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Title: New insights into low-temperature oxidation of propane from synchrotron photoionization mass spectrometry and multi-scale informatics modeling

Abstract

We studied low-temperature propane oxidation at P = 4 Torr and T = 530, 600, and 670 K by time-resolved multiplexed photoionization mass spectrometry (MPIMS), which probes the reactants, intermediates, and products with isomeric selectivity using tunable synchrotron vacuum UV ionizing radiation. The oxidation is initiated by pulsed laser photolysis of oxalyl chloride, (COCl)2, at 248 nm, which rapidly generates a ~1:1 mixture of 1-propyl (n-propyl) and 2-propyl (i-propyl) radicals via the fast Cl + propane reaction. At all three temperatures, the major stable product species is propene, formed in the propyl + O2 reactions by direct HO2 elimination from both n- and i-propyl peroxy radicals. The experimentally derived propene yields relative to the initial concentration of Cl atoms are (20 ± 4)% at 530 K, (55 ± 11)% at 600 K, and (86 ± 17)% at 670 K at a reaction time of 20 ms. The lower yield of propene at low temperature reflects substantial formation of propyl peroxy radicals, which do not completely decompose on the experimental time scale. In addition, C3H6O isomers methyloxirane, oxetane, acetone, and propanal are detected as minor products. Our measured yields of oxetane and methyloxirane, which are coproducts of OH radicals, suggest amore » revision of the OH formation pathways in models of low-temperature propane oxidation. The experimental results are modeled and interpreted using a multiscale informatics approach, presented in detail in a separate publication (Burke, M. P.; Goldsmith, C. F.; Klippenstein, S. J.; Welz, O.; Huang H.; Antonov I. O.; Savee J. D.; Osborn D. L.; Zádor, J.; Taatjes, C. A.; Sheps, L. Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions. J. Phys. Chem A. 2015, DOI: 10.1021/acs.jpca.5b01003). Additionally, we found that the model predicts the time profiles and yields of the experimentally observed primary products well, and shows satisfactory agreement for products formed mostly via secondary radical–radical reactions.« less

Authors:
 [1];  [2];  [1];  [3];  [1];  [1];  [1];  [3];  [1]
+ Show Author Affiliations
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Columbia Univ., New York, NY (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1235294
Report Number(s):
SAND-2015-4303J
Journal ID: ISSN 1089-5639; 590427
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 119; Journal Issue: 28; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; low-temperature autoignition; propane oxidation; photoionization mass spectrometry; hydrocarbon oxidation; peroxy radicals; kinetics modeling

Citation Formats

Welz, Oliver, Burke, Michael P., Antonov, Ivan O., Goldsmith, C. Franklin, Savee, John David, Osborn, David L., Taatjes, Craig A., Klippenstein, Stephen J., and Sheps, Leonid. New insights into low-temperature oxidation of propane from synchrotron photoionization mass spectrometry and multi-scale informatics modeling. United States: N. p., 2015. Web. doi:10.1021/acs.jpca.5b01008.
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Welz, Oliver, Burke, Michael P., Antonov, Ivan O., Goldsmith, C. Franklin, Savee, John David, Osborn, David L., Taatjes, Craig A., Klippenstein, Stephen J., & Sheps, Leonid. New insights into low-temperature oxidation of propane from synchrotron photoionization mass spectrometry and multi-scale informatics modeling. United States. https://doi.org/10.1021/acs.jpca.5b01008
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Welz, Oliver, Burke, Michael P., Antonov, Ivan O., Goldsmith, C. Franklin, Savee, John David, Osborn, David L., Taatjes, Craig A., Klippenstein, Stephen J., and Sheps, Leonid. Fri . "New insights into low-temperature oxidation of propane from synchrotron photoionization mass spectrometry and multi-scale informatics modeling". United States. https://doi.org/10.1021/acs.jpca.5b01008. https://www.osti.gov/servlets/purl/1235294.
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@article{osti_1235294,
title = {New insights into low-temperature oxidation of propane from synchrotron photoionization mass spectrometry and multi-scale informatics modeling},
author = {Welz, Oliver and Burke, Michael P. and Antonov, Ivan O. and Goldsmith, C. Franklin and Savee, John David and Osborn, David L. and Taatjes, Craig A. and Klippenstein, Stephen J. and Sheps, Leonid},
abstractNote = {We studied low-temperature propane oxidation at P = 4 Torr and T = 530, 600, and 670 K by time-resolved multiplexed photoionization mass spectrometry (MPIMS), which probes the reactants, intermediates, and products with isomeric selectivity using tunable synchrotron vacuum UV ionizing radiation. The oxidation is initiated by pulsed laser photolysis of oxalyl chloride, (COCl)2, at 248 nm, which rapidly generates a ~1:1 mixture of 1-propyl (n-propyl) and 2-propyl (i-propyl) radicals via the fast Cl + propane reaction. At all three temperatures, the major stable product species is propene, formed in the propyl + O2 reactions by direct HO2 elimination from both n- and i-propyl peroxy radicals. The experimentally derived propene yields relative to the initial concentration of Cl atoms are (20 ± 4)% at 530 K, (55 ± 11)% at 600 K, and (86 ± 17)% at 670 K at a reaction time of 20 ms. The lower yield of propene at low temperature reflects substantial formation of propyl peroxy radicals, which do not completely decompose on the experimental time scale. In addition, C3H6O isomers methyloxirane, oxetane, acetone, and propanal are detected as minor products. Our measured yields of oxetane and methyloxirane, which are coproducts of OH radicals, suggest a revision of the OH formation pathways in models of low-temperature propane oxidation. The experimental results are modeled and interpreted using a multiscale informatics approach, presented in detail in a separate publication (Burke, M. P.; Goldsmith, C. F.; Klippenstein, S. J.; Welz, O.; Huang H.; Antonov I. O.; Savee J. D.; Osborn D. L.; Zádor, J.; Taatjes, C. A.; Sheps, L. Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions. J. Phys. Chem A. 2015, DOI: 10.1021/acs.jpca.5b01003). Additionally, we found that the model predicts the time profiles and yields of the experimentally observed primary products well, and shows satisfactory agreement for products formed mostly via secondary radical–radical reactions.},
doi = {10.1021/acs.jpca.5b01008},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 28,
volume = 119,
place = {United States},
year = {Fri Apr 10 00:00:00 EDT 2015},
month = {Fri Apr 10 00:00:00 EDT 2015}
}
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    The multichannel n -propyl + O 2 reaction surface: Definitive theory on a model hydrocarbon oxidation mechanism
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