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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (4): 279-283.    下一篇

研究论文

激光诱导的亚硝酸与二苯醚的反应机理

李萍, 董文博, 张仁熙, 房豪杰, 黄丽, 侯惠奇*   

  1. (复旦大学环境科学研究所 上海 200433)
  • 投稿日期:2006-09-18 修回日期:2006-10-24 发布日期:2007-02-28
  • 通讯作者: 侯惠奇

Reaction Mechanism of Diphenyl Ether with Nitrous Acid by Transient Absorption Spectrum Technique

LI Ping; DONG Wen-Bo; ZHANG Ren-Xi; FANG Hao-Jie; HUANG Li; HOU Hui-Qi*   

  1. (Institute of Environmental Science, Fudan University, Shanghai 200433)
  • Received:2006-09-18 Revised:2006-10-24 Published:2007-02-28
  • Contact: HOU Hui-Qi

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被引次数

9 | 1

355 nm光照下利用瞬态吸收光谱技术进行了有氧、无氧条件下二苯醚与亚硝酸体系的反应机理研究, 考察了其中瞬态物种的衰减行为, 并对其光解产物进行了GC-MS分析. 研究表明, HNO2在355 nm紫外光的照射下产生的OH自由基和二苯醚反应生成C12H10O-OH 加合物, N2条件下C12H10O-OH衰减的速率常数为(1.86±0.14)×105 s－1, 在有氧条件下, C12H10O-OH可转化为C12H10O-OHO2, 衰减的速率常数为(6.6±0.4)×106 s－1. N2条件下最终产物为苯酚、2-羟基二苯醚、4-羟基二苯醚、4-硝基二苯醚.

关键词: 激光闪光光解, 二苯醚, 瞬态吸收光谱

The microscopic reaction mechanism of diphenyl ether with nitrous acid in the presence or absence of O2 was studied by laser flash photolysis. The main characteristic peaks in these transient absorption spectra were attributed and the decay trends were investigated. The final photolysis products were analyzed by using GC-MS method. OH radical obtained by nitrous acid exposed to 355 nm laser beam reacts with diphenyl ether to produce C12H10O-OH adduct. In the absence of O2 the decay constant of C12H10O-OH adduct was measured to be (1.86±0.14)×105 s－1 and the final photolysis products were phenol, o-hydroxydiphenyl ether, p-hydroxydiphenyl ether and p-nitrodiphenyl ether. While in the presence of O2 the decay constant of C12H10O-OH adduct was measured to be (6.6±0.4)×106 s－1.

Key words: laser flash photolysis, diphenyl ether, transient absorption spectrum