Chp 3 Practice Questions

1) Write down the reaction scheme for polymerization of styrene (CH 2=CHPh) intiated by
thermolysis of azobisisobutyronitrile (AIBN) including both combination and disproportionation
as possible modes of termination.
A sample of polystyrene prepared by bulk polymerization at 60°C using radioactive (14C) AIBN
as initiator, was found to have Mn = 1000 kg/mol and a radioactivity of 6x103 counts s-1g-1
(measured using a liquid-scintillation counter). Given that AIBN has a radioactivity of 6x109
counts s-1mol-1, determine the mode of termination which operated in the preparation of
polystyrene sample.

2) In a free radical polymerization rxn, what would be the effect of (a) increasing [M] 0 4 times at
constant [I]0 and (b)increasing [I]0 4 times at constant [M]0 upon:

(i) the total radical concentration at steady-state

(ii) the rate of polymerization
(iii) the number average degree of polymerization

3) Methyl methacrylate was polymerized at a mass concentration of 200 g dm -3 in toluene using

AIBN as initiator at a mass concentration of 1.64x10-2 g dm-3 and a reaction temperature of 60°C.
Calculate the initial rate of polymerization and the molar mass of poly(methyl methacrylate)
formed in the initial stages of the reaction given that the relevant rate constants at 60°C are:

Assume f=0.7, termination by combination is negligible and the density of the initial methyl
methacrylate in toluene is 860 g/dm3.

(i) initiator dissociation, kd = 8.5x10-6 s-1

(ii) propagation, kp = 367 dm3mol-1 s-1
(iii) termination, kt = 9.3x106 dm3mol-1 s-1
(iv) transfer to monomer, ktr M = 3.93x10-3 dm3mol-1 s-1
(v) transfer to solvent, ktr S = 7.34x10-3 dm3mol-1 s-1

4) Assuming that in free-radical polymerization the rate constants can be replaced by the
appropriate Arrhenius expressions. Calculate the changes in the rate of polymerization and the
degree of polymerization caused by increasing the temperature of polymerization of styrene in
benzene initiated by AIBN from 60°C to 70°C given that:

Ep = 34 kJ/mol
Et = 10 kJ/mol
Ed = 126 kJ/mol
Assume that the concentration of monomer and initiator and f remain unchanged when the
temperature is increased.