An experimental and kinetic modeling investigation on low‐temperature oxidation chemistry of 1,3,5‐trimethylcyclohexane in a jet‐stirred reactor

Very scarce studies aiming at the low-temperature chemistry of multi-alkylated cycloalkanes were reported until now, which widely exist in real transportation fuels. Thus, this work presents the first study on the low-temperature oxidation characteristics of 1,3,5-trimethylcyclohexane (T135MCH) in an atmospheric jet-stirred reactor (JSR) combined with synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) at fuel-lean (ϕ = 0.5), stoichiometric (ϕ = 1.0) and fuel-rich (ϕ = 1.5) conditions. Abundant quantitative information of species is acquired including reactants, major products, reactive hydroperoxides, fuel-specific cycloalkenes and other C₁–C₅ oxygenated intermediates. Pronounced three-stage oxidation behavior was observed including two fuel decomposition processes and one negative-temperature-coefficient (NTC) window. A detailed model incorporating both high and low-temperature reaction scheme was proposed and validated against the measured data with reasonable agreement. Representative large oxygenated intermediates were detected in this work, such as cyclic ether (CE), cyclohexylhydroperoxide (ROOH), ketohydroperoxide (KHP), olefinic hydroperoxide (OFHP) and C₉ acyclic/cyclic bi-carbonyl species whose signal profiles were further compared with the simulated mole fraction profiles justifying the occurrence of specific low-temperature chemistry. Based on the modeling analysis, the competition between the chain-branching processes forming OH and chain-propagating processes forming less reactive HO₂ or CE was found to determine the distinct oxidation behavior at different temperature regions. As temperature rises, chain-branching processes are inhibited and the accumulation of HO₂ is accelerated, which lead to the occurrence of self-combination forming H₂O₂, a chain-termination process, resulting in the NTC behavior. With the arrival of high-temperature region, H₂O₂ becomes thermally unstable and tends to dissociate to double OH via a chain-branching process, therefore triggering the second fuel decomposition via H-atom abstractions.