Rates and Mechanism of the Reduction of Vanadium(V) by Benzyl Alcohol in Aqueous Dimethylformamide

DMF 수용매에서 벤질알코올에 의한 바나듐(V)의 환원반응속도와 메카니즘

  • Chang-Su Kim (Department of Chemistry Education, Taegu University) ;
  • Woo-Sik Lee (Department of Chemistry Education, Taegu University)
  • 김창수 (대구대학교 사범대 화학교육과) ;
  • 이우식 (대구대학교 사범대 화학교육과)
  • Published : 1988.06.20

Abstract

The reaction of VO_2\;^+$ with benzyl alcohol in perchloric acid and aqueous dimethylformamide leads to the formation of $VO^{2+}$ and benzaldehyde. The products, $VO^{2+}$ and benzaldehyde, are identified by infrared spectroscopy and gas chromatography. Kinetic studies on the reaction of VO_2\;^+$ with benzyl alcohol have been carried out using visible spectroscopy. The empirical rate equation can be expressed as $-d[VO_2\;^+]/dt=2\{\\{k_O+k_H[HClO_4]\}\[VO_2\;^+][C_6H_5CH_2OH]$ The rate determining step for the reaction is the process for the formation of $VO^{2+}$ and $C_6H_5CHOH$. The activation parameters are ${\Delta}H^{\neq}=13.32{\pm}1.73\;kcalmol^{-1}$ and ${\Delta}S^{\neq}=-31.02{\pm}0.09\;calmol^{-1}K^{-1}$ for the oxidation of benzyl alcohol in aqueous dimethylformamide.

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