PRACTICAL # 3

Objective: To study the Polymerization of Styrene by Dilatometer.

Chemical:
● Monomer (styrene)
● Initiator (AZDN)

Equipment:
● Dilatometer
● Cathetometer

Theory:

Dilatometry is a thermo-analytical method for measuring the shrinkage or expansion of

materials over a controlled temperature regime.
Cathetometer is used to measure very small change in meniscus.

The conversion (X) of the monomer is directly proportional to the change in volume of the
reaction mixture, according to equation 𝑋 = 100 𝑋(𝑋𝑋 −h)/ΔV*Vₒ
Where,
● ΔV is the relative shrinkage for complete polymerization (0<ΔV<1)
● V0 is the volume of the reaction mixture at time t = 0 (cm3)
● a is the slope of the dilatometer calibration curve (a<0)
● h0 is the dilatometer scale reading at time t = 0
● h is the dilatometer scale reading at time t.

Procedure:

Take 4.4972 cm³ styrene monomer in dilatometer of capillary 1mm dia. And add initiator of
3.87 *10ˉ³ mol/l. Put dilatometer in oil bath and maintain 90°C. With time, height of liquid
in dilatometer decreases as polymerization starts but this shrinkage is so minor that’s why
we are using cathetometer to measure this. Finally place this assembly in oven at 70°C as
the result monomer evaporates and remaining is polymer (polystyrene).

Observation:

a = slope of calibration curve of dilatometer.

a = -2

The relative shrinkage for complete polymerization (ΔV) is dependent on the temperature.

T (°C) ΔV (%)
60 17
80 18.37
90 20
So, ΔV = 0.0031T²-0.3725T+28.01

And T= 90°C

ΔV = 19.595%

ΔV = 0.19595 cm³

Time (min) h(mm) h(cm) hₒ -h (cm) X(%)

0 0 0 0 0
5 0.1 0.01 -0.01 2.269
10 1 0.1 -0.1 22.695
20 3.4 0.34 -0.34 77.16
30 4.9 0.49 -0.49 111.2
40 6.9 0.69 -0.69 156.599
50 8.5 0.85 -0.085 192.912
60 10.1 1.01 -1.01 229.22
70 11.7 1.17 -1.17 265.53
Graph:

Conclusion:
In the beginning there is no conversion as initially monomer and initiator needs some
indention time. After 4-5 min conversion starts. As time increases conversion also
increases.