Lecture 1 - Recap

 Definition & formation of free radicals

 Ex. of free radicals, radical cations & anions
 Utility of free radicals
 Harmful effects of free radicals
 How to eliminate free radicals from body
 Stability of free radicals
 Factors affecting stability of free radicals
 Activation Energy
Reaction rates are related to temperature by
the Arrhenius equation:

Kr = A e -Ea/ RT

Frequency Factor (A): Fraction of collisions

with proper orientation for reaction to occur.

Activation Energy (Ea ): Minimum kinetic

energy molecules must possess to overcome
repulsions between their electron clouds
when they collide.
 Activation Energy
• Dashed lines show energy needed to overcome
barriers of represented energies.
• Area under curve represents number of molecules
with enough energy to overcome barrier.
• At higher temperatures, more molecules have the
required energy.
 Activation Energy
• Minimum energy required to reach the
transition state.
• For e.g., in chlorination of methane,
structure of transition state for the
following propagating step is:
H
H C H Cl
H
 Reaction-Energy Diagrams
• For a one-step reaction:
reactants  transition state  products
Transition state ( ‡ ):
State of highest energy between reactants and
products, unstable, and cannot be isolated.
 Rate Determining step
 Reaction intermediates are stable as long
as they don’t collide with another
molecule or atom, but they are very
reactive.
 Transition states are at energy maxima.
 Intermediates are at energy minima.
 The reaction step with highest Ea will be
the slowest, therefore rate determining
for the entire reaction.
Rate determining step is also known as
rate limiting step.
 Energy Diagram for Multistep Reaction
Reactants  transition state 
intermediate  transition state 
product
Chain Propagation
. .
Cl + CH4 HCl + CH3
. .
CH3 + Cl2 CH3Cl + Cl
Temperature dependence of Halogenation
In a halogenation reaction the rate limiting step is:
X + CH4 HX + CH3
X Ea Rate @ 300K Rate @ 500K
F 1.2 kcal 140,000 300,000
Cl 4 kcal 1300 18,000
Br 18 kcal 9 x 10-8 0.015
I 34 kcal 2 x 10-19 2 x 10-9
 With increasing Ea, rate decreases.
 With increasing temperature, rate
increases.
 Fluorine reacts explosively.
 Chlorine reacts at a moderate rate.
 Bromine must be heated to react.
 Iodine does not react (detectably).
 Halogenation of Alkanes
Experimental observations

1. There is no reaction in the dark at room

temperature.

2. Reaction will occur at high temperature in

the dark.

3. Reaction occurs at low temperature in the

presence of UV light.
 Chlorination of Methane

The most effective wavelength is blue, which is

absorbed by chlorine gas.
 The relative amounts of the various products
depend on the proportion of the two reactants
used.
 Excess of the hydrocarbon CH3Cl
 Excess of chlorine CHCl3 and CCl4
Free-Radical Chain Reaction

(1) Initiation: generates a reactive intermediate.

(2) Propagation: the intermediate reacts with a
stable molecule to produce another reactive
intermediate (and a product molecule).
(3) Termination: side reactions that destroy
the reactive intermediate.
 Initiation Step
A chlorine molecule splits homolytically into
chlorine radicals
 Propagation Step (1)
The chlorine radical collides with a methane
molecule and abstracts a H, forming another free
radical and one of the products (HCl).
 Propagation Step (2)
The methyl free radical collides with another
chlorine molecule, producing the other product
(CH3Cl) and regenerating the chlorine radical.
 Termination Steps
 Collision of any two free radicals.
 Combination of free radical with
contaminant or collision with wall.
 Reaction with other halogens
The order of reactivity of methane
substitution with halogens,
fluorine > chlorine > bromine > iodine
The order of reactivity is based on the values
of Ea for the first step of chain propagation
and ΔHo for the entire chain propagation
Fluorination has a very low value for Eact in the
first propagating step and ΔHo is extremely
exothermic.
 Chlorination
Chain Initiation
H0 (kJ mol-1) Eact (kJ mol-1)
.
Cl2 2 Cl + 242 +243
Chain Propagation
. .
Cl + CH4 HCl + CH3 +8 + 16
. .
CH3 + Cl2 CH3Cl + Cl - 109 small
Overall H0 = - 101

Chlorination has higher value for Eact in the first

propagating step than flourination and ΔHo is less
exothermic than flourination.
 Higher values of Eact and lower overall ΔHo
values which makes the reactions less vigorous
 Hydrogen abstraction step in bromination has

a very high Eact (78 kJ/mol) in comparison to

chlorination (16 kJ/mol)
Iodination has a prohibitively high value for Eact
of the first propagating step and the reaction does
not .
Chlorination of Propane
 Product Distribution

 Typical product mix: 40% 1-chloropropane

and 60% 2-chloropropane.

 Therefore, not all H’s are equally reactive.

 To compare hydrogen reactivity, find

amount of product formed per hydrogen.
 Product Distribution
 40% 1-chloropropane from 6 hydrogens
and 60% 2-chloropropane from 2 hydrogens.

 40%  6 = 6.67% per primary H and

60%  2 = 30% per secondary H

 Secondary H’s are 30%  6.67% = 4.5

times more reactive toward chlorination
than primary H’s.
 Bromination of Propane
1 C
Br Br
heat
CH3 CH2 CH3 + Br2 CH2 CH2 CH3 + CH3 CH CH3
2 C 3% 97 %

 Bromination is more selective than chlorination.

 3%  6 = 0.5% per primary H and
97%  2 = 48.5% per secondary H
 Secondary H’s are 48.5%  0.5% = 97 times more
reactive than primary H’s.
 Bromination vs. Chlorination
 Chlorination is faster than bromination.

 Chlorination is unselective, yielding a

mixture of products, but bromination is often
selective, yielding one major product.

 This difference in chlorination and

bromination can be explained by considering
the energetics of each type of reaction.
Abstraction of a 10 or 20 hydrogen by Br• is
endothermic, but it takes less energy to form
the more stable 20 radical.
Bromination Energy Diagram
Abstraction of a 10 or 20 hydrogen by Cl• is
exothermic.
Chlorination Energy Diagram
 Hammond Postulate
 Related species that are similar in energy are also
similar in structure. The structure of a transition
state resembles the structure of the closest stable
species.

 Endothermic reaction: transition state is

product-like.
 Exothermic reaction: transition state is reactant-
like.
Endothermic reaction
Exothermic reaction
 Bromination vs. Chlorination
Bromination: The rate-determining step is
endothermic, the more stable radical is formed
faster, and often a single radical halogenation
product predominates.
Chlorination: The rate-determining step is
exothermic, the transition state resembles the
starting material, both radicals are formed, and a
mixture of products results.
FOR A GIVEN REACTION, THE MORE REACTIVE
THE LESS SELECTIVE
Allylic bromination
Allylic bond is weaker then any other sp3 hybridized
C-H bonds.
Comparison of bond strength

H 2C CH CH2 H → 364 kJ/mol or 87 kcal/mol

(H 3C)3C H → 381 kJ/mol or 91 kcal/mol
(H3C)2HC H → 397 kJ/mol or 95 kcal/mol

H3CH2C H → 410 kJ/mol or 98 kcal/mol

Allylic carbon can be selectively halogenated using
NBS(N-bromosuccinimide) in presence of light or
peroxides
Thus,

NBS
hv or ROOR, heat

Br
NBS
hv or ROOR, heat

Br
 Mechanism:
O O

Initiation: N Br
hv N. Br.

O O

Propagation:

H Br. CH. HBr (1)

CH. Br Br Br Br.

(2)
Generation of low concentration of Br2

O O

N Br H Br N H Br2

O O

Used in step 2 (Propagation)

Thus, an alkene with C-H bonds undergo two
different reactions depending on the reaction
conditions Br

Br 2 Br
CCl 4
h v N BS
or
RO
OR

Br
 Low concentration of bromine favours allylic
bromination