Abstract
AbstractAn expression for the free energy of a monodisperse polymer solution which incorporates volume changes upon mixing is obtained from a two‐component van der Waals model. When contributions to the thermodynamic quantities from the hard‐core interactions are neglected, expressions similar to those of Flory–Huggins–Debye for the spinodal and critical conditions are obtained. Partial molecular volumes instead of the pure molecular volumes appear in these expressions. The thermodynamic fluctuations of the system, which cause the Rayleigh and Brillouin light scatering, are also expressed in terms of the parameters of the polymer solution in a simple fashion. A limitation to the standard Debye procedure of associating the excess scattering to the solute concentration fluctuations is pointed out.
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