分子热力学前沿基础理论研究中的新理论2:有机分子的半金属结构理论与有机纯质的ΔH_(f g)~0理论式

New theory in the front of theoretical basis research of molecular thermodynamics 2 semi - metal structural model of organic molecules and theoretic equation of ΔH_(f g)~0 of pure organic compound

分析了国际科技界声誉卓著的Benson法及其在理论上的缺陷,根据分子热力学理论模型-有机分子的半金属结构理论提出计算△Hfg0的理论式,经用42类不同结构类型780种有机化合物实测值验算,平均误差1.47%,误差≤2%的占总数的97%以上,本法物理意义明确,精确度比Benson法高6.7倍,显著优于文献中各式。

After analyzing the drawbacks of the Benson' s equation for estimating ΔHfg0, a new theoretical formula is proposed. According to molecular orbital theory and taking into consideration the interactions among all the atoms of a molecule and restrictions in a whole molecule which depend on the electron effect, the author discovered the fact of relative independence of groups or bonds. By applying the matrix method, a semi - theoretical formula was derived. To check this equation, the data of 780 organic polar and nonpolar compounds were used with an average error of 1. 47% for 780 experimental values. Its accuracy is over 6. 7 times higher than that of the famous Benson method recommended by Reid et al. This method is far better than the other methods reported in literature. The use of the distribution of electron cloud (or electron effect) to deal with the interaction among bonds or groups is creative and an important breakthrough in this field, which is why in this method 101 parameters were used for calculation, much less than the 623 used by Benson but with wider application and higher accuracy. These results show that Eq. 5 is of great significance in the development of thermochemistry and its practical application.