CHEMICAL KINETICS DR.

KAVITHA C N

Chemical Kinetics
The Chemical kinetics is the branch of chemistry which deals with study of rate of reaction and the factors
influencing it.
The study of chemical kinetics includes:
(1) Rate of the reactions and rate laws.
(2) Effect of temperature, pressure, concentration and catalyst, on the rate of a reaction.
(3) Mechanism by which a reaction occurs.
The studies have also been useful in selecting optimum conditions for getting maximum yields of several
industrial products.

Consider a reaction, A+B ⎯⎯→ C +D

As the reaction progresses, the concentration of reactant keeps on falling with time and the
concentration of the product goes on increasing with time. Hence, the rate of the reaction can be expressed
in terms of decrease in concentration of reactant or increase in concentration of the product.
The rate of reaction is defined as the change in concentration of any one of the reactant or products in
unit time at a given temperature.

𝑑[𝐴] 𝑑[𝐵] 𝑑[𝐶] 𝑑[𝐷]

rate, 𝑟 = − =− =+ =+
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡

Consider a reaction, 2A+B ⎯⎯→ 3C +D

1 𝑑[𝐴] 𝑑[𝐵] 1 𝑑[𝐶] 𝑑[𝐷]

𝑟=− =− =+ =+
2 𝑑𝑡 𝑑𝑡 3 𝑑𝑡 𝑑𝑡

Rate law:
The rate of a reaction is directly proportional to the reactant concentrations, each concentration
being raised to some power.
A+B ⎯⎯→ C +D

𝑟 ∝ [𝐴]𝑥 [𝐵]𝑦

𝑟 = 𝑘[𝐴]𝑥 [𝐵]𝑦
The proportionality constant k is called the rate constant for the reaction.
When, [A]=[B]=[C]=1mol/dm3
Thus, rate constant may be defined as the specific reaction rate when molar concentrations of the reactants
is taken to be unity.
 CHEMICAL KINETICS DR. KAVITHA C N

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.

Rate law for any reaction cannot be predicted by merely looking at the balanced chemical equation, i.e.,
theoretically but must be determined experimentally.

Order of a Reaction:
The order of a reaction is defined as the sum of the power of the concentration terms raised in the
rate-law.
𝒓 = 𝒌[𝑨]𝒙 [𝑩]𝒚

x = order of reaction w.r.t. A

y = order of reaction w.r.t. B
Overall order of reaction(n) = x + y

Examples:
First order reaction, 𝟐𝐍𝟐 𝐎𝟓 → 𝟒𝐍𝐎𝟐 + 𝐎𝟐 r = k[𝐍𝟐 𝐎𝟓 ] order=1

Second order reaction, 𝐇𝟐 + 𝐈𝟐 → 𝟐𝐇𝐈 r = k[𝐇𝟐 ]1 [𝐈𝟐 ]1 order=1+1=2

𝟐𝐍𝐎𝟐 → 𝟐𝐍𝐎 + 𝐎𝟐 r = k[𝐍𝐎𝟐 ]2 order=2

Third order reaction, 𝟐𝐍𝐎 + 𝟐𝐇𝟐 → 𝐍𝟐 + 𝟐𝐇𝟐𝐎 r = k[𝐇𝟐 ][𝐍𝐎]2 order=1+2=3
Zero order reaction: A reaction in which rate is independent of concentration of reactants.

A⎯⎯→ B
𝑑[𝐴]
𝑟=− = 𝑘[𝐴]0 =k
𝑑𝑡
For example,

1. The thermal decomposition of HI on gold surface.

𝐴𝑢 0
2HI(g) →⎯⎯ H2(g) + I2(g) 𝑟 = 𝑘[𝐻𝐼] =k

2. Decomposition of ammonia in presence of molybdenum or tungsten.

Pt
2NH3(g) →⎯ N2(g) + 3H2(g)
At high p, the metal surface gets saturated with gas molecules. So, a further change in reaction conditions is
unable to alter the amount of ammonia on the surface of the catalyst making rate of the reaction
independent of its concentration.
3. The photochemical reaction between hydrogen and chlorine.
hv
H2(g) + Cl2(g) →⎯⎯ 2HCl(g)
 CHEMICAL KINETICS DR. KAVITHA C N

Pseudo–first order reactions:

Reactions which are not truly of the first order but under certain conditions reactions become that of first order are
called pseudo unimolecular reaction.

For example: 1. Hydrolysis of ester in presence of acid

CH3COOC2H5 + H2O → CH3COOH + C2H5OH

r = k [CH3COOC2H5] [H2O]

Since, hydrolysis takes place in the excess of H2O and change in concentration of H2O is negligible.

Practically, [H2O] =constant.

r = k’ [CH3COOC2H5] Where k’ = k [H2O].

The reaction is actually second-order but in practice it is found to be first-order. Thus, it is a pseudo-first order
reaction.

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

Molecularity of a reaction
The molecularity of an elementary reaction is the number of reactant molecules involved in a reaction.

(a) Unimolecular reactions: (molecularity = 1)

𝐁𝐫𝟐 → 𝟐𝐁𝐫

(b) Bimolecular reactions: (molecularity = 2)

𝐂𝐇𝟑 𝐂𝐎𝐎𝐂𝟐 𝐇𝟓 + 𝐇𝟐 𝐎 → 𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 + 𝐂𝟐 𝐇𝟓 𝐎𝐇

𝐇𝟐 + 𝐈𝟐 → 𝟐𝐇𝐈

(c) Termolecular reactions: (molecularity = 3)

𝟐𝐍𝐎 + 𝐎𝟐 → 𝟐𝐍𝐎𝟐
𝟐𝐍𝐎 + 𝐂𝐥𝟐 → 𝟐𝐍𝐎𝐂𝐥

The probability that more than three molecules can collide and react simultaneously is very small. Hence,
reactions with the molecularity three are very rare and slow to proceed. It is, therefore, evident that
complex reactions involving more than three molecules in the stoichiometric equation must take place in
more than one step.
 CHEMICAL KINETICS DR. KAVITHA C N

Molecularity of Reaction Order of Reaction

It is the number of atoms or molecules involved in a It is the sum of powers of the concentration terms
chemical reaction. in the rate law equation.

Molecularity of reaction is always a whole number. Order of reaction may be whole number or fraction
It cannot be zero. or zero.

It is calculated from stochiometric /balanced It is determined experimentally.

equation.

molecularity is applicable only for elementary Order of reaction is for overall reaction. It is
reactions. molecularity of complex reaction has no applicable to elementary as well as complex
significance. reactions

Order of a reaction & units of rate Constant:

The units of rate constant for a given reaction can be determined by starting with the appropriate rate
equation for the reaction.
For a nth order reaction- A → Product
𝑑[𝐴]
𝑟=− = 𝑘[𝐴]𝑛
𝑑𝑡
1 𝑑[𝐴]
𝑘=−
[𝐴]𝑛 𝑑𝑡
1 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
=−
[𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛]𝑛 𝑡𝑖𝑚𝑒

conc= mol L-1 or mol dm-3 and Time = min or s

 CHEMICAL KINETICS DR. KAVITHA C N

Expression for the rate constant for second order reaction (a = b)

Consider a second order reaction, when both the reactants are same.

A+A ⎯⎯→ p
2A ⎯⎯→ P
let the initial concentration of A is a mol dm-3. After time t, if x mol dm-3 of A react to form of product. Then
the concentration of A will be (a – x).

The differential rate expression of the reaction

𝑑𝑥
∝ [𝐴]2
𝑑𝑡
𝑑𝑥
= 𝑘[𝐴]2
𝑑𝑡
where, k is rate constant or velocity constant
𝑑𝑥
= 𝑘(𝑎 − 𝑥)2
𝑑𝑡
𝑑𝑥
∫ = ∫ 𝑘𝑑𝑡
(𝑎 − 𝑥)2
1
= 𝑘𝑡 + 𝑐 − − − (1)
(𝑎 − 𝑥)
where, C is integration constant
1
when t = 0 and x=0 in equation (1) c=
𝑎
Substituting this value in equation (1)
1 1
= 𝑘𝑡 +
(𝑎 − 𝑥) 𝑎
1 1
− = 𝑘𝑡
(𝑎 − 𝑥) 𝑎
𝑎 − (𝑎 − 𝑥)
𝑘𝑡 =
𝑎(𝑎 − 𝑥)

𝑎−𝑎+𝑥
𝑘𝑡 =
𝑎(𝑎 − 𝑥)
 CHEMICAL KINETICS DR. KAVITHA C N

𝑥
𝑘𝑡 =
𝑎(𝑎 − 𝑥)
1 𝑥
𝑘= [ ]
𝑡 𝑎(𝑎 − 𝑥)
Expression for the rate constant for second order reaction when the reactants are different (a ≠ b)
A+B P

2.303 𝑏(𝑎 − 𝑥)
𝑘= [𝑙𝑜𝑔 ]
𝑡(𝑎 − 𝑏) 𝑎(𝑏 − 𝑥)

Half-life time of a reaction (t1/2):

The half-life of a reaction is the time required for the reaction to be half completed.
Or
The time in which the concentration of a reactant is reduced to one half of its initial concentration.
𝑥
𝑘𝑡 = [ ]
𝑎(𝑎 − 𝑥)
1 𝑥
𝑡= [ ]
𝑘 𝑎(𝑎 − 𝑥)
When t=t1/2, a=a/2
𝑎
1 2
𝑡1/2 = [ ]
𝑘 𝑎(𝑎 − 𝑎)
2
𝑎
1 2
𝑡1/2 = [ 𝑎 ]
𝑘 𝑎( )
2
1
𝑡1/2 =
𝑘𝑎
1
𝑡1/2 
𝑎
Half –life time of a second order reaction is inversely proportional to the initial concentration of the
reactant.