Radical Reactivity in the Condensed Phase: Intermolecular versus Intramolecular Reactions of Alkoxy Radicals.

ABSTRACT: Condensed-phase alkoxy (RO) radicals can undergo unimolecular (e.g., intramolecular H atom abstraction) reactions as well as bimolecular (intermolecular H atom abstraction) reactions, though the competition between these two channels is not well constrained. Here, we examine this branching by generating RO radicals from the photolysis of a large alkyl nitrite (C20H41ONO) in hexanes and nebulizing the mixture into an aerosol mass spectrometer for analysis. Product ions associated with unimolecular (isomerization) reactions were observed to increase upon photolysis. However, no formation of the C20 alcohol (C20H41OH, the expected product from RO + RH reactions) was observed, suggesting that bimolecular reactions are at most a minor channel for this condensed-phase system (involving saturated

SUBMITTER: Carrasquillo AJ 

PROVIDER: S-EPMC5348301 | biostudies-literature | 2015 Jun

REPOSITORIES: biostudies-literature