高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (10): 1896.

• 研究论文 • 上一篇    下一篇

水相中·OH,·H和ea-q与2-氯酚反应机理研究

董文博1, 王淑惠1, 姚思德2, 侯惠奇1   

  1. 1. 复旦大学环境科学研究所, 上海 200433;
    2. 中国科学院上海原子核研究所辐射化学开放实验室, 上海 201800
  • 收稿日期:2001-04-16 出版日期:2002-10-24 发布日期:2002-10-24
  • 通讯作者: 侯惠奇(1945年生),男,博士,教授,博士生导师,从事微观反应动力学及环境化学等研究.E-mail:fdesi@fudan.edu.cn E-mail:fdesi@fudan.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:29777003)资助

Mechanism Studies on Reactions of ·OH,·H和ea-q with 2-Chlorophenol in Aqueous Solutions

DONG Wen-Bo1, WANG Shu-Hui1, YAO Si-De2, HOU Hui-Qi1   

  1. 1. Institute of Environmental Science, Fudan University, Shanghai 200433;
    2. Laboratory of Radiation Chemistry, Institute of Nuclear Research, The Chinese Academy of Sciences, Shanghai 201800, China
  • Received:2001-04-16 Online:2002-10-24 Published:2002-10-24

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摘要： 利用脉冲电子束辐解水产生·OH自由基、·H及水合电子(ea-q),研究了这些活性粒子在多种条件下与水相中2-氯酚的微观反应机理,对其瞬态光谱中的主要吸收峰做了归属,并初步考察了这些瞬态物种的生长、衰减等行为.研究表明,·OH自由基与2-氯酚在碱性条件下可直接反应生成邻氯代酚氧自由基,速率常数为1.0×109L·mol-1·s-1,也有部分·OH自由基与2-氯酚反应先生成OH-加合物,再进一步消除水分子生成邻氯代酚氧基;在酸性条件下要经过OH-加合物.·H则与2-氯酚反应生成H-加合物;ea-q可直接从2-氯酚分子夺氯,在近中性和碱性环境中,该反应的速率常数分别为1.25×109L·mol-1·s-1和6.3×108L·mol-1·s-1.

关键词: 2-氯酚, 脉冲辐解, 瞬态吸收光谱, 自由基

Abstract: Pulse radiolysis of aqueous 2-chlorophenol in dilute solutions under different conditions was studied. The main characteristic peaks in these transient absorption spectra were attributed and the build-up/decay trends of several transient species were investigated. Under alkaline conditions, the reaction of ·OH radical and 2-chlorophenol produces o-chlorinated phenoxyl radical with a rate constant of 1.0×109 L·mol -1·s-1; while under acid conditions, the initial product is mainly OH-adduct. The reaction between ·H and 2-chlorophenol produces H-adduct. In alkaline and nearly neutral solutions, ea-q can capture Cl directly from 2-chlorophenol with a rate constant 1.25×109 L·mol-1·s-1and 6.3×108 L·mol-1·s-1, respectively.

Key words: 2-Chlorophenol, Pulse radiolysis, Transient absorbance spectra, Free radical

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