Reaction kinetics and implications of the decomposition and formation of C2H4O isomers

Acetaldehyde, ethylene oxide , and vinyl alcohol are three C 2 H 4 O isomers that are ubiquitous in combustion over a wide temperature range. A comprehensive reaction kinetics study has been performed for reactions that occur on the same C 2 H 4 O potential energy surface , mainly including the unimolecular reactions of three C 2 H 4 O isomers and the recombination reaction of CH 3 with HCO. Temperature- and pressure-dependent rate coefficients were updated or newly predicted by performing quantum chemical calculations coupled with RRKM/master equation simulations. The dominance of C C bond fission is reconfirmed for acetaldehyde decomposition at higher temperatures. The negligible contribution of CH 4  + CO channel from usual tight intramolecular H-shift transition state provides indirect evidence for previously reported roaming mechanism that was proposed to explain the observation of CH 4  + CO in acetaldehyde pyrolysis . For ethylene oxide pyrolysis , current experiment and kinetic prediction have a good consistency in branching ratios between the formation of acetaldehyde and vinyl alcohol products. The radicals of CH 3  + HCO can also be directly generated from ethylene oxide through a well-skipping reaction mechanism especially at higher temperatures. For CH 3  + HCO recombination, we highlight the importance of CH 3 CO + H channel that was often overlooked previously. Kinetic simulations show that the incorporation of updated rate coefficients and newly identified channels results in a measurable influence on C2 chemistry , indicating the possibility and necessity of further improvement of core mechanism in combustion kinetic models .