Conventional methods fail to measure cp (omega) of glass-forming liquids.
The specific heat is frequency dependent in highly viscous liquids. By solving the full one-dimensional thermoviscoelastic problem analytically it is shown that, because of thermal expansion and the fact that mechanical stresses relax on the same time scale as the enthalpy relaxes, the plane thermal-wave method does not measure the isobaric frequency-dependent specific heat c{p}(omega) . This method rather measures a "longitudinal" frequency-dependent specific heat, a quantity defined and detailed here that is in between c{p}(omega) and c{V}(omega) . This result means that no reliable wide-frequency measurements of c{p}(omega) on liquids approaching the calorimetric glass transition exist. We briefly discuss consequences for experiment.
Christensen
Tage
T
DNRF centre Glass and Time, IMFUFA, Department of Sciences, Roskilde University, Postbox 260, DK-4000 Roskilde, Denmark.
Olsen
Niels Boye
NB
Dyre
Jeppe C
JC