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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (1): 112-116. 上一篇    下一篇

研究论文

瞬态吸收光谱研究水相中三苯基锡与•OH自由基反应机理

曹长青，黄丽，张仁熙，董文博*，侯惠奇*   

  1. (复旦大学环境科学研究所 上海 200433)
  • 投稿日期:2007-06-04 修回日期:2007-08-20 发布日期:2008-01-14
  • 通讯作者: 侯惠奇

Study on the Reaction Mechanism of Triphenyltin with OH Radical in Aqueous Phase by Transient Absorbance Spectra

CAO Chang-Qing HUANG Li ZHANG Ren-Xi DONG Wen-Bo* HOU Hui-Qi*   

  1. (Institute of Environmental Science, Fudan University, Shanghai 200433)
  • Received:2007-06-04 Revised:2007-08-20 Published:2008-01-14
  • Contact: HOU Hui-Qi

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利用激光闪光光解技术进行了有氧、无氧条件下氯化三苯基锡与亚硝酸水溶液的紫外光解反应研究。研究表明，•OH和三苯基锡阳离子(Sn(C6H5)3+)反应生成了瞬态粒子Sn(C6H5)3+-OH，其二级反应速率常数为(7.9±1.2)×109 L mol-1 s-1。在N2饱和条件下，Sn(C6H5)3+-OH以单分子方式衰减，其衰减速率常数为(1.15±0.15)×105 s-1；在O2饱和条件下，表观一级衰减常数增加为(1.87±0.25)×105 s-1，这是由于Sn(C6H5)3+-OH能够与O2发生作用生成Sn(C6H5)3+-OHO2，其二级反应速率常数为(6.0±2.9) ×107 L mol-1 s-1。

关键词: 激光闪光光解, 瞬态吸收光谱, 氯化三苯基锡, 羟基自由基

The reaction of triphenyltin with nitrous acid in aqueous phase in the presence and absence of O2 was studied by laser flash photolysis technique. The main characteristic peaks in these transient absorption spectra were attributed and the build-up/decay trends were investigated. Triphenyltin cation reacts with OH radical to produce Sn(C6H5)3+-OH adduct and the reaction rate was measured to be (7.9±1.2)×109 L mol-1 s-1. Sn(C6H5)3+-OH adduct decayed at a constant of (1.87±0.25)×105 s-1 and (1.15±0.15)×105 s-1 in the presence and absence of O2 respectively, and the decay rate in the presence O2 was higher due to the reaction between Sn(C6H5)3+-OH and O2 to produce Sn(C6H5)3+-OHO2 at a rate constant of (6.0±2.9) ×107 L mol-1 s-1 .

Key words: laser flash photolysis, transient absorption spectra, triphenyltin chloride, •, OH radical