Calorimetric versus kinetic glass transitions in viscous monohydroxy alcohols

An extensive comparison of calorimetric and dielectric measurements is carried out for generic molecular liquids and monohydroxy alcohols with focus on the identification of the dielectric modes which are associated with the glass transition. For generic liquids, the calorimetric glass transition temperatures (Tg-cal) are always greater than their kinetic counterparts (Tg-kin), but the difference remains below 3 K. Also, the nonexponentiality parameters of the Tool-Narayanaswamy-Moynihan-Hodge model applied to the calorimetric data and the stretching exponents of the dielectric measurements show remarkable agreement. The same behavior is found for glass-forming monohydroxy alcohols, provided that the faster and smaller non-Debye relaxation rather than the large dielectric Debye process is assigned to the structural relaxation. The study emphasizes that the dielectric signature of the glass transition in monohydroxy alcohols is a dispersive loss peak that is faster and significantly smaller than the prominent Debye feature.