The impact of the third O2 addition reaction network on ignition delay times of neo-pentane
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- Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- RWTH Aachen Univ. (Germany). Inst. for Combustion Technology
- National Univ. of Ireland, Galway (Ireland). MaREI, Ryan Inst., Combustion Chemistry Centre
- Univ. of Helsinki (Finland)
- Physikalisch-Technische Bundesanstalt, Braunschweig (Germany)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Univ. of Science and Technology of China, Hefei (China). National Synchrotron Radiation Lab.
In this work, we studied the oxidation of neo-pentane by combining experiments, theoretical calculations, and mechanistic developments to elucidate the impact of the 3rd O2 addition reaction network on ignition delay time predictions. The experiments are based on photoionization mass spectrometry in jet-stirred and time-resolved flow reactors allowing for sensitive detection of the keto-hydroperoxide (KHP) and keto-dihydroperoxide (KDHP) intermediates. With neo-pentane exhibiting a unique symmetric molecular structure, which consequently results only in single KHP and KDHP isomers, theoretical calculations of ionization and fragment appearance energies and of absolute photoionization cross sections enabled the unambiguous identification and quantification of the KHP intermediate. Its temperature and time-resolved profiles together with calculated and experimentally observed KHP-to-KDHP signal ratios were compared to simulation results based on a newly developed mechanism that describes the 3rd O2 addition reaction network. A satisfactory agreement has been observed between the experimental data points and the simulation results, thus adding confidence to the model's overall performance. Finally, this mechanism was used to predict ignition delay times reported previously in shock tube and rapid compression machine experiments (J. Bugler et al., Combust. Flame 163 (2016) 138–156). While the model accurately reproduces the experimental data, simulations with and without the 3rd O2 addition reaction network included reveal only a negligible effect on the predicted ignition delay times at 10 and 20 atm. According to model calculations, low temperatures and high pressures promote the importance of the 3rd O2 addition reactions.
- Research Organization:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Organization:
- Academy of Finland; National Natural Science Foundation of China (NSFC); USDOE; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
- Grant/Contract Number:
- AC02-05CH11231; AC02-06CH11357; AC52-07NA27344; NA0003525
- OSTI ID:
- 1782519
- Report Number(s):
- LLNL-JRNL--796728; 998291
- Journal Information:
- Proceedings of the Combustion Institute, Journal Name: Proceedings of the Combustion Institute Journal Issue: 1 Vol. 38; ISSN 1540-7489
- Publisher:
- ElsevierCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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