分子热力学前沿基础领域中的新理论4:论有机纯质的分子结构与临界压力理论方程

New theory in the front of theoretical basis research of molecular thermodynamics 4: on molecular structure of organic compound and theoretical equation of critical pressure

根据分子热力学理论,分析阐明纯质的临界压力JDc的微观机理及Lydersen,Wilson等在国际学术界享有盛誉的学者和Joback,Constantinou-Gani(C-G)等的著名公式普适性差,误差大等缺陷。在文献[1]创立的有机分子的半金属结构理论指导下提出一个计算Pc的理论方程,经用极性与非极性纯质等38种结构类型428个纯质Pc实测值检验、其平均误差仅1.72%,达到实验允许误差范围的高水平,计算精度比Joback式高3.6倍,比Wilson-Jasperson(W-J)式,Marrero-Pardillo(M-P)式高3.2倍以上,比MXXC法高4.41倍,是临界性质的计算化学领域中的一个重大突破。

From the point of view of molecular dynamic theory, the mechanism of critical pressure for pure substance was creative in the field. As the same time, the applicability of the famous formulas (the formulas of Riedel' s, lyderson' s, Joback' s, Constantinou - Gani' s, Wilson - Jasperson and Marrero - Pardillo' s were evaluate in text) for estimation critical pressure is not good. All methods give average error of about 5 -6%. A theoretical equation for estimating critical pressure was presented under the guide of semi - metal structure model of organic molecular derived from the literature[1]. When applied to 428 compounds of 38 structural types, including polar and nonpolar, its average error was only 1.72% and it reached high level in the experimental allowance error range. Its accuracy is about 3. 5 times as high as that of Joback' s method, and about 4. 5 times that of C - G method. This study is significant breakthrough in the calculating chemistry of critical properties.