Prigogine-Defay ratio of glassy freezing scales with liquid fragility

Abstract: A detailed study of published experimental data for a variety of materials on the incremental variation of heat capacity, thermal expansion, and compressibility at glassy freezing reveals a striking dependence of the Prigogine-Defay ratio R on the fragility index m. At high m, R approaches values of ~1, the Ehrenfest expectation for 2nd order continuous phase transitions, while R reaches values > 20 for low fragilities. We explain this correlation by the degree of separation of the glassy freezing temperature from a hidden phase transition into an ideal low-temperature glass.