论文部分内容阅读
将单取代烷烃的性质视为烷基、取代基各自的贡献以及烷基和取代基之间相互作用的贡献之和.用烷基中C-C键和C-H键的键邻接矩阵特征根之和ΣX1CC和ΣX1CH描述烷基的结构特征,以取代基的电负性和单取代甲烷与甲烷之间的热力学性质之差表征取代基对所研究的热力学性质的影响,并用烷基的极化效应指数与取代基电负性的乘积来定量烷基和取代基之间的相互作用.用上述参数对单取代烷烃(RX,X=OH,NH2,NO2,Cl,Br,I,SH,CN等)的气相热容CpΘ、标准摩尔熵SmΘ及标准摩尔生成吉布斯自由能ΔfGΘm建立定量相关模型,交叉验证表明这些模型都具有良好的稳定性和预测能力.
The properties of monosubstituted alkanes are taken as the sum of the contributions of the alkyl groups, the respective contributions of the substituents, and the contribution of the interaction between the alkyl groups and the substituents. The sum of the eigenvalues of the adjacency matrix ΣX1CC and ΣX1CH describes the structural characteristics of alkyl groups, characterizing the effect of substituents on the thermodynamic properties studied, based on the electronegativity of the substituents and the difference in the thermodynamic properties between the monosubstituted methane and methane, and using the indices of polarization effect of alkyl groups with substitutions Based on the product of the electronegativity of the alkyl group and the substituent of the substituent.For the gas phase of monosubstituted alkanes (RX, X = OH, NH2, NO2, Cl, Br, I, SH, CN, etc.) The heat capacity CpΘ, the standard molar entropy SmΘ and the Gibbs free energy ΔfGΘm for the standard molar generation were used to establish quantitative correlation models. Cross-validation showed that these models all had good stability and predictive ability.