H_2O_2/[C_nMIm]HCO_3对CEES的消毒动力学及机理  

Kinetics and Mechanism of Decontamination Reaction of CEES in H_2O_2/[C_nMIm]HCO_3

作　　者：王志成[1] 习海玲[1,2] 孔令策[1] 赵三平[1] 左言军[1] 

机构地区：[1]防化研究院 [2]国民核生化灾害防护国家重点实验室,北京102205

出　　处：《高等学校化学学报》2016年第12期2191-2198,共8页Chemical Journal of Chinese Universities

基　　金：国民核化生灾害防护国家重点实验室项目(批准号:SKLNBC2012-09)资助~~

摘　　要：合成了4种不同烷基链长的1-烷基-3-甲基咪唑碳酸氢盐([C_nMIm]HCO_3,n=2,4,6,8)离子液体(ILs),并以H_2O_2水溶液(质量分数30%)为氧化剂,研究了H_2O_2在[C_nMIm]HCO_3离子液体、H_2O和C_2H_5OH中对芥子气模拟剂2-氯乙基乙基硫醚(CEES)的消毒能力,考察了离子液体烷基链长、H_2O_2/CEES摩尔比和反应温度对消毒率的影响,并对反应活化能和产物进行了分析.结果表明,H_2O_2在不同溶剂中对CEES的消毒能力依次为[BMIm]HCO_3>[EMIm]HCO_3>[HMIm]HCO_3>[OMIm]HCO_3>C2H5OH>H2O.对于CEES在[BMIm]HCO_3中形成的20 mg/m L的毒剂溶液,当n(H_2O_2)∶n(CEES)=10时,H_2O_2可在30 min内消毒99.58%的CEES,且该体系具有一定的低温(243 K)消毒能力.该反应为一级反应,活化能为15.59k J/mol,低于单一过碳酸钠与CEES的反应活化能.化学发光测试结果表明,在碳酸氢根活化过氧化氢(BAP)体系中,咪唑基离子液体可抑制亚砜被超氧阴离子(·O_2^-)过度氧化为砜.A series of environmentally benign 1-n-alkyl-3-methylimidazolium bicarbonate ionic liquids（ILs）（[CnMIm]HCO3,n = 2,4,6,8） was synthesized and hydrogen peroxide was employed in decontamination against 2-chloroethyl ethyl sulfide（CEES,a mustard agent simulant） in these ILs. The influencing factors such as ILs alkyl chain length,oxidant/CEES molar ratio and temperature were tested and the activation energy,reaction product in H2O2/[BMIm]HCO3was analyzed. The results indicated that the solvents species can affect decontamination efficacy against CEES and they were in the following sequences： [BMIm]HCO3〉[EMIm]HCO3〉[HMIm]HCO3〉[OMIm]HCO3〉C2H5OH〉 H2 O. In H2O2/[BMIm]HCO3 system,99. 58%of the CEES was oxidized mainly to corresponding sulfoxide after 30 min at the concentration of 20 mg/m L and O/S molar ratio of 10. The apparent activation energy of CEES oxidized by H2O2/[BMIm]HCO3was 15. 59 k J/mol. Moreover,the superoxide radical anion（·O-2） could be produced and oxidized ILs to 2-imidazolone,which inhibited the formation of corrosive sulfone. The result indicated that H2O2/[BMIm]HCO3system may be a new option for decontamination against CEES.

关 键 词：离子液体 洗消 2-氯乙基乙基硫醚 碳酸氢根活化过氧化氢 

分 类 号：O643.11[理学—物理化学]