过碳酸钠/钼酸钠体系对2-氯乙基乙基硫醚的降解机理与动力学研究
KINETICS AND MECHANISM OF THE DEGRADATION REACTION OF 2-CHLORORTHYL ETHYL SULFIDE BY SODIUM PERCARBONATE/ SODIUM MOLYBDATE
-
摘要: 研究了不同温度下过碳酸钠/钼酸钠体系和单一过碳酸钠对芥子气模拟剂2-氯乙基乙基硫醚(2-CEES)降解动力学规律,建立了相应的反应速率方程;利用液质联用技术分析了降解产物,并利用顺磁共振技术检测了过碳酸钠/钼酸钠体系产生的活性成分,推测了反应机理.结果表明,两种体系对2-CEES降解反应均为一级反应,过碳酸钠/钼酸钠体系对2-CEES消毒的活化能为8.36 kJ·mol-1,单一过碳酸钠对2-CEES降解的活化能为44.73 kJ·mol-1,添加钼酸钠能有效降低反应活化能,提高反应速率;主要降解产物为C2H5S(O)C2H4OH、C2H5S(O)C2H4Cl、C2H5S(O2)C2H4OH以及C2H5S(O)C2H3,体系产生的主要活性物种为单线态氧1O2,推测反应同时存在水解与氧化反应.Abstract: The kinetics of degradation reaction of 2-chlororthyl ethyl sulfude(2-CEES)in sodium percarbonate/sodium molybdate system and single sodium percarbonate were studied at different temperatures, and the corresponding reaction rate was calculated. The reaction mechanism was proposed based on the analysis of the degradation products by LC-MS and reactive species by ESR.The results show that both systems are first-order reactions. The activation energy of sodium percarbonate/sodium molybdate on 2-CEES degradation is 8.36 kJ·mol-1,and that of single sodium percarbonate is 44.73 kJ·mol-1. The activation energy was reduced and the reaction rate was improved by adding sodium molybdate.The main degradation products are C2H5S(O)C2H4OH,C2H5S(O)C2H4Cl,C2H5S(O2)C2H4OH and C2H5S(O)C2H3. The main reactive species is singlet oxygen. The reaction mechanism is suggested to be a concerted reaction of hydrolysis and oxidation.
-
Key words:
- 2-chloroethyl ethyl sulfide /
- sodium percarbonate /
- sodium molybdate /
- kinetics /
- mechanism
-
-
[1] 赵国辉,寿伟椿. 军用毒剂化学[M]. 北京:防化指挥工程学院,1985 [2] 宗清文.过碳酸钠的合成及应用[J].实验技术与管理,2000,6:57-59 [3] Aubry J M.Search for singlet oxygen in the decomposition of hydrogen peroxide by mineral compounds in aqueous solutions[J].J Am Chem Soc,1985,107:5844-5849 [4] Aubry J M.Bouttemy,S. Preparative oxidation of organic compounds in microemulsions with singlet oxygen generated chemically by the sodium molybdate/hydrogen peroxide system[J].J Am Chem Soc, 1997,119:5286-5294 [5] Wagner G W, Procell L R, Yang Y C,et al. Molybdate/peroxide oxidation of mustard in microemulsions[J]. Langmuir,2001,17:4809-4811 [6] [7] 董元彦,李宝华,路福绥.物理化学[M].北京:科学教育出版社,2001 [8] Aubry J M.Chemical sources of singlet oxygen. 3.Peroxidation of water-soluble singlet oxygen carriers with the hydrogen peroxide-molybdate system[J]. J Org Chem,1989, 54:726-728 [9] Niu Q J, Foote C S.Singlet molecular oxygen generation from the decomposition of sodium peroxotungstate and sodium peroxomolybdate[J]. Inorg Chem,1992, 31:3472-3476 -
点击查看大图
计量
- 文章访问数: 819
- HTML全文浏览数: 750
- PDF下载数: 438
- 施引文献: 0
下载:
