화학공학소재연구정보센터
Macromolecules, Vol.34, No.18, 6450-6455, 2001
A critical study of the entropy-volume relation of chain molecules in the fluid state: Computer simulation of n-undecane and comparison with experimental PVT data
A conventional method of estimating conformational entropy change at the melting point of polymers has been set forth in Mandelkern's book. The entropy separation according to this method involves a hypothetical assumption that the volume of the isotropic fluid may be compressed to that of the solid state without affecting the configurational part of the entropy of molecules. In this work, we have extensively examined the volume dependence of thermal pressure coefficient gamma = (deltaP/deltaT)(V) = (deltaS/deltaV)(T) of n-undecane. Molecular dynamic simulations were performed using the software package Insight II/Discover. In the standard calculation, a cubic box containing 30 n-undecane molecules was used under the conventional periodic boundary conditions. The experimental observations were well reproduced by the MD simulation performed as above, and accordingly the gamma vs specific volume (v(sp)) relations derived from the simulation are favorably compared with those obtained from the experimental PVT data. The gamma values remain quite insensitive to v(sp) over a wide range at given temperatures. Values of the trans fraction were found to decrease with an increase in temperature, while they tend to remain quite insensitive to pressure (0-200 MPa). It was concluded on this basis that the aforementioned treatment of the volume change at the phase transition seems to be supported by the present analysis.