化学学报 ›› 2004, Vol. 62 ›› Issue (12): 1115-1122. 上一篇    下一篇

研究论文

利用瞬态吸收光谱技术研究水体中苯与亚硝酸的交叉反应机理

朱承驻1, 欧阳彬1, 房豪杰1, 董文博1, 郑志坚2, 赵庆祥3, 侯惠奇1   

  1. 1. 复旦大学环境科学研究所, 上海, 200433;
    2. 复旦大学环境科学与工程系, 上海, 200433;
    3. 华东理工大学资源与环境工程学院, 上海, 200237
  • 投稿日期:2003-11-19 修回日期:2004-01-31 发布日期:2014-02-17
  • 通讯作者: 侯惠奇,E-mail:fdesi@fudan.edu.cn E-mail:fdesi@fudan.edu.cn
  • 基金资助:
    上海市科技发展基金(No.022312116)资助项目.

Study on the Cross-Reaction Mechanism of Aqueous Benzene with Nitrous Acid in Dilute Solutions by Transient Absorption Spectrum Technique

ZHU Cheng-Zhu1, OUYANG Bin1, FANG Hao-Jie1, DONG Wen-Bo1, ZHENG Zhi-Jian2, ZHAO Qing-Xiang3, HOU Hui-Qi1   

  1. 1. Institute of Environmental Science, Shanghai 200237;
    2. Department of Environmental Science and Engineering, Fudan University, Shanghai 200433;
    3. Resources and Environmental Engineering Institute, East China University of Science and Technology, Shanghai 200237
  • Received:2003-11-19 Revised:2004-01-31 Published:2014-02-17

利用瞬态吸收光谱技术进行了有氧、无氧条件下苯与亚硝酸水溶液复相体系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和NO+,·OH自由基和苯反应生成C6H6-OH adduct,反应速率常数为8.9×109 L·mol-1·s-1,在有氧条件下C6H6-OH adduct进一步氧化为C6H6-OHO2,反应速率常数3.3×108 L·mol-1·s-1; NO+自由基和苯作用形成C6H6-NO complex,然后进一步分解.

关键词: 激光闪光光解, 苯, HNO2, 瞬态吸收光谱, 自由基

The cross-reaction microscopic mechanism of aqueous benzene with nitrous acid in the presence of O2 or absence of O2 in dilute solutions was studied by laser flash photolysis. The main characteristic peaks in these transient absorption spectra were attributed and the build-up/decay trends of several transient species were investigated. ·OH radical and nitrosonium cation (NO+) can be produced in aqueous solution of nitrous acid exposed to 355 nm laser beam. NO+ reacts with benzene to produce C6H6-NO complex. The rate constant of the reaction between ·OH radical and benzene was measured to be 8.9×109 L·mol-1·s-1. The transient product C6H6-OH adduct reacts with O2 to form C6H6-OHO2 with the rate constant of 3.3×108 L·mol-1·s-1. The final photolysis products were analyzed by using GC/MS method and the possible reaction pathways were also discussed.

Key words: laser flash photolysis, benzene, nitrous acid, transient absorption spectrum, free radical