Cu（Ⅲ）二过碘酸配离子氧化1，3-丙二胺的反应动力学及机理  

Kinetics and Mechanism of Oxidation of 1,3-Propanediamine by Diperiodatocuprate（ Ⅲ ） in Alkaline Medium

作　　者：单金缓[1] 王晓倩[1] 韩冲[1] 王芳[1] 

机构地区：[1]河北大学化学与环境科学学院,河北保定071002

出　　处：《河北大学学报（自然科学版）》2010年第1期43-48,共6页Journal of Hebei University(Natural Science Edition)

基　　金：河北省自然科学基金资助项目（295066）

摘　　要：为了给有机合成反应路径提供有利的依据，用分光光度法研究了在298．2～313．2K的碱性介质中二过碘酸合铜（Ⅲ）（DPC）酸根配离子氧化1，3-丙二胺（PDA）的反应动力学及机理．实验结果表明：反应对氧化剂DPC是一级，对还原剂PDA的表观反应级数（nap），1〈nap〈2时准一级速率常数kobs随[OH（-]增大而增大，碘酸根离子对反应速率起阻碍作用，且离子强度对反应有弱的负盐效应．据此提出了氧化反应的机理并求出了速控步骤的速率常数及298．2K时的活化参数．In order to provide a strong basis for the path of organic synthesis, the kinetics of oxidation of 1,3-propanediamine （PDA） by diperiodatocuprater（ Ⅲ） （DPC） in alkaline medium have been studied by spectrophotometry in a temperature range of 298. 2-313. 2 K. The reaction showed pseudo-first order with respect to DPC and 1〈naq〈2 to PDA. It was found that the pseudo-first order rate constant kobs increased with the increase of [OH^-], periodate had a retarding effect on the reaction rate. There is a weak negative salt effect. Based on the experimental results, a probable reaction mechanism of oxidation was proposed. The rate equation derived from the mechanism can explain all the experimental phenomena. The activation parameters along with the rate constants of the rate-determined step were calculated and discussed, and thermodynamic quantities were also determined.

关 键 词：二过碘酸合铜(Ⅲ) 1 3-丙二胺 氧化还原反应 

分 类 号：O643.12[理学—物理化学]