作　　者： ; ;

机构地区： 浙江大学化学系

出　　处： 《化学反应工程与工艺》 1992年第2期127-135,共9页

摘　　要： 研究了 C_5H_5N+CH_3I 和(CH_3CO)_2O+C_2H_5OH 两个反应的过渡态模型及其动力学溶剂效应。结果表明,体系中含有各向异性的芳环分子时,由于位置效应粒子间产生了强烈的相互作用,因此提出了新的求取过渡态分子参量的方法,并应用了不同的过渡态模型及其相应的分子参量来描述这种相互作用,更接近实际地反映了过渡态模型的性质与动力学介质效应的内在关系,以及反应物和过渡态与溶剂分子之间的相互作用。计算了上述反应在各种纯溶剂和混合溶剂中,不同温度下的速率常数。结果与实验值能较好地符合。 In this paper,the transition state models of the reactions between pyridine and methyl iodide, and acetic anhydride and ethanol have been investigated,and their kinetic solvent effects were calculated.The results showed that when the system contains the anisotropic aromatic molecules strong interactions between particles will occur by the space-effects.According to this conclusion,a new method for calculation of the molecular parameters of the transition state was presented.Based on this method,these interactions were described by using various transition state models and corresponding molecular parameters,so the relation between the properties of the model and the kinetic medium effects as well as the interactions of the reactants and the transition states with solvent molecules can be better reflected.The calculated rate constants for the above reactions in various pure or mixed solvents and their temperature dependence were in good agreement with the experimental values.

关 键 词： 溶剂效应 过渡态模型 反应动力学

领　　域： [理学] [理学]