Kauzmann's paradox and the glass transition

Biophys Chem. 2003 Sep;105(2-3):411-20. doi: 10.1016/s0301-4622(03)00105-4.

Abstract

Kauzmann showed that the entropy of a liquid decreases rapidly on cooling towards the kinetic glass transition temperature and extrapolates to unreasonable values at lower temperature. The temperature where the extrapolated liquid entropy meets the crystal entropy is now called the Kauzmann temperature. Thermodynamics, with Planck's statement of the third law, shows that the entropy of a liquid cannot be less than the entropy of a glass with the same enthalpy. This is the thermodynamic condition violated by the Kauzmann extrapolation and it suggests a thermodynamic glass transition. Simulations show that, for the simple models studied and regardless of how the liquid entropy is extrapolated, the Kauzmann temperature cannot be reached because the entropy of glasses with the same enthalpy as the liquid is greater than that of the crystal.

MeSH terms

  • Crystallization
  • Phase Transition
  • Temperature
  • Thermodynamics*
  • Water / chemistry*

Substances

  • Water