Evidences of Nonideal Mixing in Poly(ethylene Glycol)/Organic Solvent Mixtures by Brillouin Scattering

Abstract

The concentration dependence of the hypersonic properties of solutions of poly(ethylene glycol) of mean molecular mass 600 g/mol (PEG600) in benzene and toluene has been investigated by Brillouin scattering. The two solvents are very similar in structure and chemical properties, but while benzene is nonpolar, toluene possess a modest dipole. In both solvents a high-frequency relaxation process has been observed at high concentrations which has been assigned to conformational rearrangements of the polymeric chains, triggered by reorientation of the side groups. In both cases, the concentration dependence of the adiabatic compressibility deviates significantly from linearity, indicating the existence of nonideal mixing phenomena driven by aggregation processes taking place in the systems. However, there is no temperature dependence for solutions of PEG600 in benzene; on the contrary, the results obtained for solutions of PEG600 in toluene are noticeably dependent on the temperature. The comparison of the experimental data with the results of previous experiments on similar systems allows a general picture for weakly interacting mixtures of hydrogen-bonded systems and organic solvents to be developed. In particular, in the presence of a nonpolar solvent molecule the local structure of the mixture is dominated by solute self-association processes and any resulting solute-solvent correlation is barely induced by excluded volume effects. At high enough dilution the self-aggregation of solute molecules produces a variety of new local topologies that cannot be observed in bulk solute, and as a consequence, the concentration evolution of the system is too rich to be described in terms of a linear combination of a few components over the whole concentration range. The situation seems to be simpler for the polar toluene solvent molecules, where a three-component model seems able to fit the experimental concentration dependence of the hypersonic velocity. This result is interpreted to imply that the interaction between the solvent dipoles and the active sites of the solute produces a relatively stable heterocoordination, while the relevance of self-association is partially reduced.