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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >On the Uncertainties in the Rate Coefficients for OH Reactions with Hydrocarbons, and the Rate Coefficients of the 1,3,5-Trimethylbenzene and m-Xylene Reactions with OH Radicals in the Gas Phase
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On the Uncertainties in the Rate Coefficients for OH Reactions with Hydrocarbons, and the Rate Coefficients of the 1,3,5-Trimethylbenzene and m-Xylene Reactions with OH Radicals in the Gas Phase

机译：气相中OH与烃类反应的速率系数的不确定性以及气相中OH基与1,3,5-三甲苯和间二甲苯反应的速率系数的不确定性

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摘要

Rate coefficients for the gas-phase reactions of 1,3,5-trimethylbenzene (TMB) and m-xylene with the OH radical relative to 10 reference compounds were measured yielding (57.3 ±5.3) × l0↑(-12) and (22.0 ± 2.7) × 10↑(-12) cm↑(3) molecule↑-1) s250L?-1), respectively (uncertainties are 2σ). These uncertainties arise from a combination of the uncertainty of the reference rate coefficients and experimental errors; thus, the average uncertainty for the rate coefficients of the 10 reference compounds must be less than or equal to the scatter observed in this study. For 16 and 21 measurements with TMB and m-xylene, the observed scatter was ±10% and ±12%, respectively. The average of the uncertainties is significantly smaller than the uncertainties that are frequently assumed or recommended, which range from ±15 to 35%. Absolute rate coefficients for the reaction of TMB and m-xylene with ozone are also reported. Relative rate coefficients for reaction with OH for di-n-butyl ether, methylcyclohexane, cyclopentane, toluene, and cyclohexane of 28.9 ±2.3, 9.4 ±0.6, 4.8 ±0.6, 5.5 ±0.5, and 7.2 ±0.6 (× 10↑(-12) cm↑(3) molecule↑(-1) s↑(-1)) were also measured (uncertainties indicate the whole range of scatter).
机译：测量了1,3,5-三甲苯（TMB）和间二甲苯与OH自由基的气相反应相对于10种参考化合物的速率系数，得出（57.3±5.3）×10↑（-12）和（22.0分别为±2.7）×10↑（-12）cm↑（3）分子↑-1）s250L？-1）（不确定度为2σ）。这些不确定性来自参考速率系数的不确定性和实验误差的结合;因此，这10种参考化合物的速率系数的平均不确定度必须小于或等于本研究中观察到的散射。对于使用TMB和间二甲苯进行的16次和21次测量，观察到的散射分别为±10％和±12％。不确定度的平均值明显小于通常假定或推荐的不确定度，其范围为±15％至35％。还报道了TMB和间二甲苯与臭氧反应的绝对速率系数。与OH反应的二正丁基醚，甲基环己烷，环戊烷，甲苯和环己烷的相对速率系数为28.9±2.3、9.4±0.6、4.8±0.6、5.5±0.5和7.2±0.6（×10↑（- 12）cm↑（3）分子↑（-1）s↑（-1））也进行了测量（不确定性表明整个散射范围）。

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