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芥子气模拟剂苯甲硫醚在改性H2O2溶液中的两阶段氧化

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赵三平, 习海玲, 王琦. 芥子气模拟剂苯甲硫醚在改性H2O2溶液中的两阶段氧化[J]. 环境化学, 2014, 33(9): 1546-1552. doi: 10.7524/j.issn.0254-6108.2014.09.005
引用本文: 赵三平, 习海玲, 王琦. 芥子气模拟剂苯甲硫醚在改性H2O2溶液中的两阶段氧化[J]. 环境化学, 2014, 33(9): 1546-1552. doi: 10.7524/j.issn.0254-6108.2014.09.005
shu
ZHAO Sanping, XI Hailing, WANG Qi. Two-step oxidation of thioanisole as yperite (HD) simulant by modified aqueous H2O2 solution[J]. Environmental Chemistry, 2014, 33(9): 1546-1552. doi: 10.7524/j.issn.0254-6108.2014.09.005
Citation: ZHAO Sanping, XI Hailing, WANG Qi. Two-step oxidation of thioanisole as yperite (HD) simulant by modified aqueous H2O2 solution[J]. Environmental Chemistry, 2014, 33(9): 1546-1552. doi: 10.7524/j.issn.0254-6108.2014.09.005
shu

芥子气模拟剂苯甲硫醚在改性H2O2溶液中的两阶段氧化

  • 1.

    国民核生化灾害防护国家重点实验室, 北京, 102205

  • 基金项目:

    国民核生化灾害防护国家重点实验室基础研究项目（SKLNBC2012-09，SKLNBC2013-06）资助.

Two-step oxidation of thioanisole as yperite (HD) simulant by modified aqueous H2O2 solution

  • 1.

    State Key Laboratory of NBC Protection for Civilian, Beijing, 102205, China

  • Fund Project:

  • 摘要: 以苯甲硫醚（PhSMe）为芥子气模拟剂，以NH3和NaOH为改性试剂，研究了改性H2O2溶液对硫醚的两阶段氧化产物、动力学与反应机制.改性H2O2溶液中，苯甲亚砜（PhS（O）Me）和苯甲砜（PhS（O）2Me）是仅有的两种氧化产物.随改性剂的加入和pH升高，PhSMe的初级氧化（PhSMe→PhS（O）Me）经历了质子催化氧化、溶剂辅助氧转移两种不同的催化氧化机制，表观动力学常数随pH呈“三段式”变化，两种反应机制的相对贡献取决于溶液的pH.PhSMe的次级氧化反应（PhS（O）Me→PhS（O）2Me）比初级氧化反应慢得多，其产物PhS（O）2Me的产率与改性H2O2溶液的pH呈指数相关.pH和反应时间相同时，NH3改性H2O2溶液的PhS（O）2Me产率明显低于NaOH改性H2O2溶液.超氧阴离子（O2-）是导致PhS（O）Me→PhS（O）2Me的活性氧，NH3通过抑制O2-产率而降低了硫醚类过度氧化的风险.
    Abstract: In the present work, thioanisole (PhSMe) was used as a simulant of yperite (HD), while NH3 and NaOH were used as alkaline modifiers to study the oxidation products, kinetics and mechanisms of the two-step oxidation of sulfides by alkaline-modified H2O2. The results indicated that PhS(O)Me and PhS(O)2Me were the only two oxidation products of PhSMe in modified H2O2 solution. Two different mechanisms of catalytic oxidation, proton-catalyzed oxidation and solvent-aided oxygen transfer, contributed to the primary oxidation of PhSMe(PhSMe→PhS(O)Me), and relative contributions of these two mechanisms strongly depended on additive amount of the alkaline modifiers and pH of the modified solution. Observed kinetic constants of the primary oxidation of PhSMe (kobs1) showed a three-stage profile with pH in both NH3 and NaOH modified H2O2 solution. While secondary oxidation of PhSMe (PhS(O) Me→PhS(O)2Me) was much slower than the primary oxidation, and the yield of PhS(O)2Me depended exponentially on pH of the modified H2O2 solutions. Compared to NaOH modified H2O2 solution, NH3 modified H2O2 solution produced much less PhS(O)2Me at same pH and reaction time. Superoxide anions (O2-) was the reactive oxygen in same for the secondary oxidation of PhSMe, and addition of NH3 into the alkaline H2O2-based decontaminants could reduce the risks of over oxidation of sulfide since NH3 can react with O2- to consume the oxidant.
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  • 收稿日期:  2013-11-08
赵三平, 习海玲, 王琦. 芥子气模拟剂苯甲硫醚在改性H2O2溶液中的两阶段氧化[J]. 环境化学, 2014, 33(9): 1546-1552. doi: 10.7524/j.issn.0254-6108.2014.09.005
引用本文: 赵三平, 习海玲, 王琦. 芥子气模拟剂苯甲硫醚在改性H2O2溶液中的两阶段氧化[J]. 环境化学, 2014, 33(9): 1546-1552. doi: 10.7524/j.issn.0254-6108.2014.09.005
shu
ZHAO Sanping, XI Hailing, WANG Qi. Two-step oxidation of thioanisole as yperite (HD) simulant by modified aqueous H2O2 solution[J]. Environmental Chemistry, 2014, 33(9): 1546-1552. doi: 10.7524/j.issn.0254-6108.2014.09.005
Citation: ZHAO Sanping, XI Hailing, WANG Qi. Two-step oxidation of thioanisole as yperite (HD) simulant by modified aqueous H2O2 solution[J]. Environmental Chemistry, 2014, 33(9): 1546-1552. doi: 10.7524/j.issn.0254-6108.2014.09.005
shu

芥子气模拟剂苯甲硫醚在改性H2O2溶液中的两阶段氧化

  • 1. 国民核生化灾害防护国家重点实验室, 北京, 102205
  • 收稿日期:  2013-11-08
基金项目:

国民核生化灾害防护国家重点实验室基础研究项目（SKLNBC2012-09，SKLNBC2013-06）资助.

摘要: 以苯甲硫醚（PhSMe）为芥子气模拟剂，以NH3和NaOH为改性试剂，研究了改性H2O2溶液对硫醚的两阶段氧化产物、动力学与反应机制.改性H2O2溶液中，苯甲亚砜（PhS（O）Me）和苯甲砜（PhS（O）2Me）是仅有的两种氧化产物.随改性剂的加入和pH升高，PhSMe的初级氧化（PhSMe→PhS（O）Me）经历了质子催化氧化、溶剂辅助氧转移两种不同的催化氧化机制，表观动力学常数随pH呈“三段式”变化，两种反应机制的相对贡献取决于溶液的pH.PhSMe的次级氧化反应（PhS（O）Me→PhS（O）2Me）比初级氧化反应慢得多，其产物PhS（O）2Me的产率与改性H2O2溶液的pH呈指数相关.pH和反应时间相同时，NH3改性H2O2溶液的PhS（O）2Me产率明显低于NaOH改性H2O2溶液.超氧阴离子（O2-）是导致PhS（O）Me→PhS（O）2Me的活性氧，NH3通过抑制O2-产率而降低了硫醚类过度氧化的风险.

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