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56 Polystyrene

consuming they usually are not used for routine measure-

ments. The viscosity of a solution of polystyrene provides a

simple and rapid method for estimating molecular weights.

Relative viscosity, nreU is the ratio of the times for solution

and solvent to flow through a capillary. This value minus one,

divided by the concentration (in g/100 ml) is the specific

viscosity, nsp. If specific viscosity is measured for several con-

centrations and extrapolated to zero concentration, intrinsic

viscosity [rj]0 is obtained; the relationship of intrinsic viscosity

to molecular weight can be expressed [??]„ = KMa. The

values of K and a vary for different solvents. In a poor solvent

such as methyl ethyl ketone the polymer molecules have a

tendency to coil up; in a good solvent such as benzene they

are less coiled and appear to be longer.

Constants can be determined by measuring the intrinsic

viscosity and the weight average or number average molecular

weights of polystyrene samples having a wide range of aver-

age molecular weights. These may be unfractionated samples

prepared either at different temperatures or with different

initiator concentrations in order to obtain different molecular

weights. Fractions with different molecular weights of more

narrow distribution also may be obtained from a single sam-

ple by fractional precipitation.

The constant a may vary from 0.5 in a very poor solvent

to a maximum of 0.8 in a good solvent where the chains are

coiled at random. Some typical values are given below for

fractionated and unfractionated samples:

Table 3.1. Constants for Polystyrene Solutions



Fractions a

Benzene, 30°C



Unfractionated a
Generated on 2013-04-10 17:11 GMT /

Benzene, 30°C

Public Domain, Google-digitized /


Fractions a

Methyl ethyl ketone, 30°C



Fractions b

Methyl ethyl ketone, 25 °C



» Osmotic pressure.

b Light scattering.