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Title: Non-Boltzmann Effects in Chain Branching and Pathway Branching for Diethyl Ether Oxidation

Abstract

Low-temperature (LT) engine applications have several potential benefits, including reduced emissions and increased efficiency. Attaining these benefits requires accurate kinetic modeling of LT chain branching, which depends heavily on ketohydroperoxide (KHP) decomposition. For diethyl ether (DEE), a promising biofuel, current estimates of the KHP decomposition rate constant are largely based on empirical fits to data. In this study, we investigate the most important KHP isomer in DEE LT oxidation by applying variable reaction coordinate transition state theory to the main pathway for KHP decomposition: OO bond fission to produce •OH and a keto-alkoxy radical, •OQ'O. We also use ab initio kinetics methods to investigate the decomposition of •OQ'O, where we find dominant branching to acetic acid, with the remaining flux going to CH3C(O)OCHO. Additionally, new time-resolved measurements of DEE and acetic acid concentrations during LT (450–600 K) DEE oxidation are obtained in a laser photolysis flow reactor coupled with multiplexed photoionization mass spectrometry. These new experimental data, along with jet-stirred reactor data in the literature, are compared with the predictions of a recent DEE mechanism (Tran et al. Proc. Comb. Inst. 2019, 37, 511-519) that was modified with the newly calculated ab initio rate constants for KHP and •OQ'O decomposition.more » The predictions of the modified mechanism are quite poor when compared to the experimental data; this is primarily due to the new KHP ⇌ •OQ'O + •OH rate constant, which is 1–2 orders of magnitude slower than empirical values employed in recent mechanisms. To reconcile the new KHP rate constant and the experimental data, we explore and quantify the possible role of non-Boltzmann (nB) reaction sequences. The nB reactions have a substantial effect on both the overall mechanism reactivity and the •OQ'O branching to acetic acid. We also provide guidance on the proper implementation of nB reactions in kinetic mechanisms.« less

Authors:
 [1];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Brown Univ., Providence, RI (United States)
  3. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1878167
Grant/Contract Number:  
AC02-06CH11357; FWP-59044; SC0019489; 17-SC-20-SC
Resource Type:
Accepted Manuscript
Journal Name:
Energy and Fuels
Additional Journal Information:
Journal Volume: 35; Journal Issue: 21; Journal ID: ISSN 0887-0624
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mulvihill, Clayton R., Danilack, Aaron D., Goldsmith, C. Franklin, Demireva, Maria, Sheps, Leonid, Georgievskii, Yuri, Elliott, Sarah N., and Klippenstein, Stephen J. Non-Boltzmann Effects in Chain Branching and Pathway Branching for Diethyl Ether Oxidation. United States: N. p., 2021. Web. doi:10.1021/acs.energyfuels.1c02196.
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Mulvihill, Clayton R., Danilack, Aaron D., Goldsmith, C. Franklin, Demireva, Maria, Sheps, Leonid, Georgievskii, Yuri, Elliott, Sarah N., & Klippenstein, Stephen J. Non-Boltzmann Effects in Chain Branching and Pathway Branching for Diethyl Ether Oxidation. United States. https://doi.org/10.1021/acs.energyfuels.1c02196
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Mulvihill, Clayton R., Danilack, Aaron D., Goldsmith, C. Franklin, Demireva, Maria, Sheps, Leonid, Georgievskii, Yuri, Elliott, Sarah N., and Klippenstein, Stephen J. Wed . "Non-Boltzmann Effects in Chain Branching and Pathway Branching for Diethyl Ether Oxidation". United States. https://doi.org/10.1021/acs.energyfuels.1c02196. https://www.osti.gov/servlets/purl/1878167.
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@article{osti_1878167,
title = {Non-Boltzmann Effects in Chain Branching and Pathway Branching for Diethyl Ether Oxidation},
author = {Mulvihill, Clayton R. and Danilack, Aaron D. and Goldsmith, C. Franklin and Demireva, Maria and Sheps, Leonid and Georgievskii, Yuri and Elliott, Sarah N. and Klippenstein, Stephen J.},
abstractNote = {Low-temperature (LT) engine applications have several potential benefits, including reduced emissions and increased efficiency. Attaining these benefits requires accurate kinetic modeling of LT chain branching, which depends heavily on ketohydroperoxide (KHP) decomposition. For diethyl ether (DEE), a promising biofuel, current estimates of the KHP decomposition rate constant are largely based on empirical fits to data. In this study, we investigate the most important KHP isomer in DEE LT oxidation by applying variable reaction coordinate transition state theory to the main pathway for KHP decomposition: OO bond fission to produce •OH and a keto-alkoxy radical, •OQ'O. We also use ab initio kinetics methods to investigate the decomposition of •OQ'O, where we find dominant branching to acetic acid, with the remaining flux going to CH3C(O)OCHO. Additionally, new time-resolved measurements of DEE and acetic acid concentrations during LT (450–600 K) DEE oxidation are obtained in a laser photolysis flow reactor coupled with multiplexed photoionization mass spectrometry. These new experimental data, along with jet-stirred reactor data in the literature, are compared with the predictions of a recent DEE mechanism (Tran et al. Proc. Comb. Inst. 2019, 37, 511-519) that was modified with the newly calculated ab initio rate constants for KHP and •OQ'O decomposition. The predictions of the modified mechanism are quite poor when compared to the experimental data; this is primarily due to the new KHP ⇌ •OQ'O + •OH rate constant, which is 1–2 orders of magnitude slower than empirical values employed in recent mechanisms. To reconcile the new KHP rate constant and the experimental data, we explore and quantify the possible role of non-Boltzmann (nB) reaction sequences. The nB reactions have a substantial effect on both the overall mechanism reactivity and the •OQ'O branching to acetic acid. We also provide guidance on the proper implementation of nB reactions in kinetic mechanisms.},
doi = {10.1021/acs.energyfuels.1c02196},
journal = {Energy and Fuels},
number = 21,
volume = 35,
place = {United States},
year = {Wed Oct 20 00:00:00 EDT 2021},
month = {Wed Oct 20 00:00:00 EDT 2021}
}
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