物理化学学报 >> 2005, Vol. 21 >> Issue (04): 367-371.doi: 10.3866/PKU.WHXB20050405

研究论文 上一篇    下一篇

355 nm光照下大气液相中HNO2与C6H5Cl的反应机理

朱承驻; 张仁熙; 房豪杰; 赵庆祥; 侯惠奇   

  1. 复旦大学环境科学研究所, 上海 200433; 华东理工大学资源与环境工程学院, 上海 200237
  • 收稿日期:2004-08-17 修回日期:2004-11-08 发布日期:2005-04-15
  • 通讯作者: 侯惠奇 E-mail:fdesi@fudan.edu.cn

Study on the Reaction Mechanism of Chlorobenzene with Nitrous Acid in Atmospheric Aqueous Phases Initiated by Irradiation of 355 nm UV Light

ZHU Cheng-Zhu; ZHAGN Ren-Xi; FANG Hao-Jie; ZHAO Qing-Xiang; HOU Hui-Qi   

  1. Institute of Environmental Science, Fudan University, Shanghai 200433； College of Resources and Environmental Engineering, East China University of Science and Technology, Shanghai 200237
  • Received:2004-08-17 Revised:2004-11-08 Published:2005-04-15
  • Contact: HOU Hui-Qi E-mail:fdesi@fudan.edu.cn

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摘要： 利用瞬态吸收光谱技术进行了有氧、无氧条件下氯苯与亚硝酸水溶液的交叉反应机理研究，初步考察了这些瞬态物种的生长与衰减等行为, 并对其光解产物进行了GC/MS分析.研究表明，HNO2在355 nm紫外光的照射下可产生•OH自由基, •OH和氯苯反应生成C6H5Cl•••OH，反应速率常数为（6.6～7.0）×109 L•mol-1•s-1; 在有氧条件下C6H5Cl•••OH可氧化为C6H5Cl•••OHO2, 反应速率常数为(1.6 ± 0.2)×109 L•mol-1•s-1,然后进一步分解; C6H5Cl•••OH衰减或与亚硝酸等作用可形成多种含硝基的化合物或醌类物质.

关键词: 激光闪光光解, 氯苯, HNO2, 瞬态吸收光谱, •, OH自由基

Abstract: The reaction microscopic mechanism of aqueous solution of chlorobenzene with nitrous acid in the presence of O2 and absence of O2 was studied by laser flash photolysis. The main characteristic peaks in these transient absorbance spectra were attributed and the build-up/decay trends of several transient species were investigated. •OH radical can be produced in aqueous solution of nitrous acid exposed to 355 nm laser beam. The rate constant of the reaction between •OH radical and chlorobenzene was measured to be （6. 6～7. 0）×109 L•mol-1•s-1. The transient product C6H5Cl-OH reacted with O2 to form C6H5Cl-OHO2 with a rate constant of (1. 6±0. 2) ×109 L•mol-1•s-1. The photolysis products were analyzed by GC/MS method and the possible reaction pathways were discussed.

Key words: Laser flash photolysis, Chlorobenzene, Nitrous acid, Transient absorption spectra, •, OH radical