UNIT – 4: CHEMICAL KINETICS

Chemical Kinetics:-

The branch of chemistry which deals with the study of the

speeds or the rates of chemical reactions, the factors affecting the rates of the
reactions and the mechanism by which the reactions proceed is known as
chemical kinetics.

Classification of Reactions on the Basis of Rates:-

(1) Very Fast Reactions:-

Takes place instantaneously (time taken is 10-12 to
10-16 second) eg. Ionic reactions.
AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(aq)
NaOH(aq) + HCl(aq) → Na+(aq)+Cl-(aq) + H2O(l)

(2) Very Slow Reactions:-

May take days or months eg. Rusting of iron.

(3) Reactions Which are Neither Very Slow Nor Very Fast but Take
Place at Moderate Speeds:-
(1) CH3COOC2H5 + H2O →CH3COOH + C2H5OH
(2) C12H22O11 + H2O → C6H12O6 + C6 H12O6
Sucrose glucose fructose
(3) NH4NO2 → 2H2O + N2
(4) H2O2 → H2O + ½ O2

Rate of Reaction:-

The rate of reaction is the change in the concentration of

any one of the reactants or products per unit time.

R → P

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 UNIT – 4: CHEMICAL KINETICS

Rate of reaction =
𝐃𝐞𝐜𝐫𝐞𝐚𝐬𝐞 𝐢𝐧 𝐭𝐡𝐞 𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐚 𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭
𝐓𝐢𝐦𝐞 𝐢𝐧𝐭𝐞𝐫𝐯𝐚𝐥

Rate of reaction =
𝐈𝐧𝐜𝐫𝐞𝐚𝐬𝐞 𝐢𝐧 𝐭𝐡𝐞 𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐚 𝐩𝐫𝐨𝐝𝐮𝐜𝐭
𝐓𝐢𝐦𝐞 𝐢𝐧𝐭𝐞𝐫𝐯𝐚𝐥

Rate of reaction = − = +
∆[𝐑] ∆[𝐏]
∆𝐭 ∆𝐭

eg. PCl5 → PCl3 + Cl2

Rate of reaction = − = + =+
∆[𝐏𝐂𝐥𝟓 ] ∆[𝐏𝐂𝐥𝟑 ] ∆[𝐂𝐥𝟐 ]
∆𝐭 ∆𝐭 ∆𝐭

In general,

a A + b B → c C + d D

Rate of reaction = − 𝒂 𝑿 =− 𝒃 𝑿 = +𝒄𝑿 =+ 𝒅 𝑿

𝟏 ∆[𝐀] 𝟏 ∆[𝐁] 𝟏 ∆[𝐂] 𝟏 ∆[𝐃]
∆𝐭 ∆𝐭 ∆𝐭 ∆𝐭

Units of rate of reaction = mol 𝑳−𝟏 𝑺−𝟏 or mol 𝑳−𝟏 𝒎𝒊𝒏−𝟏 .

Average Rate of Reaction:-

Above definition average rate of reaction

(𝒓𝒂𝒗 ) = − = +
∆[𝐑] ∆[𝐏]
∆𝐭 ∆𝐭

Instantaneous Rate of Reaction:-

The rate of reaction at any instant of time

is the rate of change of concentrations of any one of the reactants or products at
that particular instant of time.

R → P

𝒓𝒊𝒏𝒔𝒕 = − = +
𝐝[𝐑] 𝐝[𝐏]
𝐝𝐭 𝐝𝐭

Ramesh Kumar Maurya Sir

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 UNIT – 4: CHEMICAL KINETICS

Calculation of Rates from Plot of Concentration of a Reactant

versus Time:-

𝒓𝒊𝒏𝒔𝒕 = − = - slope
𝐝[𝐑]
𝐝𝐭

𝒓𝒂𝒗 = − = − (𝒕𝟐−𝒕 𝟏)
∆[𝐑] (𝒙 −𝒙 )
∆𝐭 𝟐 𝟏

Calculation of Rate from Plot of Concentration of a Product

versus Time:-

𝒓𝒂𝒗 = + = + (𝒕𝟐−𝒕 𝟏)
∆[𝐏] (𝒙 −𝒙 )
∆𝐭 𝟐 𝟏

𝒓𝒊𝒏𝒔𝒕 = = slope
𝐝[𝐏]
𝐝𝐭

Expressing the Rate of Reaction in Terms of Different

Reactants and Products:-

2 N2O5 → 4NO2 + O2

Rate of decomposition (disappearance) of N2O5 = −

d[N 2 O 5 ]
𝑑𝑡

Rate of formation of NO2 =+

𝑑[𝑁𝑂2 ]
𝑑𝑡

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 UNIT – 4: CHEMICAL KINETICS

Rate of formation of O2 =+
𝑑[𝑂2 ]
𝑑𝑡

Rate of reaction = -½ = +¼ = +
d[N 2 O 5 ] 𝑑[𝑁𝑂2 ] 𝑑[𝑂2 ]
𝑑𝑡 𝑑𝑡 𝑑𝑡

N2 + 3H2 → 2NH3

Rate of reaction =− =− 3 𝑋 =+ 2 𝑋
𝑑[𝑁2 ] 1 𝑑[𝐻2 ] 1 𝑑[𝑁𝐻3 ]
𝑑𝑡 𝑑𝑡 𝑑𝑡

Hg (l) + Cl2(g) → HgCl2(s)

Rate of reaction = − = =+
∆[Hg ] ∆[Cl 2 ] ∆[HgC l 2 ]
−
∆t ∆t ∆t

2HI(g) → H2(g) + I2(g)

Rate of reaction =− 2 𝑋 =+ =+
1 ∆[HI ] ∆[H 2 ] ∆[I 2 ]
∆t ∆t ∆t

5𝑩𝒓−
(𝒂𝒒) + 𝑩𝒓𝑶𝟑 (𝒂𝒒) + 𝟔𝑯(𝒂𝒒) → 3Br2(aq) + 3H2O(l)
− +

𝒅[𝑩𝒓− ] 𝒅[𝑩𝒓𝑶− 𝒅[𝑯+ ]

Rate = − 𝟓 𝑿 =− =
𝟏 𝟑] 𝟏 𝟏 𝒅[𝑩𝒓𝟐 ]
𝒅𝒕 𝒅𝒕
−𝟔𝑿 𝒅𝒕
= +𝟑𝑿 𝒅𝒕

a A + b B → x X + y Y

Rate = − 𝒂 =−𝒃 =+𝑿 = +𝒚

𝟏 𝐝[𝐀] 𝟏 𝐝[𝐁] 𝟏 𝐝[𝐗] 𝟏 𝐝[𝐘]
𝐝𝐭 𝐝𝐭 𝐝𝐭 𝐝𝐭

(Q) For the reaction R → P, the concentration of a reactant changes

from 0.03 M to 0.02 M in 25 minutes. Calculate the average rate of
reaction using units of time both in minutes and seconds.

Ans:- 𝒓𝒂𝒗 = − =− = = 4 𝑋 10−4 mol 𝐿−1 𝑚𝑖𝑛−1

∆[𝐑] 0.02 – 0.03 0.01
∆𝐭 25 25

𝒓𝒂𝒗 = − =− = = 6.67 X 10-6 mole L-1 second-1

∆[𝐑] 0.02 – 0.03 0.01
∆𝐭 25 X 60 1500

(Q) 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.

Ans:- 2 A → product.

100 𝑋 10 −3
𝑟𝑎𝑣 =− 2 =− 2 = + 20 = = 5x10-3 mol L-1.
1 ∆[𝐴] 1 (0.4 – 0.5) 0.1
∆𝑡 10 20

Ramesh Kumar Maurya Sir

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 UNIT – 4: CHEMICAL KINETICS

Factors Influencing Rate of a Reaction:-

(1) Nature of the Reactants:-

2NO(g) + O2(g) → 2NO2(g)--------Fast
2CO(g) + O2(g) → 2CO2(g)--------Slow.

(2) Concentration of the Reactants:-

Greater are the concentration of the
reactants, faster is the reaction and vice versa.
(3) Temperature:-
The rate of reaction increases with increase of temperature.
(4) Presence of Catalyst:-
Catalyst alters the rate of reaction.
(5) Surface Area of the Reactants:-
For a reaction involving a solid reactant or
catalyst, the smaller is the particle size i.e. greater is the surface area, the
faster is reaction.

(6) Presence of Light:-

hυ
H2 + Cl2 ───→ 2HCl.

Dependence of Rate on Concentration of Reactants:-

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 UNIT – 4: CHEMICAL KINETICS

As a chemical reaction proceeds, the concentration of the reactants keeps on

decreasing while those of the products keep on increasing. However, the rate of
reaction is found to decrease. This shows that the rate of reaction is directly
related to the concentration of reactants.

Law of mass Action → Guldberg and Waage

aA + bB → products

Rate ∝ [𝐴]𝑎 [𝐵]𝑏

Rate = k [𝐴]𝑎 [𝐵]𝑏

Experimentally, the rate of the reaction is found to depend upon 𝛼 concentration

terms of A and β concentration terms of B.

Rate ∝ [𝐴]𝛼 [𝐵]𝛽

Rate = k [𝐴]𝛼 [𝐵]𝛽

It is called rate law.

Rate Law:-

Rate law is the expression which expresses the rate of reaction in

terms of molar concentrations of the reactants with each term raised to some
power, which may or may not be same as the stoichiometric coefficient of that
reactant in the balanced chemical equation.

Rate law is determined experimentally.

(1) 2NO(g) + O2(g) → 2NO2(g)

Rate = k [NO]2 [O2]

= k [NO]2 [O2]
d[R]
− 𝑑𝑡

(2) CHCl3 + Cl2 → CCl4 + HCl

Rate = k [CHCl3] [Cl2]1/2
(3) CH3COOC2H5 + H2O → CH3COOH + C2H5OH
Rate = k [CH3COOC2H5]1 [H2O]0

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 UNIT – 4: CHEMICAL KINETICS

Order of a Reaction:-

The sum of power of the concentration of the reactants

in the rate law expression is called the order of that chemical reaction.

(a) Rate = k[A]½ [B]3/2

Order of reaction =2 + = = 2
1 3 4
2 2
(b) Rate = k[A]3/2 [𝐵]−1
Order of reaction = –1= ½
3
2

Elementary Reactions:-

The reactions taking place in one step are called

elementary reactions.

Complex Reactions:-

When a sequence of elementary reactions gives us

the products, the reactions are called complex reactions.

Eg. [O] [O] 4[O]

C2H6 + [O] → C2H5OH ───→ CH3CHO────→CH3COOH────→2CO2 + 2H2O

Units of Rate Constants:-

aA + bB → product

rate = k [𝐴]𝛼 [𝐵]𝛽

α + β = n = order of reaction

𝑚𝑜𝑙 𝐿−1 𝑠𝑒𝑐 −1

k = =
Rate
(conc )𝑛 (𝑚𝑜𝑙 𝐿−1 )𝑛

Unit of k = mol1-n Ln-1sec-1

Zero order reaction → molL-1sec-1.

First order reaction→ sec-1

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 UNIT – 4: CHEMICAL KINETICS

Second order reaction → L mol-1 sec-1

3rd order reaction → mol-2 L2 sec-1.

Molecularity of a Reaction:-

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.

NH4NO2 → N2 + 2H2O Unimolecular

2HI → H2 + I2 Biomolencular

2NO + O2 → 2NO2 Termolecular.

KClO3 + 6FeSO4 + 3H2SO4 → KCl + 3Fe2(SO4)3 + 3H2O

Complex reactions take place in a sequence of a number of steps. Each of these

step reactions is called an elementary reaction. Molecularity has no meaning for
the complex reaction.

The overall rate of the reaction depends upon the slowest step. Hence, the
slowest step is called the rate determining step.

2H2O2 ──────→ 2H2O + O2

(1) H2O2 + I − ────→ H2O + IO−

(2) H2O2 + IO− ───→ H2O + I − + O2

Rate =− 𝟐 = k [H2O2] [𝐈 − ]
𝟏 𝒅[𝑯𝟐 𝑶𝟐 ]
𝒅𝒕
Order w.r.t. H2O2 = 1
Order w.r.t. I − = 1
Overall order of reaction = 2

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Distinction between Order and Molecularity of a Reaction:-

(1) Order of a reaction is an experimental quantity. It can be zero and
even a fraction but moleclarity cannot be zero or a non integer.
(2) Order is applicable to elementary as well as complex reaction whereas
molecularity is a applicable only for elementary reaction. For complex
reaction molecularity has no meaning.
(3) For complex reaction, order is given by the slowest step and
molecularity of the slowest step is same as the order of the overall
reaction.

½
(Q) For a reaction, A + B → product; the rate law is given by,r = k [a]
. What is the order of the reaction?

Ans:- r = K [A]½ [B]2

Order of reaction = ½ + 2 = 2.5

(Q) The conversion of molecules X to Y follows second order kinetics. If

concentration of X is increased to three times, how will it effect the rate
of formation of Y.

Ans:- X → Y

Rate = k [X]2

=+ = k [X]2
d[X] d[Y]
− dt dt

Let concentration of X = a molL-1.

Concentration of X increases by 3 times = 3a molL-1

Rate = K = a2

Rate = K(3a)2 = k x 9a2

= 9 ka2

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 UNIT – 4: CHEMICAL KINETICS

Thus, the rate of reaction will become 9 times. Hence, rate of formation of Y will
increase 9 times.

Integrated Rate Equation:-

Zero order reaction means that the rate of the

reaction is proportional to zero power of the concentration of reactants.

R → P

Rate = −
d[R]
dt
= 𝑘[𝑅]0

= k
d[R]
− dt

─ d[R]= k dt

Integrating both sides.

[R] = ─ kt + I ---------------(1)

I = constant of integration.

At t = 0, [R] = [R]0

[R]0 = initial concentration of the reaction

I = [R]0

[R] = - kt + [R]0

kt = [R]0 – [R]

k =
[𝑅]0 − [𝑅]
𝑡

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 UNIT – 4: CHEMICAL KINETICS

Eg. (1) Some enzyme catalysed reactions and reactions which occur on metal
surfaces are a few examples of zero order reaction.

(3) The decomposition of gaseous ammonia on a hot platinum surface is a

zero order reaction at high pressure.

1130K
2NH3(g) ──────→ N2(g) + 3H2(g)
Pt Catalyst

Rate = k [NH3]0 = k.

(4) 2HI(g) ───→ H2(g) + I2(g)

Rate = k [HI]0

First Order Reactions:-

The rate of the reaction is proportional to the first

power of the concentration of the reactant R.

R → P

Rate = −
d[R]
dt
= 𝑘[𝑅]

= ─ k dt
𝑑[𝑅]
[𝑅]

Integrating the equation:-

=
𝑑[𝑅]
[𝑅]
−𝑘𝑑𝑡

ln [R] = - kt + I

When t =0, [R] = [R]0

ln [R]0 = I

ln [R] = -kt + ln[R]0

ln [R]0 – ln [R] = kt

Ramesh Kumar Page Maurya Sir

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 UNIT – 4: CHEMICAL KINETICS

ln = kt
[𝑅]0
[𝑅]

k = ln [𝑅]0
1 [𝑅]
𝑡

At time t1-

ln [R]1 = -kt1 + ln[R]0 --------(1)

At time t2-

ln [R]2 = -kt2 + ln[R]0 --------(2)

ln [R]1 – ln [R]2 = - (kt1 – kt2)

ln = - k(t1 – t2)
[𝑅]1
[𝑅]2

k = ln 1
1 [𝑅]
(𝑡 2 −𝑡 1 ) [𝑅]2

ln = kt
[𝑅]0
[𝑅]

= 𝑒 𝑘𝑡
[𝑅]0
[𝑅]

[R]0 = [R] ekt

[R] = [R]0 𝑒 −𝑘𝑡

k = log [𝑅]0
2.303 [𝑅]
𝑡

k = log [𝑅]0
2.303 [𝑅]
𝑡

log [𝑅]0 =
[𝑅] 𝑘𝑡
2.303

Ramesh Kumar Page Maurya Sir

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 UNIT – 4: CHEMICAL KINETICS

Eg. (1) C2H4(g) + H2(g) → C2H6(g)

Rate = k [C2H4]

(2)All natural and artificial radioactive decay of unstable nuclei take place by first
order kinetics.

(3) Decomposition of N2O5 and N2O are some more examples of first order
reaction.

Q. The initial concentration of N2O5 in the following first order reaction

N2O5(g) → 2NO2(g) + ½ O2(g) was 1.24 x 10-2 mol L-1 at 318 K. The
concentration of N2O5 after 60 minutes was 0.20 x 10-2 mol L-1. Calculate
the rate constant of the reaction at 318 K.

Ans:- [R]0 = 1.24 x 10-2 molL-1

[R] = 0.20 x 10-2 molL-1

t = 60 min

k = log [𝑅]0
2.303 [𝑅]
𝑡

1.24 𝑋 10 −2
k =
2.303
60
𝑙𝑜𝑔 0.20 𝑋 10 −2

k = 0.7924 =0.03041 min-1.

2.303
60
𝑋

Integrated Rate Equation for First Order Gas Phase Reactions:-

A(g) → B(g) + C(g)

Let 𝑝𝑖 be the initial pressure of A and pt the total pressure at time ‘t’.

Total pressure pt = pA + pB + pC

pA, pB and pC are the partial pressures of A, B and C respectively.

Ramesh Kumar Page Maurya Sir

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 UNIT – 4: CHEMICAL KINETICS

If x atm be the decrease in pressure of A at time t and 1 mole each of B and C

is being formed, the increase in pressure of B and C will also be x atm each.

A (g) → B (g) + C (g)

At t =0 𝑝𝑖 atm 0 atm 0 atm

At time t (𝑝𝑖 –x) x x

P t = pA + pB + pC

Pt = 𝑝𝑖 – x + x + x = 𝑝𝑖 + x

x = Pt – 𝑝𝑖

pA = 𝑝𝑖 – x

= 𝑝𝑖 – Pt + 𝑝𝑖

pA = 2𝑝𝑖 – Pt

k = log 𝑖
2.303 𝑝
𝑡 𝑝𝐴

k = log
2.303 𝑝𝑖
𝑡 (2𝑝 𝑖 −𝑝 𝑡 )

k = log(𝟐𝒑 −𝒑
𝟐.𝟑𝟎𝟑 𝒑𝒊
𝒕 𝒊 𝒕)

Q. The following data obtained during the first order thermal

decomposition of N2O5(g) at constant volume?

2 N2O5(g) → 2N2O4(g) + O2(g)

Time / s Total pressure / atm

0 0.5

100 0.512

Calculate the rate constant.

Ramesh Kumar Page Maurya Sir

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 UNIT – 4: CHEMICAL KINETICS

Ans. 2N2O5 → 2N2O4 + O2

t = 0 0.5 atm 0 0

At time t (0.5 – 2x) 2x x

pt = 0.5 – 2x + 2x + x = 0.5 + x

x = Pt – 0.5

𝑝𝑁2 𝑂5 = 0.5 – 2(Pt – 0.5)

= 0.5 – 2 (0.512 – 0.500)

= 0.5 – 2 x 0.012

= 0.500 – 0.024

= 0.476 atm.

k =
2.303 𝑝
𝑡
𝑙𝑜𝑔 𝑝 𝑖
𝑁2𝑂5

=
2.303 0.500
100
𝑙𝑜𝑔 0.476

=
2.303
100
𝑙𝑜𝑔1.05042

= = 4.9x10-4 s-1.
2.303 𝑋 0.0212
100

Half – Life of a Reaction:-

The half – life of a reaction is the time in which

the concentration of a reactant is reduced to one half of its initial concentration. It
is represented by 𝑡1 .
2

For zero order reaction-

k =
[𝑹]𝟎 −[𝑹]
𝒕

At t = 𝒕𝟏/𝟐 , [R] = ½[R]0

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 UNIT – 4: CHEMICAL KINETICS

k =
[𝑹]𝟎 −[𝑹]𝟎
𝟐𝒕𝟏/𝟐

𝒕𝟏/𝟐 =
[𝑹]𝟎
𝟐𝒌

𝒕𝟏/𝟐 ∝ [R]0

𝟏
𝒕𝟏/𝟐 ∝ 𝒌

𝒕𝟏/𝟐 for a zero order reaction is directly proportional to the initial concentration of
the reactants and inversely proportional to the rate constant.

For the first order reaction-

k = log [𝑹]𝟎
𝟐.𝟑𝟎𝟑 [𝑹]
𝒕

t = 𝒕𝟏/𝟐 [R] =
[𝑹]𝟎
𝟐

k =
𝟐.𝟑𝟎𝟑 [𝑹]𝟎 𝑿 𝟐
𝒍𝒐𝒈
𝒕𝟏/𝟐 [𝑹]𝟎

=𝒕
𝟐.𝟑𝟎𝟑
𝒍𝒐𝒈 𝟐
𝟏/𝟐

𝒕𝟏/𝟐 = =
𝟐.𝟑𝟎𝟑 𝐱 𝟎.𝟑𝟎𝟏𝟎 𝟎.𝟔𝟗𝟑
𝐤 𝐤

𝒕𝟏/𝟐 =
𝟎.𝟔𝟗𝟑
𝐤

For zero order reaction, 𝒕𝟏/𝟐 ∝ [R]0.

For first order reaction, 𝒕𝟏/𝟐 is independent of [R]0.

Q: A first order reaction is found to have a rate constant,k = 5.5x10-14 s-1.

Find the half–life of the reaction.

Ans:- 𝒕𝟏/𝟐 =
𝟎.𝟔𝟗𝟑
𝐤

=
𝟎.𝟔𝟗𝟑
𝟓.𝟓 𝑿 𝟏𝟎−𝟏𝟒

𝟎.𝟔𝟗𝟑 𝑿 𝟏𝟎𝟏𝟒
=
𝟓.𝟓

𝒕𝟏/𝟐 =1.26 x 1013 s.

Ramesh Kumar Page Maurya Sir

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 UNIT – 4: CHEMICAL KINETICS

Q. Show that in a first order reaction, time required for completion of

99.9% is 10 times of half – life ( 𝒕𝟏/𝟐 ) of the reaction.

Ans:- 𝒕𝟏/𝟐 =
𝟎.𝟔𝟗𝟑
𝐤

t =
𝟐.𝟑𝟎𝟑 [𝑹]𝟎
𝒌
𝒍𝒐𝒈 [𝑹]

t =
𝟐.𝟑𝟎𝟑 𝟏𝟎𝟎
𝒌
𝒍𝒐𝒈 𝟎.𝟏

t =
𝟐.𝟑𝟎𝟑
𝒌
𝒍𝒐𝒈𝟏𝟎𝟎𝟎

=
𝟐.𝟑𝟎𝟑 𝑿 𝟑
𝒌

= ≈ 10
𝒕 𝟐.𝟑𝟎𝟑 𝑿 𝟑 𝑿 𝒌
𝒕𝟏/𝟐 𝒌 𝑿 𝟎.𝟔𝟗𝟑

t = 𝒕𝟏/𝟐 x 10

Pseudo First Order Reaction:-

Those reactions which are not truly of the

first order but under certain conditions become reactions of the first order are
called pseudo–first order reactions.

Eg.

CH3COOC2H5 + H2O → CH3COOH + C2H5OH

t = 0 0.01 mol 10 mol 0 mol 0 mol

t 0 mol 9.9 mol 0.01 mol 0.01 mol

Rate = k/ [CH3COOC2H5] [H2O]

[H2O] = constant.

Rate = k [CH3COOC2H5]

k = k/ [H2O]

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 UNIT – 4: CHEMICAL KINETICS

The reaction behaves as first order reaction such reaction are called pseudo-first
order reactions.

(2) Inversion of cane sugar is another pseudo first order reaction.

C12H22O11 + H2O → C6 H2O6 + C6H12O6

Sucrose glucose fructose

Rate = k [C12H22O11]

Q. A first order reaction has a rate constant 1.15 x 10-3 S-1. How long will
5g of this reactant take to reduce to 3g?

Ans:- t =
𝟐.𝟑𝟎𝟑 [𝑹]𝟎
𝒍𝒐𝒈
𝒌 [𝑹]

= 1.15 𝑋 10 −3 𝑙𝑜𝑔 3
2.303 5

t =
2.303
(𝑙𝑜𝑔 5 − log 3)
1.15 𝑋 10 −3

= 1.15 𝑋 10 −3 (0.6990 ─ 0.4771)

2.303

= 4.4438 x 102 s

Q. 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.

Ans:- k =
𝟎.𝟔𝟗𝟑
𝒕𝟏/𝟐

=
0.693
60

= 1.155 x 10-2 min-1

k = 1.155 x 10-2 min-1

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 UNIT – 4: CHEMICAL KINETICS

Threshold Energy:-

The minimum energy which the colliding molecules must

have in order that the collision between them may be effective is called
threshold energy.

Activation Energy:-

The minimum extra amount of energy absorbed by the

reactant molecules so that their energy becomes equal to threshold value is
called activation energy. OR

Activation energy is the difference between the threshold energy and the
average kinetic energy of reactant molecules.

Activation energy = Threshold energy – Average kinetic energy of the reactants.

Temperature Dependence of the Rate of a Reaction:-

Most of the
chemical reactions are accelerated by increase in temperature.

eg. In a mixture of KMnO4 and H2C2O4, KMnO4 gets decolourised faster at a higher
temperature than that at a lower temperate.

“For a chemical reaction with rise in temperature by 100, the rate constant is
nearly doubled.”

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 UNIT – 4: CHEMICAL KINETICS

The temperature dependence of the rate of a chemical reaction can be accurately

explained by Arrhenius equation.

k = A.𝒆−𝑬𝒂/𝑹𝑻

A = Arrhenius factor or frequency factor Or Pre – exponential factor

R = Gas constant.

Ea = Activation energy (J/mol)

Eg. H2 (g) + I2(g) → 2HI(g)

According to Arrhenius, this reaction can take place only when a molecule of
hydrogen and a molecule of iodine collide to form an unstable intermediate. It
exists for a very short time and then breaks up to farm two molecular of
hydrogen iodide.

When the reactant molecules absorbs energy, their bonds are loosened and new
loose bonds are formed between them. The intermediate thus formed is called an
activated complex or transition state complex. It is unstable and immediately
dissociates to form the stable products.

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 UNIT – 4: CHEMICAL KINETICS

NE is the number of molecular with energy E and NT is total number of

molecules.

The peak of the curve represents the kinetic energy possessed by the maximum
fraction of the molecules and is called most probable kinetic energy. If the point
‘a’ represents threshold energy, the shaded area abcd represents the fraction of
molecules having energy greater than threshold value.

When the temperature is increased to T+10, the fraction of molecules having

kinetic energy greater than threshold value is represented by the shaded area
abef which is almost double than the area abcd.

Thus, the increase in the rate of reaction with increase in temperature is mainly
due to increase in the number of effective collision.

Quantitavily,

𝑬𝒂
k = A.𝒆−𝑹𝑻

A = Pre – exponential factor OR frequency factor (it means frequency of binary

collisions the reacting molecules per second per litre)

Ea = Energy of activation.

R = Gas constant

T = Absolute temperature.

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 UNIT – 4: CHEMICAL KINETICS

A and Ea are collectively called Arrhenius parameter.

𝑬𝒂
𝒆−𝑹𝑻 corresponds to the fraction of molecules that have kinetic energy greater
than Ea.

ln k = ln A −
𝐸𝑎
𝑅𝑇

If the value of the rate constant at temperatures T1 and T2 are k1 and k2

respectively.

ln k1 = ln A − 𝑹𝑻𝒂
𝑬
𝟏

ln k2 = ln A − 𝑹𝑻𝒂
𝑬
𝟐

ln k2 – ln k1 = ln A − 𝑹𝑻𝒂 − ln A +
𝑬 𝑬𝒂
𝟐 𝑹𝑻𝟏

=
𝒌𝟐 𝑬𝒂 𝟏 𝟏
𝒍𝒏 ( − )
𝒌𝟏 𝑹 𝑻𝟏 𝑻𝟐

= 𝑹𝒂 (𝑻
𝒌𝟐 𝑬 𝟏 𝟏
𝒍𝒏 𝒌𝟏
−𝑻 )
𝟏 𝟐

=
𝒌𝟐 𝑬𝒂 𝟏 𝟏
𝒍𝒐𝒈 𝒌𝟏 𝟐.𝟑𝟎𝟑𝑹 𝑻𝟏
−𝑻
𝟐

=
𝒌𝟐 𝑬𝒂 𝟏 𝟏
𝒍𝒐𝒈 ( − )
𝒌𝟏 𝟐.𝟑𝟎𝟑𝑹 𝑻𝟏 𝑻𝟐

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 UNIT – 4: CHEMICAL KINETICS

(Q) The rate constants of a reaction at 500 K and 700 K are 0.02 S-1 and 0.07
S-1 respectively.

Calculate the values of Ea and A.

Ans:- 𝒍𝒐𝒈 =
𝒌𝟐 𝑬𝒂 𝟏 𝟏
𝒌𝟏 𝟐.𝟑𝟎𝟑𝑹 𝑻𝟏
−𝑻
𝟐

=
𝟎.𝟎𝟕 𝑬𝒂 𝟕𝟎𝟎−𝟓𝟎𝟎
𝒍𝒐𝒈 ( )
𝟎.𝟎𝟐 𝟐.𝟑𝟎𝟑 𝑿 𝟖.𝟑𝟏𝟒 𝟕𝟎𝟎 𝑿 𝟓𝟎𝟎

log 3.5 =
𝑬𝒂 𝟐𝟎𝟎
𝟐.𝟑𝟎𝟑 𝑿 𝟖.𝟑𝟏𝟒
𝑿 𝟑𝟓𝟎𝟎𝟎𝟎

0.5441=
𝑬𝒂
𝟐.𝟑𝟎𝟑 𝑿 𝟖.𝟑𝟏𝟒 𝑿 𝟏𝟕𝟓𝟎

Ea = 18231.43 J

ln k = ln A −
𝑬𝒂
𝑹𝑻
─

log k = log A − 𝟐.𝟑𝟎𝟑𝑹𝑻

𝒂 𝑬

log 0.02 = log A − 𝟐.𝟑𝟎𝟑 𝑿 𝟖.𝟑𝟏𝟒 𝑿 𝟓𝟎𝟎

𝟏𝟖𝟐𝟑𝟏.𝟒𝟑

log A = ─2 + 0.3010 +
𝟏𝟖𝟐𝟑𝟏.𝟒𝟑
𝟗𝟓𝟕𝟑.𝟓𝟕𝟏

= ─2 + 0.3010 + 1.90435

= 2.20535 – 2 = 0.20535

A = Antilog 0.20535

A = 1.604

Q. The first order rate constant the decomposition of ethyl iodide by the
reaction

C2H5I(g) → C2H4(g) + HI(g)

at 600 K is 1.60 x 10-5 S-1 . Its energy of activation is 209 KJ/mol.

Calculate the rate constant of the reaction at 700 K.

Ans:-

𝒍𝒐𝒈 𝒌𝟐 = 𝟐.𝟑𝟎𝟑 ( 𝟐 𝟏)
𝒌 𝒂 𝑬 𝑻 −𝑻
𝟏 𝑹 𝑻 𝑿𝑻 𝟏 𝟏

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 UNIT – 4: CHEMICAL KINETICS

𝒍𝒐𝒈 𝟏.𝟔 𝑿 𝟐𝟏𝟎−𝟓 = ( )

𝒌 𝟐𝟎𝟗𝟎𝟎𝟎 𝟕𝟎𝟎 – 𝟔𝟎𝟎
𝟐.𝟑𝟎𝟑 𝐱 𝟖.𝟑𝟏𝟒 𝟕𝟎𝟎 – 𝟔𝟎𝟎

= 2.59892

= Antilog 2.59892
𝒌𝟐
𝟏.𝟔 𝑿 𝟏𝟎−𝟓

= 3.971 x 102

k2 = 1.6 x 10-5 X 3.971 x 102

= 6.3536 x 10-3 S-1.

Effect of Catalyst:-

A catalyst is a substance which increases the speed of a

reaction without itself undergoing any chemical change. eg.

Eg. Heat
2KClO3 ────→ 2KCl + 3O2
MnO2
According to intermediate complex formation theory, the reactants first combine
with the catalyst to form an intermediate complex which is short- lived and
decomposes to form the products and regenerating the catalyst.

(1) A small amount of the catalyst is sufficient to bring about a large change in
the rate of reaction.
(2) A catalyst cannot initiate a reaction. It can only accelerate the rate of
reaction.

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 UNIT – 4: CHEMICAL KINETICS

(3) A catalyst does not alter the free energy change (∆G) of a reaction.
(4) A catalyst does not alter the enthalpy change (∆H) of the reaction.
(5) A catalyst takes part in the reaction but is regenerated without any chemical
change at the end of the reaction.
(6) For a reversible reaction, it accelerates the speed of forward reaction as well
as that of backward reaction to the same extent. Hence, it does not disturb
the equilibrium.

Collision Theory of Chemical Reactions:-

Collision theory put forward by

Max Trautz and William Lewis. According to this theory, the reactant molecules are
assumed to be hard spheres and reaction is postulated to occur 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).

A + B → products.

Rate = 𝒁𝑨𝑩 .𝒆−𝑬𝒂 /𝑹𝑻 Where ZAB represents the collision frequency of reactants.

𝒆−𝑬𝒂/𝑹𝑻 represents the fraction of molecules with energies equal to or greater than
Ea.

The collisions in which molecules collide with sufficient kinetic energy (called
threshold energy) and proper orientation so as to facilitate breaking of bond
between reacting species and formation of new bonds to form products are
called as effective collisions.

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 UNIT – 4: CHEMICAL KINETICS

The proper orientation of reactant molecules lead to bond formation whereas

improper orientation makes them simply bounce back and no products are
formed.

To account for effective collisions, another factor P, called the probability factor
or steric factors is introduced.

Rate =𝑷. 𝒁𝑨𝑩 .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.

(Q) The rate of the chemical reaction doubles for an increase of 10K in
absolute temperature from 298K. Calculate Ea.

Ans:- = ( 𝟐 𝟏)
𝒌𝟐 𝑬𝒂 𝑻 −𝑻
𝒍𝒐𝒈
𝒌𝟏 𝟐.𝟑𝟎𝟑 𝑹 𝑻𝟏 𝑿 𝑻𝟏

=
𝟐𝒌 𝑬𝒂 𝟏𝟎
𝒍𝒐𝒈 ( )
𝒌 𝟐.𝟑𝟎𝟑 𝑿 𝟖.𝟑𝟏𝟒 𝟐𝟗𝟖 𝑿 𝟑𝟎𝟖

0.3010 = 𝟐.𝟑𝟎𝟑 𝑿𝒂𝟖.𝟑𝟏𝟒 𝑿 𝟐𝟗𝟖 𝑿 𝟑𝟎𝟖

𝑬 𝟏𝟎

Ea =
𝟎.𝟑𝟎𝟏𝟎 𝐱 𝟐.𝟑𝟎𝟑 𝐱 𝟖.𝟑𝟏𝟒 𝐱 𝟐𝟗𝟖 𝐱 𝟑𝟎𝟖
𝟏𝟎

= 52897.8 J mol-1

Ea = 52.8978 KJ mol-1

(Q) The activation energy for the reaction 2HI(g) → H2(g) + I2(g) is 209.5
KJ mol-1 at 581 K. Calculate the fraction of molecules of reactants having
energy equal to or greater than activation energy?

Ans:- Ea = 209500 J mol-1

T = 581 K.

𝑬𝒂
k = A.𝒆−𝑹𝑻

𝑬𝒂
= 𝒆−𝑹𝑻 =
𝒌 𝑵𝑬𝒂
𝑨 𝑵𝑻

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 UNIT – 4: CHEMICAL KINETICS

𝑙𝑛 𝑁𝐸 = − 𝑅𝑇𝑎
𝑁 𝐸
𝑇

𝑙𝑜𝑔 𝑁𝐸 =− 2.303𝑎 𝑅𝑇
𝑁 𝐸
𝑇

= Antilog (− 2.303 𝑋 8.314 𝑋 581 )

𝑁𝐸 209500
𝑁𝑇

= Antilog – 18.83232

= Antilog -18 -1 +1- 0.16768

= 19.16768

= 1.471 x 10-19

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