Abstract
The entropy of melting ΔSm is divided into three parts according to Starkweather and Boyd: the entropy change due to disordering of molecular arrangements ΔSdis at constant volume, the change of chain conformations ΔSc and the entropy arising from the change of volume of ΔSv. ΔSv was evaluated from the experimental results on the P–V–T relations for linear polyethylene and eicosane, where the volume dependence of the value of (∂S/∂V)T=(∂P/∂T)V is taken into consideration. ΔSdis was estimated with the aid of the thermodynamic data for simple spherical molecules such as Ar and CCl4. As results the conformational entropy of melting ΔSc was obtained as 1.51 cal/CH2 mol deg for polyethylene and 1.94 cal/CH2 mol deg for eicosane, which are in good agreement with the theoretical predictions of several authors.
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Tsujita, Y., Nose, T. & Hata, T. Thermodynamic Properties of Polyethylene and Eicosane. II. Conformational Entropy of Melting. Polym J 3, 587–590 (1972). https://doi.org/10.1295/polymj.3.587
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DOI: https://doi.org/10.1295/polymj.3.587
