Journal of Chemical Physics p. 3460 - 3466 (1980)
Update date:2022-08-24
Topics:
Desando, M. A.
Walker, S.
Baarschers, W.H.
Dielectric absorption studies have been made of a number of aromatic sulfides, sulfoxides, and sulfones in a polystyrene matrix at a variety of temperatures in the frequency range of 102-105 Hz, and in three cases between 104-107 Hz.One compound, bis (4-pyridyl) sulfide, was also examined as a pure compressed solid in the frequency range of 104-107 Hz.The Eyring parameters have been determined and used to characterize the relaxation processes.Low enthalpies of activation (ca.15 kJ mol-1) have been estimated for an intramolecular relaxation process of diphenyl, bis (4-tolyl) and bis (4-pyridyl) sulfide, and rotation about the C-S bond in these symmetrical aromatic sulfides would, thus, be expected to occur quite readily.These low barriers are to be contrasted with those for the molecular relaxation values of 60-78 kJ mol-1 for diphenyl, bis(4-tolyl) and bis(4-chlorophenyl) sulfoxides and sulfones.The enthalpies of activation (ca.39 kJ mol-1) for the molecular relaxation of the disklike molecules, dibenzothiophene and its oxides, are also lower than those for the corresponding nonplanar diphenyl sulfur oxides.
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