Osmotic and small-angle X-ray and neutron scattering (SAXS and SANS) m
easurements are reported for poly(vinyl acetate)-toluene solutions and
gels containing a controlled amount of free poly(vinyl acetate) (PVAc
) chains. The thermodynamic response of the gel was found to differ si
gnificantly from that of the corresponding polymer solution. This devi
ation is interpreted in terms of a reduction in the volume fraction of
the network polymer participating in the thermodynamic concentration
fluctuations. No significant difference was detected in the thermodyna
mic properties of PVAc gels containing different amounts of free PVAc
chains. The radius of gyration of the free chains trapped in the swoll
en network, determined by SANS, was found to be significantly smaller
than their unperturbed dimension. The observed chain contraction is co
nsistent with predictions of the theory of random media.