Chain Reactions: Nikolai Nikolaevic Semenov 1896-1986, Nobel 1956

Lecture 18
Chain reactions
Nikolai Nikolaevic Semenov

1896-1986, Nobel 1956
Chain reactions are examples of complex reactions, with complex rate

expressions.
In a chain reaction, the intermediate produced in one step generates an
intermediate in another step.
This process goes on.
Intermediates are called chain carriers. Sometimes, the chain carriers
are radicals, they can be ions as well. In nuclear fission they are
neutrons.
There are several steps in a chain reaction.

1. Chain initiation
This can be by thermolysis (heating) or photolysis (absorption of light)
leading to the breakage of a bond.
CH3CH3 2.CH3
2. Propagation
In this the chain carrier makes another carrier.
CH3 + CH3CH3 CH4 + CH2CH3
3. Branching
One carrier makes more than one carrier.
O + H2O HO + HO
(oxygen has two unpaired electrons)
4. Retardation
Chain carrier may react with a product reducing the rate of formation
of the product.
H + HBr H2 + Br
Retardation makes another chain carrier, but the product concentration
is reduced.
5. Chain termination
Radicals combine and the chain carriers are lost.
CH3CH2. + CH3CH2 CH3CH2CH2CH3
6. Inhibition
Chain carriers are removed by other processes, other than termination,
say by foreign radicals.
CH3CH2 + R CH3CH2R
All need not be there for a given reaction.
Minimum necessary are,
Initiation, propagation and termination.
How do we account for the rate of laws of chain reactions?

Look at the thermal decomposition of acetaldehyde. This appears to
follow three-halves order in acetaldehyde.
Overall reaction,
CH3CHO(g) CH4(g) + CO(g) d[CH4]/dt = k[CH3CHO]3/2
The mechanism for this reaction known as Rice-Herzfeld
is as follows.
Product
(a) Initiation:
(b) Propagation:
(c) Propagation:
(d) Termination:
CH3CHO CH3 + CHO

CH3CHO + CH3 CH4 + CH3CO
CH3CO CH3 + CO
CH3 + CH3 CH3CH3
mechanism
R = ka [CH3CHO]
R = kb [CH3CHO] [CH3]
R = kc [CH3CO]
R = kd [CH3]2
Although the mechanism explains the principal products, there are

several minor products such as acetone (CH3COCH3) and propanal
(CH3CH2CHO).
The rate equation can be derived on the basis of steady-state
approximation. The rate of change of intermediates may be set equal to
zero.
d[CH3]/dt = ka[CH3CHO] kb[CH3][CH3CHO] + kc[CH3CO]
-2kd[CH3]2 = 0
d[CH3CO]/dt = kb[CH3][CH3CHO] kc[CH3CO] = 0
The sum of the two equation is,

ka[CH3CHO] 2kd[CH3]2 = 0
The steady-state concentration of CH3 radicals is,
[CH3] = (ka/2kd)1/2 [CH3CHO]1/2
If follows that the rate of formation of CH4 is
d[CH4]/dt = kb[CH3][CH3CHO] = kb (ka/2kd)1/2 [CH3CHO]3/2
Thus the mechanism explains the observed rate expression. It is sure that
the true rate law is more complicated than that observed experimentally.
There are several cases where the reaction is complicated.
An example is,
H2(g) + Br2(g) 2HBr(g) d[HBr]/dt = k[H2][Br2]3/2
{[Br2] + k[HBr]}
The following mechanism has been proposed to account for this rate law.
(a) Initiation: Br2 + M Br + Br + M R = ka[Br2][M]
where M is either Br2 or H2.
(b) Propagation: Br + H2 HBr + H
R = kb[Br][H2]
H + Br2 HBr + Br R = kb[H][Br2]
(c) Retardation: H + HBr H2 + Br R = kc[H][HBr]
(d) Termination: Br + Br + M Br2 + M* R = kd[Br]2 [M]
The third body collision removes the excess energy.
There can be other recombinations also, such as H. + H. and H. + Br..

The net rate of formation of HBr is,
d[HBr]/dt = kb[Br][H2] + kb[H][Br2] kc[H][HBr]
We can apply stead state.
d[H]/dt = kb[Br][H2] - kb[H][Br2] - kc[H][HBr] = 0
d[Br]/dt = 2ka[Br2][M] kb[Br][H2] + kb[H][Br2] + kc[H][HBr]
-2kd[Br]2 [M] = 0
[Br] = (ka/kd)1/2 [Br2]1/2
[H] = kb(ka/kd)1/2 [H2][Br2]1/2/{kb[Br2] + kc[HBr]}
Substitute in the HBr rate law.

d[HBr]/dt = 2kb(ka/kd)1/2[H2][Br2]3/2/{[Br2] + (kc/kb)[HBr]}
If it is compared with the experimental rate law one can see,
k = 2kb(ka/kd)1/2 k = kc/kb
Presence of HBr in the denominator indicates that it is an inhibitor.
Presence of Br2 in the denominator is because of the fact that its
presence removes reactive radicals from the chain mechanism.
If we plot HBr concentration as a function of time, it will reach a
maximum as increased presence of HBr will retard the reaction.
R
[HBr]
Explosions
There are two kinds: thermal and chain-branching.
Thermal: This is because in an exothermic reaction if the energy
cannot escape, the reaction rate increases fast due to concentration
of energy.
Chain-branching: In this case, there are chain branching reactions
and the number of carriers grows exponentially.
An example of the latter type,
2H2(g) + O2(g) 2H2O(g)
The mechanism is very complex. Yet there are these steps, which
explain explosion.
Initiation: H2 + O2 OH + OH
H2 + OH H + H2O
O2 + H O + OH (branching)
O + H2 OH + H (branching)
H + O2 + M HO2 + M*
Propagation:
The explosions depend on temperature and pressure.

This is explained in the figure below
Regions of explosion
At low pressures the chain carriers can reach the walls and get lost.
No explosion happens. As the pressure is increased along the
dotted line shown, the radicals react before reaching the walls and
the reaction suddenly becomes explosive. This is the first explosion
limit. In the second explosion limit, the pressure of the products is
high so that reactions of the type, O2 + H. .O2H occur. These
recombination reactions become efficient as the excess energy
can be removed by three body collisions. Then the reaction goes
smoothly. In the third explosion limit, thermal explosion occur.
In this limit, reaction such as HO2. + H2 H2O2 + H.
dominates the elimination of HO2. by the walls.

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Lecture 18

Nikolai Nikolaevic Semenov

Chain reactions are examples of complex reactions, with complex rate

There are several steps in a chain reaction.

How do we account for the rate of laws of chain reactions?

CH3CHO CH3 + CHO

Although the mechanism explains the principal products, there are

The sum of the two equation is,

There can be other recombinations also, such as H. + H. and H. + Br..

Substitute in the HBr rate law.

The explosions depend on temperature and pressure.

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