Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts

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Abstract

Peroxy (RO 2 ) and alkoxy (RO) radicals are prototypical intermediates in any hydrocarbon oxidation. In this work, we use computational methods to (1) study the mechanism and kinetics of the RO 2 + OH reaction for previously unexplored "R" structures (R = CH(O)CH 2 and R = CH 3 C(O)) and (2) investigate a hitherto unaccounted channel of molecular growth, R′O 2 + RO. On the singlet surface, these reactions rapidly form ROOOH and R′OOOR adducts, respectively. The former decomposes to RO + HO 2 and R(O)OH + O 2 products, while the main decomposition channel for the latter is back to the reactant radicals. Decomposition rates of R′OOOR adducts varied between 103 and 0.015 s -1 at 298 K and 1 atm. The most long-lived R′OOOR adducts likely account for some fraction of the elemental compositions detected in the atmosphere that are commonly assigned to stable covalently bound dimers.

Original languageEnglish
Pages (from-to)2051-2057
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume10
Issue number9
DOIs
Publication statusPublished - 2 May 2019
Publication typeA1 Journal article-refereed

Publication forum classification

  • Publication forum level 3

ASJC Scopus subject areas

  • General Materials Science
  • Physical and Theoretical Chemistry

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