高等学校化学学报

高等学校化学学报 ›› 1997, Vol. 18 ›› Issue (11): 1842.

• 论文 • 上一篇    下一篇

二过碘酸含铜(Ⅲ)配离子氧化异丙胺的动力学及机理

宋文玉, 李振华, 王安周   

  1. 河北大学化学系, 保定 071002
  • 收稿日期:1996-08-09 出版日期:1997-11-24 发布日期:1997-11-24
  • 通讯作者: 宋文玉, 男, 50岁, 副教授
  • 作者简介:宋文玉, 男, 50岁, 副教授

Kinetics and Mechanism of Oxidation of iso-Propyl Amine by Diperiodatocuprate (Ⅲ) Complex Ion

SONG Wen-Yu, LI Zhen-Hua, WANG An-Zhou   

  1. Department of Chemistry, Hebei University, Baoding 071002
  • Received:1996-08-09 Online:1997-11-24 Published:1997-11-24

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被引次数

44

摘要： 在碱性价质中于30～45℃区间,用分光光度法研究了二过碘酸含铜(Ⅱ)配离子(DPC)氧化异丙胺(PA)的动力学．结果表明：反应对DPC为一级,对PA的表观反应级数为1.15～1.39级；准一级([PA]0≥[Cu(Ⅲ)]0)速率常数kobs随[OH－]和[IO4-]cx的增加而减小；在氮气保护下反应体系能引发丙烯酰胺聚合,表明有自由基参与反应．此外,还观察到对速率有负盐效应．据此,提出了包括DPC离解出一个H2IO63-的前期平衡和[Cu(HIO6)]－与PA之间生成加成物的反应机理．

关键词: 二过碘酸含铜(Ⅲ), 异丙胺, 氧化还原, 动力学及机理

Abstract: The kinetics of oxidation of iso-propyl amine(PA) by diperiodatocuprate(Ⅲ)complex ion was studied by spectrophotometry in alkaline medium in the temperature range of30～45℃ The reaction rate showed the first order dependence in oxidant, and 1.15-1.39order dependence in PA.It reveals that the pseudo first-order ([PA]0>[Cu (Ⅲ)0]) rateconstant, kobs, decreases with the increase in [OH-] and the increase in [IO4]cx(KIO4] addedexternally), which implicates that before the rate-determining step there is a pre-equilibriumin which one of the two periodate ligands of the oxidant is dissociated after the protonation toform a reactive monoperiodatocuprate (Ⅲ) ion.Under the protection of nitrogen the reactionsystem Induced the polymerization of acrylamide indicating the participation of free radicals.Anegative salt effect on rate was observed.Based on the observations a mechanism involving a pre-equilibration and an adduct formation between [Cu(HIO6)]- and PAwasproposed.The rate equation derived from the mechanism could be used to explain all the theexperimental observations and the pre-equilibration constants, rate constants of the rate-determining step together with the activation parameters were evaluated.

Key words: Diperiodatocuprate(Ⅲ), iso-Propyl amine, Redox reaction, Kinetics and mechanism

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