| 赵三平,习海玲,左言军,王琦.Na2MoO4催化H2O2氧化芥子气模拟剂苯甲硫醚的动力学与产物[J].分子催化,2015,(1):45-51 |
| Na2MoO4催化H2O2氧化芥子气模拟剂苯甲硫醚的动力学与产物 |
| Oxidation Kinetics and Products of Methyl Phenyl Sulfide，a Sulfur Mustard Simulant by Sodium Molybdate Catalyzed Hydrogen Peroxide Solution |
| 投稿时间：2014-06-10 修订日期：2014-12-20 |
| DOI： |
| 中文关键词: 钼酸钠，过氧化氢，芥子气，苯甲硫醚，95Mo NMR |
| 英文关键词:molybdate, hydrogen peroxide, methyl phenyl sulfide, 95Mo NMR |
| 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 |
|
| 摘要点击次数: 1836 |
| 全文下载次数: 3372 |
| 中文摘要: |
| 以苯甲硫醚（PhSMe）作为化学毒剂芥子气的模拟剂，研究了Na2MoO4催化H2O2溶液氧化PhSMe的两阶段反应动力学及其产物分布。PhSMe在Na2MoO4催化H2O2溶液中生成了苯甲亚砜（PhS(O)Me）和苯甲砜（PhS(O)2Me）。相对无催化H2O2溶液，Na2MoO4催化在加快了将PhSMe氧化为PhS(O)Me的同时，也将过度氧化产物PhS(O)2Me的产率提高了两个数量级。95MoNMR测试表明，MoO42-与H2O2反应生成了钼酸盐过氧配合物MoOx(OO)(4-x)2-，当H2O2/ MoO42-＞5时，Mo (O2)42-是主要的活性物种，通过直接氧转移方式导致硫醚→亚砜→砜的氧化。 |
| 英文摘要: |
| In this paper, we studied the oxidation kinetics and products distribution of methyl phenyl sulfide (PhSMe), a commonly used simulant of mustard gas (HD), in aqueous H2O2 solution catalyzed by sodium molybdate. Methyl phenyl sulfoxide (PhS(O)Me) and methyl phenyl sulfone(PhS(O)2Me) are two oxidation products of PhSMe in the catalyzed H2O2 solution. The apparent rate constant of the primary oxidation (PhSMe→PhS(O)Me) (kap1) and secondary oxidation (PhS(O)Me→PhS(O)2Me) (kap2) in Na2MoO4-H2O2 solution are two orders of magnitude larger than kap1 and kap2 in alkali-modified H2O2 solution without any catalyst respectively. 95Mo NMR tests of the Na2MoO4-H2O2 solution indicate that MoOx(OO)(4-x)2- would be formed in the solution and Mo(O2)42- seems to be the major reactive intermediate at the mole ratio of H2O2/ MoO42-=10 used in the kinetic test. The yield of PhS(O)2Me on reaction time in Na2MoO4 catalyzed H2O2 solution is not significantly inhibited by free radical scavengers and antioxidants, and a direct oxygen transfer from O-O in Mo(O2)42- to the S atom is supposed to be responsible for the primary and secondary oxidation of sulfides. |
| HTML 查看全文 查看/发表评论 下载PDF阅读器 |
