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In our previous report, an empirical partition function,for polyethylene ( PE ) was determined based on a pressure ( P V) – temperature ( T V) – volume ( V ) – entropy ( S V) equation of state where the variables,  P V,  T Vand  S V, were isochoric variables with  V  = const. evaluated by using the experimental  P-V-T  data and the isobaric heat capacity,  C P,  at 1 atm. In this work we describe the proposal of a modified, reformed partition function of the Debye model,where theis expressed by the summation of the terms of  T ,  T−1  and  T3  and the Boltzmann factors offor  i  = 1, 2, 3 and 6. The modified reformed pressure,at constant volume calculated based on theshowed that the Boltzmann factors,for  i  = 3 and 6 were dominant and increased with increasing temperature and theterms were negative and decreased with increasing temperature, while the modified reformed entropy,showed that the Boltzmann factors offor  i  = 3 and 6 were also dominant and increased with increasing temperature and theterm increased rapidly over a higher temperature range. All Boltzmann factors offor  i  = 1, 2, 3 and 6 in the modified reformed isochoric heat capacity,  C V,m-RD, calculated based on thewere positive, which was different from that in the previous work where one negative Boltzmann factor was observed.

journal of macromolecular science, part b

Empirical Determination of the Partition Function of Polyethylene Based on Its Pressure-Volume-Temperature-Entropy Isochoric Equation of State. II. The Pressure and Entropy Expressed by the Modified Partition Function