Rate constants of CH3O2 + NO2 CH3O2NO2 and C2H5O2 + NO2 C2H5O2NO2 reactions under atmospheric conditions
Rate constants of CH3O2 + NO2 CH3O2NO2 and C2H5O2 + NO2 C2H5O2NO2 reactions under atmospheric conditions
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大气条件下 CH3O2 NO2 CH3O2NO2 和 C2H5O2 NO2 C2H5O2NO2 反应的速率常数
DOI：
10.1002/kin.21466
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发表时间：
2020
影响因子：
1.5
通讯作者：
Kajii Yoshizumi
中科院分区：
文献类型：
--
作者：
Kohno Nanase;Li Jiaru;Sakamoto Yosuke;Kajii Yoshizumi
Peroxy (RO2) radicals derived from short‐chain alkanes were detected by an improved technique involving combined fluorescence assay by gas expansion and laser‐induced fluorescence (FAGE‐LIF) and chemical conversion under atmospheric conditions (298 K and 1 bar). The suitability of the system for measuring RO2kinetics was tested using the CH3O2+ NO2+ M CH3O2NO2+ M reaction. CH3O2radicals were generated by the OH + CH4→ CH3+ H2O reaction and subsequent O2addition. The CH3O2radicals were monitored using the LIF intensity of the OH radicals, which were converted from CH3O2radicals by chemical reaction with NO and O2. The decay rates of CH3O2radicals were measured at various NO2concentrations, and the bimolecular rate constant was determined to bek= (3.9 ± 0.3) × 10−12cm3molecule−1s−1. The result is consistent with the literature value, thus demonstrating the validity of the improved system. We also constructed a fitting equation for the simultaneous determination of the forward and reverse reaction rates because the thermal decomposition of CH3O2NO2was not negligible. From the global fitting analysis using the fitted equation, the decomposition rate of CH3O2NO2was determined to bek= 2.0 ± 0.6 s−1. Furthermore, we investigated the C2H5O2+ NO2+ M C2H5O2NO2+ M reaction. The forward reaction rate was approximately 1.7 times faster than that of the CH3O2+ NO2+ M reaction: = (6.5 ± 0.4) × 10−12cm3molecule−1s−1, and the reverse reaction rate was 3.6 ± 0.7 s−1. These results agree with the previous estimates.
