Extreme Low-Temperature Combustion Chemistry: Ozone-Initiated Oxidation of Methyl Hexanoate

The accelerating chemical effect of ozone addition on the oxidation chemistry of methyl hexanoate [CH3(CH2)4C(= O)OCH3] was investigated over a temperature range from 460 to 940 K. Using an externally heated jet-stirred reactor at p = 700 Torr (residence time τ = 1.3 s, stoichiometry ψ = 0.5, 80% argon dilution), we explored the relevant chemical pathways by employing molecular-beam mass spectrometry with electron and single-photon ionization to trace the temperature dependencies of key intermediates, including many hydroperoxides. In the absence of ozone, reactivity is observed in the so-called low-temperature chemistry (LTC) regime between 550 and 700 K, which is governed by hydroperoxides formed from sequential O2 addition and isomerization reactions. At temperatures above 700 K, we observed the negative temperature coefficient (NTC) regime, in which the reactivity decreases with increasing temperatures, until near 800 K, where the reactivity increases again. Upon addition of ozone (1000 ppm), the overall reactivity of the system is dramatically changed due to the time scale of ozone decomposition in comparison to fuel oxidation time scales of the mixtures at different temperatures. While the LTC regime seems to be only slightly affected by the addition of ozone with respect to the identity and quantity of the observed intermediates, we observed an increased reactivity in the intermediate NTC temperature range. Furthermore, we observed experimental evidence for an additional oxidation regime in the range near 500 K, herein referred to as the extreme low-temperature chemistry (ELTC) regime. Experimental evidence and theoretical rate constant calculations indicate that this ELTC regime is likely to be initiated by H abstraction from methyl hexanoate via O atoms, which originate from thermal O3 decomposition. The theoretical calculations show that the rate constants for methyl ester initiation via abstraction by O atoms increase dramatically with the size of the methyl ester, suggesting that ELTC is likely not important for the smaller methyl esters. Experimental evidence is provided indicating that, similar to the LTC regime, the chemistry in the ELTC regime is dominated by hydroperoxide chemistry. However, mass spectra recorded at various reactor temperatures and at different photon energies provide experimental evidence of some differences in chemical species between the ELTC and the LTC temperature ranges.