Alkanes have only strong sigma bonds.

The electrons in the C-C and C-H sigma bonds

are shared equally by the bonding atoms.
So none of the atoms in an alkane has any significant charge. Therefore alkanes are
neither nucleophiles nor electrophiles.
Alkanes therefore are relatively unreactive compounds.

 Halogenation and combustion are the only reaction that alkanes undergo (without any metal
catalyst).

 When a bond breaks so that both of its electrons stay with one of the atoms, the
process is called heterolytic bond cleavage.
But when each of the atoms retain one of the bonding electrons the process is called
homolytic.
Homolysis results in the formation of radicals.
A radical is a species containing an atom with an unpaired electron.
A radical is highly reactive.

 Heat or light supplies energy

required to break the Cl-Cl bond.
The clorine radical than removes
a hydrogen atom from alkane,
forming HCl and methyl radical.
The methyl radical removes
Chlorine from Cl2, forming
choloro methane and another
chlorine radical.
This chlorine radical removes a
hydrogen atom from another
molecule of methane.
A propagation step is one that
propagates the chain.
Any two radicals in the reaction
mixture can combine to a
molecules molecule in which all
electrons are paired.
The combination of two radicals
is called a termination step
because it helps bring the
reaction to an end by decreasing
Radical Chain reaction
the number of radicals available
This particular one is called a radical substitution reaction.

 To maximize amount of
monohalogenated product,
a radical substitution
reaction should be carried
out in presence of excess
alkane.
Increases the probability
that halogen radical will
collide with a molecule of
alkane rather than with a
molecule of alkyl halide.
If halogen radical removes
a hydrogen from a
molecule of alkyl halide
rather than from a
molecule of alkane, a
dihalogenated product is
formed.

 Radicals are classified

according to the carbon
that bears the unpaired
electron.
Primary radicals have
unshared electrons on a
primary carbon.
Alkyl groups stabilize
radicals by
hyperconjugation.

 Stabilization of a
carbocation results from
overlap between filled
orbital of a C-H or C-C sigma
bond and an empty p
orbital.
Stabilization of a radical
results from overlap
between a filled orbital of a
C-H or C-C sigma bond and
a p orbital containing one
electron- a three electron
system.
Both electron are in bonding
MO in the two electron
system where as one goes
to antibonding MO in the
three electron system.

 Two different alkyl halides

are obtained from
monochlorination of
butane.

 Easier to remove a
hydrogen atom from a
secondary carbon to
form secondary radical
than it is to remove a
hydrogen atom from a
primary carbon to form
a primary radical.
The more stable the
radical the more easily
it is formed.

 Probability (the
number of hydrogen
that can be removed
that lead to the
formation of a
particular product) and
reactivity (the relative
rate at which a
particular radical is
formed) must be taken
into account when
determining the
relative amounts of the
products obtained from
the radical chlorination
of an alkane.

 Radical halogenation
of an alkane is a
useful reaction
because it is only
way to convert an
inert alkane into a
reactive compound.
Once halogen is
introduced it can be
replaced by a variety
of other substituents.

 The relative rates of

radical formation by
bromine radical is
different from the
relative rate of radical
formation by a chlorine
radical.
In this case the reativity
factor is more important
than the probability
factor.

 Why is the relative

rates of radical
formation different
when a bromine
radical rather than
a chlorine radical
is used as the
hydrogenremoving reagent?

 Bromination is
much slower than
chlorinaion.
The activation
energy for
removing a
hydrogen atom
by a bromine
radical is about
4.5 times greater
than that for
removing a
hydrogen atom
by a chlorine
radical.

Reativity-selectivity principle states that the greater the reactivity,

the less selective it will be.

The reation of a chlorine

radical with an alkane to
form primary, sec,
tertiary radical is
exothermic, the
transition state
resemble the reactants.
Bromine radical with an
alkane is endothermic,
so the transition
resembles the product.
Since there are
significant differences
between the product
radicals, there are
significant differences in
the activation energy.
Chlorine makes primary,
sec and tert radicals
with equal ease wheras
bromine radical has

 The fluorine radical

is the most reactive
of the halogen
radicals.
The iodine radical
is the least reactive
of the halogen
radicals.

 The addition of HBr to 1-butane forms 2-bromobutane, because the electrophile (H+) adds
to the sp2 carbon bonded to most hydrogen.
For 1-bromobutane, need to make bromine an electrophile.

 The weak O-O bond of the

peroxide readily breaks
homolytically in the presence
or heat to form alkoxy
radicals.
The alkoxy radical complets
its octet by removing a
hydrogen atom from HBr,
forming a bromine radical.
The bromine radical now
seeks electron to complete its
octet.
Combines with one electrons
of the pi bond to form C-Br.
The second electron of the pi
bond is the unpaired electron
in the resulting alkyl radical.
The alkyl radical removes a
hydrogen atom from another
molecule of HBr to produce a
molecule of the alkyl halide
product and another bromine

 For radical addition of HCl

the first propagation step is
exothermic and the second
is endothermic.
For HI, the first propagation
step is endothermic and
second is exothermic.
Only for radical addition of
HBr are both propagation
steps exothermic.
Termination steps are
always exothermic, because
only bond making occurs.
Therefore when both
propagation steps are
exothermic can propagation
complete successfully with
termition.