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OH/OD Initiated Oxidation of Isoprene in the Presence of O_2 and NO

机译:O_2和NO存在下OH / OD引发的异戊二烯氧化

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摘要

The kinetics of the isoprene-OH/OD reaction in the presence of 02 and NO have been studied using laser photolysis/laser-induced fluorescence.We report pressure and temperature-dependent rate constants for the addition of OH/OD to isoprene are in good agreement with previous studies.On the basis of simulations to OH cycling curves,we find a value of(9.0(+-)3.0)x 10~(-12)molecule~(-1)cm~3 s~(-1)for the overall reaction rate constant of hydroxy peroxy radical with NO at 298 K.We report a rate constant for 02 addition to the hydroxy alkyl radical of(2.3(+-)2.0)x 10~(-1)2 molecule~(-1)cm~3 s~(-1)at 298 K.We find little generation of OH from the OD initiated oxidation of isoprene,and no significant differences in OH and OD cycling,suggesting that H-shift isomerization is the major pathway for d-hydroxy alkoxy radicals,in agreement with theoretical predictions.
机译:使用激光光解/激光诱导的荧光研究了在02和NO存在下异戊二烯-OH / OD反应的动力学,我们报告了在异戊二烯中添加OH / OD的压力和温度相关的速率常数在模拟OH循环曲线的基础上,我们得出(9.0(+-)3.0)×10〜(-12)分子〜(-1)cm〜3 s〜(-1)的值在298 K时羟基过氧自由基与NO的总反应速率常数。我们报告了(2.3(+-)2.0)x 10〜(-1)2分子〜(-在298 K时1)cm〜3 s〜(-1)。我们发现OD引发的异戊二烯氧化几乎不会产生OH,OH和OD循环也没有显着差异,这表明H转移异构化是产生H的主要途径d-羟基烷氧基自由基,与理论预测一致。

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