Chemical Kinetics Lecture - 6 7 July

Chemical Kinetics
LECTURE 6 Maastering…Half-life
Dr Monica Bedi
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Chemical Kinetics L-6
Half-life
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 as t1/2.
Half-life of zero order reaction
For a zero order reaction.
k= [R]0 - [R]
t
t1/2 for a zero order reaction is directly proportional to the initial

concentration of the reactants.
Half-life of first order reaction
For the first order reaction

2.303 [R]0
k= log
t R
[R]0
at t1/2 [R] =
2
So, the above equation becomes
2.303 [R]0
k= log
t1/2 [R]/2
2.303
Or t1/2 = log 2
k
2.303
t1/2 = ⨉ 0.301
k
0.693
t1/2 =
k
For a first order reaction, half-life period is constant, i.e., it is independent

of initial concentration of the reacting species.
For zero order reaction t1/2 ∝ [R]0. For first order reaction t1/2 is
independent of [R]0.
Half-life of zero order reaction
In general, for the reaction of nth order
Thus, it is clear from above that
i. For zero order reaction; t1/2 ∝ [A]0

ii. For first order reaction; t1/2 ∝ 1/[A]0
iii. For second order reaction; t1/2 ∝ 1/[A]0
iv. For third order reaction; t1/2 ∝ 1/[A]20
Can you crack it !
Calculate the half-life period of a first order reaction from their rate
constants given below
1. 200 s-1 2. 2 min-1
3. 5 year-1
Can you crack it !
The decomposition of a substance follows first order kinetics. If its

concentration is reduced to ⅛ of its initial value in 12 minutes, the rate
constant of the decomposition system is
A. min.-1 B. min.-1
C. min.-1 D. min.-1
Can you crack it !
The half-life for radioactive decay of 14C is 5730 years. An
archaeological artifact containing wood had only 80% of the 14C
found in a living tree. Estimate the age of the sample.
log 1.25 = 0.0969

Pseudo first order reactions
When a reaction of higher order under special conditions

follows first order kinetics then such reactions are called
pseudo first order reactions.
For a reaction
A + B ⟶ AB
If conc. Of B is large enough so that it does not change
appreciably during the reaction, then the rate will depend
only upon the conc. Of A it will follow the kinetics of first
order.
H+
Eg. CH3COOC2H5 + H2O CH3COOH + C2H5OH

Pseudo first order reactions
C12H22O11 + H 2O H+ C6H12O6 + C6H12O6

Cane sugar Glucose Fructose
Rate = k[C12H22O11]
Can you crack it !
During nuclear explosion, one of the products is 90Sr with half-

life of 28.1 years. If 1 𝛍g of 90Sr was absorbed in the bones of a
newly born baby insead of calcium, how much of it will remain
after 10 years and 60 years if it is not lost metabolically.
Can you crack it !
During nuclear explosion, one of the products is 90Sr with half-

life of 28.1 years. If 1 𝛍g of 90Sr was absorbed in the bones of a
newly born baby insead of calcium, how much of it will remain
after 10 years and 60 years if it is not lost metabolically.
Can you crack it !
The following data were obtained during the first order thermal
decomposition of N2O5(g) at constant volume
2N2O5(g) ⟶ 2N2O4(g) + O2(g)
S.No Time Total Pressure
1 0 0.5
2 100 0.512
Calculate rate constant

Can you crack it !
The following data were obtained during the first order thermal
decomposition of N2O5(g) at constant volume
2N2O5(g) ⟶ 2N2O4(g) + O2(g)
Can you crack it !
Can you crack it !
4.20 For the decomposition of azoisopropane to hexane and nitrogen

at 543 K, the following data are obtained.
t (sec) P(mm of Hg)
0 35.0
360 54.0
720 63.0
Calculate the rate constant.

Can you crack it !
t (sec) P(mm of Hg)
0 35.0
360 54.0
720 63.0
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Chemical Kinetics

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The half-life of a reaction is the time in which the concentration of a

For a zero order reaction.

t1/2 for a zero order reaction is directly proportional to the initial

For the first order reaction

So, the above equation becomes

For a first order reaction, half-life period is constant, i.e., it is independent

In general, for the reaction of nth order

Thus, it is clear from above that

i. For zero order reaction; t1/2 ∝ [A]0

1. 200 s-1 2. 2 min-1

The decomposition of a substance follows first order kinetics. If its

found in a living tree. Estimate the age of the sample.

log 1.25 = 0.0969

When a reaction of higher order under special conditions

Eg. CH3COOC2H5 + H2O CH3COOH + C2H5OH

C12H22O11 + H 2O H+ C6H12O6 + C6H12O6

During nuclear explosion, one of the products is 90Sr with half-

During nuclear explosion, one of the products is 90Sr with half-

S.No Time Total Pressure

Calculate rate constant

4.20 For the decomposition of azoisopropane to hexane and nitrogen

t (sec) P(mm of Hg)

Calculate the rate constant.

t (sec) P(mm of Hg)

Alcohol, Phenols &

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