Rate constants for the reaction of ozone with n-butyl, s-butyl and t-butyl methyl sulfides

The rate constants for the ozone reactions with n-butyl methyl sulfide (n-BMS, CH3CH2CH2CH2SCH3), sec-butyl methyl sulfide (s-BMS, CH3CH2(CH3)CHSCH3) and tert-butyl methyl sulfide (t-BMS, (CH3)3CSCH3) were measured using our smog chamber under supposedly pseudo-first-order conditions at 300±2 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are (1.23 ± 0.06)×10-19, (5.08 ± 0.19)×10?20 and (2.26 ± 0.14)×10?20 cm3·molecule-1·s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.

臭氧氧化MTBE反应动力学及其特性研究

文章针对汽油添加剂甲基叔丁基醚对环境日益严重的污染问题,在臭氧氧化MTBE反应机理研究的基础上,对反应特性及其中间产物进行了研究。动力学研究与实验结果均表明,O3氧化MTBE为准二级反应,加入H2O2,能降低反应活化能,提高反应速率,减少臭氧投加量;采用GC/FID检测MTBE及其氧化产物,以GC保留时间确定臭氧氧化MTBE的可能中间产物为叔丁醇、叔丁基甲酯及丙酮等。