H_2O_2/[C_nMIm]HCO_3对CEES的消毒动力学及机理

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_3EMIm]HCO_3HMIm]HCO_3OMIm]HCO_3C2H5OHH2O.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.

Kinetics and Mechanism of Decontamination Reaction of CEES in H2O2/[ CnMIm] HCO3?

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] HCO3 was 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> H2O. 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/mL and O/S molar ratio of 10. The apparent activation energy of CEES oxidized by H2O2/BMIm]HCO3 was 15?59 kJ/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]HCO3 system may be a new option for decontamination against CEES.