由速率方程推演反应历程的方法  

Methods of Deriving a Reaction Mechanism from Its Rate Equation

作　　者：谭亚南[1] 盛景云[1] 方维平[1] 王跃敏[1] 

机构地区：[1]厦门大学化学化工学院,福建厦门361005

出　　处：《厦门大学学报（自然科学版）》2005年第5期664-667,共4页Journal of Xiamen University：Natural Science

摘　　要：将化学反应视为抽象的“化学流”,提出“完全速率方程”的概念,并阐述其物理意义,考察了完全速率方程的各种破缺形式及其所对应的反应历程的特性及自催化作用对速率方程的影响.通过举例说明,归纳总结了由速率方程推演反应历程所应遵循的原理和规则.Supposing that the concentrations of intermediates are invariable during the course of a chemical reaction,there will be a rate equation with full form called full rate equation： γfal=（Ff-Fb）/（Fm-f-Fm-b）. The full rate equation,if a chemical reaction is regarded as chemical flow, has its physical meanings. Ff,Fb,Fm-f,Fm-b can be called forward full-flow, backward full-flow,forward flow of decreasing intermediates and backward flow of decreasing intermediates respectively. Ff is defined as multiplication of the forward rate equation of every element reaction （ER） and the definitions of Fb ,Fm-f and Fm-b are in analogy to Ff. The reaction mechanism （pathway） corresponding the full rate equation has three features： （1） every ER is reversible, （2） at least one molecule of reactants does not take part in first-step ER; （3） at least one molecule of products does not emerge in last-step ER. In most eases, the full rate equation appears as a certain kind of short forms. For example,if at least one of ERs is irreversible, then Fb =0. According to the physical meanings of rate equation and the understanding of the intermediates of the reaction concerned, we can easily derive the reaction pathway. Meanwhile the effects of autocatalysis on the form of the rate equation are also discussed.

关 键 词：化学反应 反应历程 速率方程 自催化作用 

分 类 号：O643.11[理学—物理化学]