New insights into the low-temperature oxidation of 2-methylhexane

In this work, we studied the low-temperature oxidation of a stoichiometric 2-methylhexane/O-2/Ar mixture in a jet-stirred reactor coupled with synchrotron vacuum ultraviolet photoionization molecular-beam mass spectrometry. The initial gas mixture was composed of 2% 2-methyhexane, 22% O-2 and 76% Ar and the pressure of the reactor was kept at 780 Torr. Low-temperature oxidation intermediates with two to five oxygen atoms were observed. The detection of C7H14O5 and C7H12O4 species suggests that a third O-2 addition process occurs in 2-methylhexane low-temperature oxidation. A detailed kinetic model was developed that describes the third O-2 addition and subsequent reactions leading to C7H14O5 (keto-dihydroperoxide and dihydroperoxy cyclic ether) and C7H12O4 (diketo-hydroperoxide and keto-hydroperoxy cyclic ether) species. The kinetics of the third O-2 addition reactions are discussed and model calculations were performed that reveal that third O-2 addition reactions promote 2-methylhexane auto-ignition at low temperatures. (C) 2016 by The Combustion Institute. Published by Elsevier Inc.