Preprints
https://doi.org/10.5194/egusphere-2024-920
https://doi.org/10.5194/egusphere-2024-920
28 Mar 2024
 | 28 Mar 2024

Ether and ester formation from peroxy radical recombination: A qualitative reaction channel analysis

Lauri Johannes Franzon, Marie Camredon, Richard Valorso, Bernard Aumont, and Theo Christian Kurtén

Abstract. The least volatile organic compounds participating in atmospheric new-particle formation are very likely accretion products from self- and cross-reactions of peroxy radicals (RO2). It has long been assumed that the only possible accretion product channel in this reaction is that forming a peroxide (RO2 + RO2 → ROOR + O2), but it has recently been discovered that a rapid alkoxy radical (RO) decomposition may precede the accretion step of the mechanism, forming slightly fragmented but more stable ether (ROR) or ester (RC'(O)OR) accretion products. In this work, the atmospheric implications of this new reaction channel have been explored further using a modified version of the GECKO-A software to generate a large amount of representative RO2 + RO2 reactive pairs formed from the oxidation of typical primary hydrocarbons, and applying Structure-activity relationships (SAR) to predict the potential accretion products. This data is analysed in terms of formation of low-volatility products, and new discoveries are presented on what kind of RO2 are especially efficient (and which are surprisingly inefficient) at forming accretion products. These findings are discussed in terms of atmospheric relevance of these new RO2 + RO2 reaction channels. As the generation of this data rests on several simplifications and assumptions, many open questions worthy of later studies are also raised.

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Lauri Johannes Franzon, Marie Camredon, Richard Valorso, Bernard Aumont, and Theo Christian Kurtén

Status: final response (author comments only)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on egusphere-2024-920', William Carter, 08 Apr 2024
  • RC2: 'Comment on egusphere-2024-920', Anonymous Referee #2, 02 Jul 2024
Lauri Johannes Franzon, Marie Camredon, Richard Valorso, Bernard Aumont, and Theo Christian Kurtén
Lauri Johannes Franzon, Marie Camredon, Richard Valorso, Bernard Aumont, and Theo Christian Kurtén

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Short summary
In this article we investigate the formation of large, sticky molecules from various organic compounds entering the atmosphere as primary emissions, and the degree to which these processes may contribute to organic aerosol particle mass. More specifically, we are qualitatively investigating a recently discovered chemical reaction channel for one of the most important short-lived radical compounds, peroxy radicals, and discovering which of these reactions are most atmospherically important.