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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Kinetics of the Reaction of CH3O2 Radicals with OH Studied over the 292-526 K Temperature Range
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Kinetics of the Reaction of CH3O2 Radicals with OH Studied over the 292-526 K Temperature Range

机译：在292-526 K温度范围内研究CH3O2自由基与OH反应的动力学

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摘要

Reaction of methyl peroxy radicals with hydroxyl radicals, CH3O2 + OH -> CH3O + HO2 (1a) and CH3O2 + OH -> CH2OO + H2O (1b) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 292-526 K temperature range and pressure 1 bar (bath gas He). Hydroxyl radicals were generated in the reaction of electronically excited oxygen atoms O(D-1), produced in the photolysis of N2O at 193.3 nm, with H2O. Methyl peroxy radicals were generated in the reaction of methyl radicals, CH3, produced in the photolysis of acetone at 193.3 nm, and subsequent reaction of CH3 with O-2. Temporal profiles of OH were monitored via transient absorption of light from a DC discharge H2O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The overall rate constant of the reaction is k(1a+1b) = (8.4 +/- 1.7) x 10(-11)(T/298 K)(-0.81) cm(3) molecule(-1) s(-1) (292-526 K). The branching ratio of channel 1b at 298 K is less than 5%.
机译：使用脉冲激光光解耦合瞬态UV-vis吸收光谱在292-上研究了甲基过氧自由基与羟基自由基CH3O2 + OH-> CH3O + HO2（1a）和CH3O2 + OH-> CH2OO + H2O（1b）的反应526 K温度范围和压力1 bar（浴气体He）。在电子激发的氧原子O（D-1）与H2O在193.3 nm的N2O的光解反应中产生了羟基自由基。甲基过氧自由基是在193.3 nm的丙酮光解过程中产生的甲基自由基CH3反应中生成的，随后CH3与O-2反应。通过瞬时吸收来自直流放电H2O / Ar低压共振灯的光来监测OH的时间分布。 308纳米基于分子氧存在下臭氧的形成，通过精确的原位光度法确定光解光的绝对强度。反应的总速率常数为k（1a + 1b）=（8.4 +/- 1.7）x 10（-11）（T / 298 K）（-0.81）cm（3）分子（-1）s（- 1）（292-526 K）。通道1b在298 K处的分支比小于5％。

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