Symmetric Ethers as Bioderived Fuels: Reactivity with OH Radicals

Environmental pollution and greenhouse gas emissions are major challenges faced by our society. One possible way to mitigate global warming is to cut CO2 emissions by taking a shift from conventional fuels to renewable fuels for future sustainability. Carbon neutral fuels produced in a sustainable carbon cycle can close the carbon cycle and reach net zero-carbon emission. To this end, ethers are promising renewable fuels and/or additives for future advanced combustion engines. Therefore, understanding the oxidation behavior of ethers under engine-relevant conditions is of utmost importance. In this work, the reaction kinetics of hydroxyl radicals with dimethyl ether (DME), diethyl ether (DEE), di-n-propyl ether (DPE), and di-n-butyl ether (DBE) were investigated behind reflected shock waves over the temperature range of 865–1381 K and the pressure range of 0.96–5.56 bar using a shock tube and a UV laser diagnostic technique. Hydroxyl radicals were monitored near 306.7 nm to follow the reaction kinetics. These reactions did not exhibit discernible pressure effects. The temperature dependence of the measured rate coefficients can be expressed by the following modified Arrhenius equations in units of cm3 mol–1 s–1: k1(DME+OH) = 1.19 × 1014 exp(−2469.8/T), k2(DEE+OH) = 1.27 × 107T2 exp(327.8/T), k3(DPE+OH) = 1.64 × 107T2 exp(368.4/T), k4(DBE+OH) = 9.12 × 1011T0.65 exp(−843.5/T). Our measured rate data were analyzed to obtain site-specific rates and branching ratios. Our results are compared with the available literature data wherever applicable. Furthermore, the ability of Atkinson’s structure–activity relationship (SAR) to predict the kinetic behavior of the reactions of dialkyl ethers with OH radicals was examined.