Influence of temperature and resonance-stabilization on the ortho -effect in cymene oxidation
Proceedings of the Combustion Institute(2015)
Abstract
Cymenes are monoterpene derivatives composed of a benzene ring with iso-propyl and methyl substituents, and the proximity of the two alkyl groups enables relevant analysis into the ortho-effect of polysubstituted aromatics, in which low-temperature autoignition is more facile for ortho-substitution. The initial steps of ROO-related reactions from Cl-initiated oxidation of ortho-, meta- and para-cymene were studied at low pressure (8Torr) over the temperature range 450–750K using multiplexed photoionization mass spectrometry (MPIMS). Ratios of cyclic ether formation (related to chain-propagation and OH formation) relative to HO2-loss (related to chain-termination) were measured to characterize the ortho-effect as a function of temperature. The main results are twofold:
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Key words
Cymenes,Monoterpene biofuel,Low-temperature oxidation,Ortho-effect,Resonance-stabilized radicals
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