The thermodynamic properties of unsubstituted, mono‐, and di‐substituted toluene derivatives and benzylic radicals with hydroxy, methoxy, formyl, vinyl, methyl, and ethyl substituents are calculated with the bond additivity corrected (BAC) post‐Hartree‐Fock CBS‐QB3 method. Benson's group additivity (GA) scheme is extended to toluene derivatives by determining six group additive value (GAV) and five non‐nearest neighbor interaction (NNI) parameters through least‐squares regression to a database of thermodynamic properties of 168 compounds and to benzylic radicals by defining 6 GAV and 14 NNI parameters based on a set of 168 radicals. Comparison between CBS‐QB3/BAC and GA‐calculated thermodynamic values shows that the standard enthalpies of formation generally agree within 4 kJ mol⁻¹, whereas the entropies and the heat capacities generally deviate <4 J mol⁻¹ K⁻¹. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3649–3661, 2018

中文翻译：

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通过基团加性模拟取代甲苯衍生物和苄基的热力学

使用Hartree-Fock CBS-QB3后的键加和校正（BAC）计算未取代的，具有羟基，甲氧基，甲酰基，乙烯基，甲基和乙基取代基的单取代，单取代和二取代的甲苯衍生物和苄基的热力学性质方法。Benson的基团可加性（GA）方案通过最小二乘回归确定168个化合物的热力学性质数据库和苄基来确定六个基团加和值（GAV）和五个非最近邻相互作用（NNI）参数，从而扩展到了甲苯衍生物。通过基于一组168个部首定义6个GAV和14个NNI参数。CBS-QB3 / BAC与GA计算的热力学值之间的比较表明，标准的形成焓通常在4 kJ mol ^-1之内，而熵和热容通常偏离<4 J mol ^-1 K ^-1。©2018美国化学工程师学会AIChE J，64：3649–3661，2018