Abstract
The Helmholtz free energy, A, and the Gibbs free energy, G, of polyethylene (PE) were determined based on its empirical pressure–volume–temperature–entropy equation of state, P-V-T-S Eos, and the empirical partition function, which we reported previously. The PA-VA-TA-SA Eos for the iso-Helmholtz free energy, iso-A, was determined based on the P-V-T-S Eos where the pressure (PA), volume (VA), temperature (TA), and entropy (SA) satisfied the condition that A is constant. The PG-VG-TG-SG Eos for the G being constant was also determined based on the P-V-T-S Eos. The three-dimensional (3D) plots, 3D plot, with the three axes, x = TA, y = PA, z = VA expressed by the 3D (TA, PA, VA) and the 3D (TA, VA, SA) at constant A in PE were determined, where the iso-A processes were characterized assuming that the volume and the entropy in the iso-A process decreased with increasing pressure and temperature, while in the 3D (TG, PG, VG) and 3D (TG, VG, SG) plots at constant G in PE, the volume and the entropy in the iso-G process were increasing with increasing pressure and temperature. The empirical partition function for the Helmholtz free energy was expressed by the summation of the terms of T, T2, and TCitation4, the Boltzmann factors with i = 1, 2, 3, and 6 and
and the U(V,T = 0 K) term for the zero Kelvin internal energy where the T4 term and the Boltzmann factors
with i = 6 and 3 were dominant negative factors in the A-T relation at the constant V = 1.04 cm3/g. In case of the Gibbs free energy where the partition function was expressed by the summation of the terms of T, T2, and TCitation4, the Boltzmann factors
with i = 1, 2, 3, and 6, the U(V,T = 0 K) term, PV and PV(T = 0) terms, the T2 term and the Boltzmann factors
with i = 6 and 3 were dominant negative factors in the G-T relation at 1 atm (1.01 × 10−4 GPa), while at high pressure, 1.0 GPa, the PV and PV(T = 0) terms were dominant positive factors.