Free radical polymerization is a process in which monomers undergo successive addition to

the free radical building block to form a polymer.

Polymerization of styrene (CH2=CHPh) initiated by thermolysis of azobisisobutyronitrile
(AIBN) follows the free radical polymerization mechanism involving initiation, propogation
and termination steps as shown below.
Initiation: Upon heating, azobisisobutyronitrile (AIBN) undergoes hemolytic cleavage to
produce two free radicals which will act as initiator.

Propagation: After the radical initiator is formed, it attacks a monomer. In a styrene monomer,
the electron pair in the pi bond is loosely held. The free radical uses its one electron and an
electron from pi bond to form a more stable sigma bond. This will result in formation of a
new radical and begins the polymer chain. This addition of new radical to the monomer
styrene molecule continues to form a polymer radical.

Once a chain is initiated, the chain propagates until all the monomer has been used up
completely or until chain termination occurs.
Termination: Chain termination is a process by which the polymer propagation step is
stopped. Chain termination can happen by any of the following modes.
Combination mode of termination- In this mode, two active chain ends simply couple to form
a long chain.

Disproportionation mode of termination- In this mode, a hydrogen atom from one chain end
is abstracted to another, producing a polymer with a terminal unsaturated group and a
polymer with a terminal saturated group.

The given data are;

Radioactivity of AIBN is

6 109 counts s 1mol 1

6 103 counts s 1g 1

Radioactivity of polystyrene sample is

To make a comparison between the radio activities of AIBN and polystyrene, convert the
counts s 1g 1
counts s 1mol 1
units of radioactivity of polystyrene from
to
, using its molar
1
1000 kg mol
mass, Mn average
.
Radioactivity of polystyrene is
1000 kg
6 103 counts s 1 g 1

1 mol

1000 g

9
1
1
6 10 counts s mol

1 kg

Radioactivity of polystyrene is same as that of the radical initiator, AIBN,

6 109 counts s 1mol1
.
As per the combination mode of termination, each polymer formed is having both the two
fragments formed during thermolysis of AIBN. One polymer molecule formed in this way is
stoichiometrically equivalent one AIBN molecule. So the radioactivity of the polymer formed
in this mode should be similar to that of AIBN.
As per the disproportionation mode of termination, each polymer formed is having one of the
two fragments formed during thermolysis of AIBN. Two polymer molecules formed in this
way are stoichiometrically equivalent one AIBN molecule. So the radioactivity of the
polymer formed in this mode should be half that of AIBN.
Since, radioactivity of polystyrene is same as that of the radical initiator, AIBN,
6 109 counts s 1mol1
, the mode of termination operated in the preparation of the
combination mode
polystyrene sample is
.