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氯酚溶液的γ辐照还原降解研究
摘要点击 2564  全文点击 1199  投稿时间:2012-06-21  修订日期:2012-09-05
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中文关键词  氯酚  γ辐照  还原降解  水合电子  脱氯
英文关键词  chlorophenols  Gamma irradiation  reductive degradation  hydrated electron  dechlorination
作者单位E-mail
彭云霞 清华大学核能与新能源技术研究院,北京 100084
武汉理工大学资源与环境工程学院, 武汉 430070 
yunxiapeng@foxmail.com 
何仕均 清华大学核能与新能源技术研究院,北京 100084 heshj@mail.tsinghua.edu.cn 
龚文琪 武汉理工大学资源与环境工程学院, 武汉 430070  
王建龙 清华大学核能与新能源技术研究院,北京 100084  
中文摘要
      氯酚由于氯取代基产生的诱导效应,使其容易受到亲核粒子的攻击而被还原降解. 通过测定γ辐照前后氯酚母体、Cl-离子以及反应中间产物的浓度变化,研究了4种氯酚水溶液(4-CP、2-CP、2,4-DCP、2,4,6-TCP) 与水合电子eaq-反应的降解脱氯过程. 结果表明,在水合电子eaq-还原体系中,4种氯酚的降解脱氯顺序依次为:2,4,6-TCP>2,4-DCP>2-CP>4-CP,多氯酚比单氯酚容易降解脱氯,邻位上的氯原子要比对位上的氯原子更容易去除,苯酚和Cl-是氯酚反应降解的最终产物. 另外,4种氯酚的降解和脱氯过程皆遵循一级反应动力学特征,4-CP、2-CP、2,4-DCP和2,4,6-TCP的降解反应常数分别是0.154、0.253、0.750和1.188 kGy-1,脱氯反应常数分别为0.137、0.219、0.251和 0.306 kGy-1.
英文摘要
      Because chlorine is an electron withdrawing group, the highly chlorinated phenols may react quickly with hydrated electrons rather than with hydroxyl radicals. The process of reactions of four chlorophenols (4-CP, 2-CP, 2,4-DCP, 2,4,6-TCP) with eaq- was investigated in aqueous solutions by detecting the concentration of CPs, Cl- and intermediates. In the eaq-reductive system, the experimental results showed that the order of four kinds of chlorophenol degradation and dechlorination was 2,4,6-TCP>2,4-DCP>2-CP>4-CP. The greater the chlorine content was the higher reactivity of hydrated electrons towards chlorophenols was. Furthermore, hydrated electrons may preferentially attack the ortho-position of chlorine atom rather than the para-position of chlorine atom. Phenol and Cl- were detected as the final product of the reductive reaction. Additionally, processes of degradation and dechlorination of CPs were observed as the pseudo-first-order kinetics. The reaction constant of degradation of 4-CP, 2-CP, 2,4-DCP and 2,4,6-TCP were 0.154, 0.253, 0.750 and 1.188 kGy-1, respectively. Meanwhile, the dechlorination of 4-CP, 2-CP, 2,4-DCP and 2,4,6-TCP were 0.137, 0.219, 0.251 and 0.306 kGy-1, respectively.

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