Direct kinetic measurement of the reaction of the simplest Criegee intermediate with water vapor

被引:252
作者
Chao, Wen [1 ,2 ]
Hsieh, Jun-Ting [1 ,3 ]
Chang, Chun-Hung [1 ]
Lin, Jim Jr-Min [1 ,2 ,4 ]
机构
[1] Acad Sinica, Inst Atom & Mol Sci, Taipei 10617, Taiwan
[2] Natl Taiwan Univ, Dept Chem, Taipei 10617, Taiwan
[3] Stanford Univ, Stanford, CA 94305 USA
[4] Natl Chiao Tung Univ, Dept Appl Chem, Hsinchu 30010, Taiwan
关键词
GAS-PHASE OZONOLYSIS; ABSORPTION-SPECTRUM; CARBONYL OXIDES; CH2OO; ACID; SO2; ALKENES; YIELD; ETHENE; OZONE;
D O I
10.1126/science.1261549
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Carbonyl oxides, or Criegee intermediates, are important transient species formed in the reactions of unsaturated hydrocarbons with ozone. Although direct detection of Criegee intermediates has recently been realized, the main atmospheric sink of Criegee intermediates remains unclear. We report ultraviolet absorption spectroscopic measurements of the lifetime of the simplest Criegee intermediate, CH2OO, at various relative humidity levels up to 85% at 298 kelvin. An extremely fast decay rate of CH2OO was observed at high humidity. The observed quadratic dependence of the decay rate on water concentration implied a predominant reaction with water dimer. On the basis of the water dimer equilibrium constant, the effective rate coefficient of the CH2OO + (H2O)(2) reaction was determined to be 6.5 (+/-0.8) x 10(-12) cubic centimeters per second. This work would help modelers to better constrain the atmospheric concentrations of CH2OO.
引用
收藏
页码:751 / 754
页数:4
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