On the low-temperature chemistry of 1,3-butadiene

In this paper, species versus temperature profiles were measured during the oxidation of 1,3-butadiene in a jet-stirred reactor (JSR) at 1 atm, at different equivalence ratios (& phi; = 0.5, 1.0 and 2.0), in the temperature range 600 - 1020 K. Both synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) and gas chromatography (GC) methods were used to analyze the species. The experimental results show that a large proportion of the products are aldehydes (formaldehyde, acetaldehyde, acrolein, etc.) and ketenes (ketene, methyl-ketene), with acrolein being one of the major products. Moreover, furan, 1,3-cyclopentadiene and benzene are also present as intermediates in significant amounts. The reaction pathways leading to the formation of these species are discussed in detail. A new detailed mechanism, NUIGMech1.3, was developed to simulate these new data as well as other experimental data available in the literature. The validation re-sults indicate that quantum calculations are also needed to explore the formation of some important species formed in the oxidation of 1,3-butadiene. Overall, the new 1,3-butadiene mechanism agrees well with vari-ous experimental data in the low-to high-temperature regimes and at different pressures. Flux and sensitivity analyses show that 1,3-butadiene shares some common reaction chemistry pathways with 1-and 2-butene via H atom and H O2 radical addition to the C = C double bond in 1,3-butadiene, reactions which are important for both systems. The low temperature chemistry of 1,3-butadiene is mainly controlled by the reaction path-ways of OH radical addition to the C = C double bond of the fuel molecule. The 1-buten-4-ol-3-yl radicals so formed subsequently add to O 2 and react via the Waddington mechanism, which is important in accurately simulating the oxidation and auto-ignition of 1,3-butadiene at engine relevant conditions.& COPY; 2022 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Automated summary

Species versus temperature profiles during the oxidation of 1,3-butadiene were measured in a jet-stirred reactor. The experimental results show the formation of aldehydes, ketenes, and intermediates such as furan, 1,3-cyclopentadiene, and benzene. The reaction pathways leading to the formation of these species were discussed, and a new detailed mechanism was developed to simulate the experimental data.