Determination of molecular weight by osmotic pressure method.
Osmotic pressure method is also called membrane osmometry. This method is widely used to determine the number average molecular weight of polymers. This method is based on the phenomenon of osmosis. If a pure solvent is separated from a solution through a semipermeable membrane, due to concentration (chemical potential) difference between the solvent and solution, the solvent will flow into the solution through semipermeable membrane. The pressure applied on the solution to completely stop the flow of solvent into it through semipermeable membrane is called osmotic pressure.
The theory of osmotic pressure also applies to a solution of polymers.
Ordinary solution obeys Van't Hoff equation i.e
π=cRT/M
Where π is osmotic pressure, c is concentration in mass per unit volume, R is gas constant, T is temperature and M is molar mass.
The polymer solution are non ideal. Taking into account their deviation and using thermodynamics, Memillian and Mayer modified van't Hoff equation for polymers as
π=cRT/Mₙ+ Bc²+Dc³
=> π/c=RT/Mₙ+Bc+Dc²
For dilute polymer solution concentration is small,thus
π/c=RT/Mₙ+Bc
If graph is plotted between π/c vs c ,we get a straight line having slope B and intercept RT/Mₙ.
π/c vs c. |
Thus Mₙ can be calculated.
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