Heat capacities of solid polymers

The heat capacity of a solid polymer is governed by the manner in which the internal energy is distributed over the various degrees of freedom. If the internal energy manifests itself in harmonic oscillatory motions, the heat capacity is the sum of contributions of the normal modes of motion. In practice, full frequency data are not generally available for polymers. This paper proposes an empirical method for determining the heat capacities of linear high polymers by the addition of contributions from different chain segments. A survey of heat capacity data for 30 linear high polymers and several copolymer systems has revealed that additivity is usually valid for a temperature range from about 60°K to the glass-transition temperature. A table of heat capacity contributions of a number of polymer constituents is derived which permits the calculation of unknown heat capacities to an accuracy of ±5% or better. In addition, δCp data for the increase of the heat capacity at the glass-transition temperature were found to agree with the rule of constant heat capacity increase per mole of “bead” proposed 8 years ago.