分子热力学前沿基础研究领域中的新理论8:有机分子的半金属结构理论与纯质临界温度理论方程  

In the leading basic research of molecular thermodynamics new theory 8: semi-metal structural model of organic molecules and theoretical equation of the critical temperature

作　　者：张克武[1] 张宇英[1] 

机构地区：[1]东北师范大学化学学院

出　　处：《黑龙江大学自然科学学报》2005年第6期701-706,共6页Journal of Natural Science of Heilongjiang University

基　　金：国家自然科学基金资助项目(29746002);吉林省应用基础基金资助项目;首钢总公司赞助

摘　　要：根据在临界状态时比van der Waals方程更精确的Dieterici方程,解出临界温度Tc和其分子结构参数成反比的函数关系;按照Kirchhoff定律导出纯质的Tc理论式;应用有机分子的半金属结构理论中的定理,考虑分子中非定域电子运动的特性对Tc的影响,经用各种结构类型的450个纯质的Tc实测值检验,平均误差仅0.36%,达到实验容许误差范围之内,其精度比国际上著名的Lyderson法,Wilson et al法和Joback法,Constantinou-Gani(C-G)法,Marrero-Pardillo(M-P)法高2.5～10倍.对这样的100多年来未曾有过的优异的普适性,高精度和明晰的物理意义,三方面重大突破的事实俱在.应确认其是很好的填补了国际基础理论研究领域内的空白.Based on theoretical and experimental results from spectroscopy and molecular physics, it is shown that the critical temperatures, T, in K, is directly proportional to the normal boiling points, Tb, in K, and inversely proportional to the structural paraments, According to the Kirchhoff＇s law：（δ（ΔH）/δT）p=ΔCp we have ΔHvT=ΔHvb＋∫^T Tb ΔCpdT Let T = Tc, and from the liquid theory of Lennard - Jones and Devonshire （ 1937, 1938 ） ΔCp = Cp.v - Cp.l = Constant = c1 , we have a theoretical equation as ：Tc=Tb/（0.5800＋K-K^2＋K^4）（12）To check this equation, the data of experimental value for 450 pure substances ot various structural types were types were used with an average error of 0. 36%, within the range of experimental allowable error. Of the 450 pure organic compounds, theoretic equation （12） gives 98.1% within the percent error limit ＋ 1%. Its accuracy is about 2.5 - 10 times higher than that of the Lyderson method, Wilson et al method, Joback Method, Constantinou - Gani method and Marrero -Pardillo method. This theory equation with excellent generality, high accuracy and definite physical essence was filled in the gaps in the fields of international, basic and theoretical research.

关 键 词：有机分子的半金属结构理论 临界温度 理论方程 

分 类 号：O621.3[理学—有机化学] TE6-62[理学—化学]