AbstractThe residual entropy of amorphous polyethylene (PE) at 0 K is discussed within the framework of the heat capacity (Cp). The measured Cp of the liquid was extended from the glass transition to low temperature by separately finding its three parts—the vibrational, conformational, and external contributions—and extrapolating each to low temperature. The vibrational Cp was calculated from the frequency distributions of the group vibrations on the basis of force constants obtained from experimental infrared and Raman spectra as well as the skeletal vibrations in the amorphous solid (glass) obtained from fitting of the appropriate experimental Cp to Debye functions in the form suggested by Tarasov. The conformational part of Cp was evaluated from a fit of the heat capacity of the liquid, decreased by the contributions of the vibrational and external parts, to a one‐dimensional Ising model that can be extrapolated to 0 K and requires two discrete states described by stiffness, cooperativity, and a degeneracy parameter. The external part was computed from the experimental data for expansivity and compressibility, fitted to an empirical equation of state, and modified at low temperatures in accordance with the Nernst–Lindemann approximation. The computed Cp of the liquid PE agreed with the experiment from 600 K to the beginning of the glass transition at about 260 K. Extending the heat capacity to 0 K, bypassing the freezing of the large‐amplitude conformational motion in the glass transition, led to a positive residual entropy and enthalpy and avoided the so‐called Kauzmann paradox. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1245–1253, 2002