Dielectric relaxation of polychlorinated biphenyl/toluene mixtures: component dynamics.

The dynamics of homogenous polychlorinated biphenyl (PCB54)/toluene mixtures have been investigated by means of broadband dielectric spectroscopy. The mixture presents dynamical heterogeneity, alike miscible polymer blends, which is manifested with the presence of two relaxational processes. The relatively slow one has been attributed to the motion of PCB54 in the mixture, whereas the relatively fast one was related to the toluene dynamics in the mixture. These results have been interpreted according to the self-concentration concept, first introduced to describe the dynamics of miscible polymer blends, which relies on the limited size of the cooperative length scale in glass-forming liquids. The self-concentration concept has been incorporated in the Adam-Gibbs theory of the glass transition relating the characteristic relaxation time and the length scale for structural relaxation to the configurational entropy. This allowed the determination of the cooperative length scale of PCB54 and toluene both in mixture and alone through the fitting of a single parameter, namely, that connecting the cooperative length scale to the configurational entropy. This length scale resulted to be in the range of 1-2 nm for all systems. Finally, the out-of-equilibrium dynamics of toluene induced by the selective freezing in of PCB54 has been examined and its relation to the Johari-Goldstein relaxation of pure toluene was critically discussed.