Acta Chimica Sinica ›› 2005, Vol. 63 ›› Issue (23): 2147-2152. Previous Articles     Next Articles

乙腈溶液中NO3自由基与联苯的反应机理

董文博, 朱承驻, 房豪杰, 欧阳彬, 张仁熙, 侯惠奇   

  1. 复旦大学环境科学研究所, 上海, 200433
  • 投稿日期:2005-02-05 修回日期:2005-04-22 发布日期:2014-02-14
  • 通讯作者: wbdong@fudan.edu.cn
  • 作者简介:侯惠奇,E-mail:wbdong@fudan.edu.cn
  • 基金资助:

    国家自然科学基金(No.20377009)资助项目.

Reaction Mechanism of the Nitrate Radical with Biphenyl in Acetonitrile

DONG Wen-Bo, ZHU Cheng-Zhu, FANG Hao-Jie, OUYANG Bin, ZHANG Ren-Xi, HOU Hui-Qi   

  1. Institute of Environmental Science, Fudan University, Shanghai 200433
  • Received:2005-02-05 Revised:2005-04-22 Published:2014-02-14

NO3 radical produced in the laser flash photolysis of cerium ammonium nitrate was applied to attack biphenyl in oxygen-free acetonitrile solution. The transient intermediates were identified with the nanosecond transient spectroscopic analysis and the final products were detected by GC-MS technique. A rea-sonable mechanism of the reaction was proposed. With a second-order rate constant of 8.24×109 L·mol-1·s-1, NO3 radical withdrew an electron from the biphenyl molecule to produce a charge-transfer (C-T) complex, which was sequentially transformed to σ- or p-nitrobiphenyl by elimination of a hydroxyl radical. The total first-order decay rate constant of the C-T complex was determined to be 2.30×105 s-1.

Key words: laser flash photolysis, transient absorbance spectrum, biphenyl, NO3 radical, charge-transfer complex