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Rate constants of CH3O2 + NO2 CH3O2NO2 and C2H5O2 + NO2 C2H5O2NO2 reactions under atmospheric conditions
International Journal of Chemical Kinetics ( IF 1.5 ) Pub Date : 2020-12-17 , DOI: 10.1002/kin.21466 Nanase Kohno 1 , Jiaru Li 1 , Yosuke Sakamoto 1, 2, 3 , Yoshizumi Kajii 1, 2, 3
International Journal of Chemical Kinetics ( IF 1.5 ) Pub Date : 2020-12-17 , DOI: 10.1002/kin.21466 Nanase Kohno 1 , Jiaru Li 1 , Yosuke Sakamoto 1, 2, 3 , Yoshizumi Kajii 1, 2, 3
Affiliation
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 RO2 kinetics was tested using the CH3O2 + NO2 + M 
CH3O2NO2 + M reaction. CH3O2 radicals were generated by the OH + CH4 → CH3 + H2O reaction and subsequent O2 addition. The CH3O2 radicals were monitored using the LIF intensity of the OH radicals, which were converted from CH3O2 radicals by chemical reaction with NO and O2. The decay rates of CH3O2 radicals were measured at various NO2 concentrations, and the bimolecular rate constant was determined to be k
= (3.9 ± 0.3) × 10−12 cm3 molecule−1 s−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 CH3O2NO2 was not negligible. From the global fitting analysis using the fitted equation, the decomposition rate of CH3O2NO2 was determined to be k
= 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) × 10−12 cm3 molecule−1 s−1, and the reverse reaction rate was 3.6 ± 0.7 s−1. These results agree with the previous estimates.
中文翻译：
CH3O2 + NO2的速率常数CH3O2NO2和C2H5O2 + NO2在大气条件下的C2H5O2NO2反应
通过改进的技术检测短链烷烃衍生的过氧（RO 2）自由基，该技术包括通过气体膨胀和激光诱导荧光（FAGE-LIF）进行的组合荧光测定以及在大气条件下（298 K和1 bar）的化学转化。使用CH 3 O 2 + NO 2 + M CH 3 O 2 NO 2 + M反应来测试系统测量RO 2动力学的适用性。通过OH + CH 4 →CH 3 + H 2 O反应和随后的O 2生成CH 3 O 2自由基添加。使用OH基团的LIF强度来监测CH 3 O 2基团，所述OHF基团通过与NO和O 2的化学反应从CH 3 O 2基团转化而来。在不同的NO 2浓度下测量CH 3 O 2自由基的衰减速率，确定双分子速率常数为k =（3.9±0.3）×10 -12 cm 3 分子-1 s -1。结果与文献报道值相吻合，证明了改进后系统的有效性。由于CH 3 O 2 NO 2的热分解不可忽略，因此我们还建立了一个拟合方程，用于同时确定正向和反向反应速率。通过使用拟合方程的整体拟合分析，确定CH 3 O 2 NO 2的分解速率为k = 2.0±0.6 s -1。此外，我们研究了C 2 H 5 O 2 + NO 2 + M C 2 H 5O 2 NO 2 + M反应。正向反应速率比CH 3 O 2 + NO 2 + M反应快大约1.7倍： =（6.5±0.4）×10 -12 cm 3 分子-1 s -1，反向反应速率是3.6 ±0.7 s -1。这些结果与先前的估计相符。
更新日期：2020-12-17
CH3O2NO2 + M reaction. CH3O2 radicals were generated by the OH + CH4 → CH3 + H2O reaction and subsequent O2 addition. The CH3O2 radicals were monitored using the LIF intensity of the OH radicals, which were converted from CH3O2 radicals by chemical reaction with NO and O2. The decay rates of CH3O2 radicals were measured at various NO2 concentrations, and the bimolecular rate constant was determined to be k = (3.9 ± 0.3) × 10−12 cm3 molecule−1 s−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 CH3O2NO2 was not negligible. From the global fitting analysis using the fitted equation, the decomposition rate of CH3O2NO2 was determined to be k = 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) × 10−12 cm3 molecule−1 s−1, and the reverse reaction rate was 3.6 ± 0.7 s−1. These results agree with the previous estimates.
中文翻译：
CH3O2 + NO2的速率常数CH3O2NO2和C2H5O2 + NO2在大气条件下的C2H5O2NO2反应
通过改进的技术检测短链烷烃衍生的过氧（RO 2）自由基，该技术包括通过气体膨胀和激光诱导荧光（FAGE-LIF）进行的组合荧光测定以及在大气条件下（298 K和1 bar）的化学转化。使用CH 3 O 2 + NO 2 + M CH 3 O 2 NO 2 + M反应来测试系统测量RO 2动力学的适用性。通过OH + CH 4 →CH 3 + H 2 O反应和随后的O 2生成CH 3 O 2自由基
添加。使用OH基团的LIF强度来监测CH 3 O 2基团，所述OHF基团通过与NO和O 2的化学反应从CH 3 O 2基团转化而来。在不同的NO 2浓度下测量CH 3 O 2自由基的衰减速率，确定双分子速率常数为k =（3.9±0.3）×10 -12 cm 3 分子-1 s -1。结果与文献报道值相吻合，证明了改进后系统的有效性。由于CH 3 O 2 NO 2的热分解不可忽略，因此我们还建立了一个拟合方程，用于同时确定正向和反向反应速率。通过使用拟合方程的整体拟合分析，确定CH 3 O 2 NO 2的分解速率为k = 2.0±0.6 s -1。此外，我们研究了C 2 H 5 O 2 + NO 2 + M C 2 H 5O 2 NO 2 + M反应。正向反应速率比CH 3 O 2 + NO 2 + M反应快大约1.7倍： =（6.5±0.4）×10 -12 cm 3 分子-1 s -1，反向反应速率是3.6 ±0.7 s -1。这些结果与先前的估计相符。
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