The reaction of fuel radicals with O2 is critical in controlling low-temperature autoignition in compression ignition engines, because product channels forming chain-terminating HO2 radicals compete with channels producing chain-propagating or chain-branching OH radicals. Using photoionization mass spectrometry with synchrotron-generated vacuum ultraviolet radiation as the photon source, we probed isomer-resolved product formation from the reaction of O2 with hydroxyalkyl radicals derived from C4 and C5 alcohols. We discuss the main pathways in these reactions and highlight how the alcoholic �OH group alters the reactivity when compared to alkane oxidation. Furthermore, we present evidence of a new pathway leading to the elimination of water, which we propose to be ubiquitous in alcohol oxidation.

Pathways in the low-temperature oxidation chemistry of alcohols

245th National Meeting (2013)

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