Constraining the Low-Temperature Oxidation Mechanism of n-Hexanol through the Detection and Identification of C6 Elusive Intermediates

Alcohol-based fuels are currently considered to be viable energy carriers for the transportation sector. Consequently, a comprehensive mechanistic understanding of the low-temperature oxidation of alcohols is essential for application in advanced low-temperature compression engines. In this work, a multidimensional approach involving experimental investigations, kinetic modeling, and theoretical calculations was used to provide new insights into the low-temperature oxidation mechanism of a C6 alcohol, n-hexanol (CH3(CH2)5OH), through the detection and identification of elusive C6 intermediates. The oxidation of n-hexanol was investigated in a jet-stirred reactor under stoichiometric conditions (ϕ = 1.0), an initial fuel concentration of 2%, a residence time of 2 s, a temperature range between 500 and 660 K, and a pressure of 700 Torr. The reactants, intermediates, and final products were detected and identified by means of molecular-beam mass spectrometry coupled with single-photon ionization employing tunable synchrotron-generated vacuum ultraviolet radiation. Chemical kinetic simulations were performed using a previously published kinetic model (Togbé et al., Energy Fuels 2010, 11, 5859−5875) to predict the reactivity of n-hexanol and elucidate the predominant formation pathways of the observed low-temperature species. Experimental photoionization efficiency curves in conjunction with ab initio calculations, enabled the identification of important low-temperature species, such as C6 unsaturated alcohols, C6 olefinic hydroperoxides, C6 cyclic ethers, C6 diones, and C6 ketohydroperoxides. The results of this study provide valuable insight into the mechanism of the low-temperature oxidation chemistry of n-hexanol, contributing to the development of kinetic models for the low-temperature oxidation of n-hexanol and other long-chain linear alcohols.