Issue 5, 2023

Accretion product formation in the self-reaction of ethene-derived hydroxy peroxy radicals

Abstract

In this study we revisit one of the simplest Image ID:d3ea00020f-t1.gif 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 Image ID:d3ea00020f-t2.gif, 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 [double bond, length as m-dash]ROOR) and forms in the gas-phase with a branching fraction of 23 ± 5%. We suggest a new channel in the Image ID:d3ea00020f-t3.gif chemistry leading directly to the formation of Image ID:d3ea00020f-t4.gif (together with glycolaldehyde and an alkoxy radical). Finally, by varying the ratio of the formation rate of Image ID:d3ea00020f-t5.gif and Image ID:d3ea00020f-t6.gif in our chamber, we constrain the ratio of the rate coefficient for the reaction of Image ID:d3ea00020f-t7.gif to that of Image ID:d3ea00020f-t8.gif and find that this ratio is 0.22 ± 0.07, consistent with previous flash photolysis studies.

Graphical abstract: Accretion product formation in the self-reaction of ethene-derived hydroxy peroxy radicals

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Article information

Article type
Paper
Submitted
07 Feb 2023
Accepted
19 Mar 2023
First published
20 Mar 2023
This article is Open Access
Creative Commons BY license

Environ. Sci.: Atmos., 2023,3, 882-893

Accretion product formation in the self-reaction of ethene-derived hydroxy peroxy radicals

S. E. Murphy, J. D. Crounse, K. H. Møller, S. P. Rezgui, N. J. Hafeman, J. Park, H. G. Kjaergaard, B. M. Stoltz and P. O. Wennberg, Environ. Sci.: Atmos., 2023, 3, 882 DOI: 10.1039/D3EA00020F

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