Thermodynamic, kinetic and mechanistic investigations of Piperazine oxidation by Diperiodatocuprate(III) complex in aqueous alkaline medium

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• 作者：VIJAY P PATTAR ; PRASHANT A MAGDUM ; DEEPA G PATIL…
• 关键词：Kinetics ; oxidation ; mechanism ; diperiodatocuprate(III) ; piperazine
• 刊名：Journal of Chemical Sciences
• 出版年：2016
• 出版时间：March 2016
• 年：2016
• 卷：128
• 期：3
• 页码：477-485
• 全文大小：900 KB
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• 作者单位：VIJAY P PATTAR (1)
  PRASHANT A MAGDUM (1)
  DEEPA G PATIL (1)
  SHARANAPPA T NANDIBEWOOR (1)
  
  1. P. G. Department of Studies in Chemistry, Karnatak University, Dharwad, 580 003, India
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Chemistry
  
• 出版者：Springer India
• ISSN：0973-7103

文摘

The kinetics of oxidation of piperazine by the copper complex, diperiodatocuprate(III) in alkaline medium was studied at 298 K, at an ionic strength of 2.0 x 10 −2 mol dm −3. The reaction between piperazine and diperiodatocuprate(III) in aqueous alkaline medium exhibited 1:2 stoichiometry. The oxidation products were identified by UV-Visible, GC-MS and IR spectral studies. In the present study we have obtained different kinetic observations. The reaction exhibited unit order in case of diperiodatocuprate(III), while less than unit order with respect to piperazine. The addition of alkali and periodate retarded the rate of reaction. The effects of added products, ionic strength and dielectric constant on the rate of the reaction were also studied. The active species of diperiodatocuprate(III) in alkaline media is [Cu(OH) ₂(H ₃ IO ₆)] −. The activation parameters with respect to the rate determining step and the thermodynamic quantities with respect to the equilibrium steps were evaluated and discussed. The plausible mechanism consistent with the experimental results was proposed and discussed in detail.