Determining vibrational heat capacity and thermal expansivity and their change at glass-liquid transition

The vibrational parts of a liquid's heat capacity Cp and thermal expansion coefficient alpha may be determined from dynamic measurements. The Cp data for Pd40Ni40P20 and 0.4 Ca(NO3)(2).0.6 KNO3 have been analyzed accordingly, and it is found that change in the vibrational part at liquid-glass transformation is negligible. Analysis for alpha of poly(styrene) leads to the same conclusion. There is no discontinuity in the vibrational parts of Cp and alpha on structural unfreezing in the Tg range, and hence the change in Cp and alpha at Tg is almost entirely due to change in the configurational part. Crystallization decreases the vibrational part not because the molecular mobility is lost but because the density increases.