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Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts

Tutkimustuotosvertaisarvioitu

Yksityiskohdat

AlkuperäiskieliEnglanti
Sivut2051-2057
Sivumäärä7
JulkaisuJournal of Physical Chemistry Letters
Vuosikerta10
Numero9
DOI - pysyväislinkit
TilaJulkaistu - 2 toukokuuta 2019
OKM-julkaisutyyppiA1 Alkuperäisartikkeli

Tiivistelmä

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.

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