Accretion product formation in the self-reaction of ethene-derived hydroxy peroxy radicals
Accretion product formation in the self-reaction of ethene-derived hydroxy peroxy radicals
复制标题
乙烯衍生的羟基过氧自由基自反应中的吸积产物形成
DOI：
10.1039/d3ea00020f
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Wennberg, Paul O.
中科院分区：
文献类型：
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作者：
Murphy, Sara E.;Crounse, John D.;Møller, Kristian H.;Rezgui, Samir P.;Hafeman, Nicholas J.;Park, James;Kjaergaard, Henrik G.;Stoltz, Brian M.;Wennberg, Paul O.
在这项研究中，我们回顾了最简单的反应之一：乙烯衍生的羟基过氧基的自我反应，通过·OH和O2与乙烯的顺序加成而形成。以前对该反应的研究表明，分支到“增长产物”的分支很少，“增长产物”是包含两个反应物的碳主干的化合物。在这里，CF3O−GC-CIMS被用来定量乙二醇、乙醇醛、由其产生的羟基过氧化氢和C4O4H10吸积产物的产率。这些实验是在993hpa和294K的环境室中进行的。我们提供了证据，证明吸积产物很可能是二羟基二乙基过氧化氢(HOC2H4OOC2H4OH ROOR)，并在气相中形成，支化分数为23±5%。我们建议化学中的一种新的通道直接导致(与乙醇醛和烷氧基一起)的形成。最后，通过改变和在我们的小室中的形成速率的比例，我们限制了反应的速率系数与反应的速率系数的比例，发现该比例为0.22±0.07，与以前的闪光光解研究一致。
In this study we revisit one of the simplest reactions: the self-reaction of the ethene-derived hydroxyperoxy radical formed via sequential addition of ˙OH and O2 to ethene. Previous studies of this reaction suggested that the branching to ‘accretion products’, compounds containing the carbon backbone of both reactants, was minimal. Here, CF3O− GC-CIMS is used to quantify the yields of ethylene glycol, glycolaldehyde, a hydroxy hydroperoxide produced from , and a C4O4H10 accretion product. These experiments were performed in an environmental chamber at 993 hPa and 294 K. We provide evidence that the accretion product is likely dihydroxy diethyl peroxide (HOC2H4OOC2H4OH ROOR) and forms in the gas-phase with a branching fraction of 23 ± 5%. We suggest a new channel in the chemistry leading directly to the formation of (together with glycolaldehyde and an alkoxy radical). Finally, by varying the ratio of the formation rate of and in our chamber, we constrain the ratio of the rate coefficient for the reaction of to that of and find that this ratio is 0.22 ± 0.07, consistent with previous flash photolysis studies.