A-----B-----C → A – B + C

Reactant Activated product

Complex

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 Graph representing potential energy barrier

 Arrhenius Equation:-

Where,
k = Rate constant
A = frequency factor or pre-exponential factor
Ea = Activation energy
R = Gas constant
T = Temperature

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 Graphical determination of Activation Energy
……..(1)
Taking “In” on both the sides of eqn(1)
We get
𝐸𝑎
In k = ln A -
𝑅𝑇
𝐸𝑎 1
also, In k = - + In A
𝑅 𝑇
𝐸𝑎 1
2.303 x log10k = - + 2.303 x log10A
𝑅 𝑇
−𝐸𝑎 1
So log10 k = + log10A
2.303𝑅 𝑇

y m x + c

−𝐸𝑎
Slope =
2.303𝑅

Log10K
log10 A

x
1/T

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 Determination of activation Energy(Ea)
𝑘2 𝐸𝑎 𝑇2−𝑇1
log10( )= [ ]
𝑘1 2.303𝑅 𝑇1 𝑇2

 Graphical description of effect of temperature

1) The average kinetic energy is directly proportional
to the temperature. At a given temperature, the
fraction of molecules having the kinetic Energy
equal to or greater than Ea (activation energy),
collides and leads to the formation of product.
 The total area under the curve at T1& T2 is same.
 With the increase in temperature, the fraction of
molecules processing energy larger than Ea
increases with increase in temperature, so rate of
reaction increases with increase in temperature

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 Effect of catalyst on the rate of reaction catalyst
The substance which increases the rate of reaction,
without itself being consumed in the reaction, is
called as Catalyst

 Some important points

a) The barrier for uncatalysed reaction(Ea) is larger
than of the catalysed reaction (Ea”)
b)A catalyst lowers the threshold energy.
c) The rate of catalysed reaction is larger than that of
the uncatalysed reaction

Graphical representation of potential energy

barriers for catalyst and uncatalyst reaction

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i) Graphical representation showing the
comparison of fraction of molecules for the
catalyst and uncatalyst reaction

`The End

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