AN EQUATION OF STATE THEORY FOR HYDROGEN-BONDING POLYMER MIXTURES

被引:23
作者
GRAF, JF [1 ]
COLEMAN, MM [1 ]
PAINTER, PC [1 ]
机构
[1] PENN STATE UNIV,DEPT MAT SCI & ENGN,UNIVERSITY PK,PA 16802
关键词
D O I
10.1021/j100170a061
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A molecular theory of hydrogen-bonded liquid mixtures based on a lattice model description of a fluid is formulated. Equilibrium constants are used to give a prior knowledge of the mixture's equilibrium distribution of hydrogen-bonded states before and after mixing. These equilibrium constants reflect the changes in enthalpy and entropy corresponding to the formation of the various types of hydrogen bonds that may be present and are determined independently by using infrared spectroscopic measurements. Weak polar and dispersive type interactions between the molecular species are contained in an interaction chi-parameter which is estimated by using a group contribution method. Compressibility effects are incorporated into the model by allowing a number of lattice sites to remain vacant and act as free volume. The derived free energy expression consists of four contributions: (1) A combinatorial entropy term for mixing the molecules in the hard-core state with no hydrogen bonding. (2) The lattice energy and pressure-volume term. (3) The entropic contribution of mixing free volume with the hard-core system. (4) The free energy contribution from hydrogen bonding. Using experimental data reported in previous studies, it is found that this equation of state model does not show any significant quantitative advantages in predicting the phase behavior of hydrogen-bonding polymer blends relative to a previously proposed hydrogen-bonding lattice model that ignores compressibility effects.
引用
收藏
页码:6710 / 6723
页数:14
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