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Title: Pressure-dependent competition among reaction pathways from first- and second-O 2 additions in the low-temperature oxidation of tetrahydrofuran

Here, we report a combined experimental and quantum chemistry study of the initial reactions in low-temperature oxidation of tetrahydrofuran (THF). Using synchrotron-based time-resolved VUV photoionization mass spectrometry, we probe numerous transient intermediates and products at P = 10–2000 Torr and T = 400–700 K. A key reaction sequence, revealed by our experiments, is the conversion of THF-yl peroxy to hydroperoxy-THF-yl radicals (QOOH), followed by a second O 2 addition and subsequent decomposition to dihydrofuranyl hydroperoxide + HO 2 or to γ-butyrolactone hydroperoxide + OH. The competition between these two pathways affects the degree of radical chain-branching and is likely of central importance in modeling the autoignition of THF. We interpret our data with the aid of quantum chemical calculations of the THF-yl + O 2 and QOOH + O 2 potential energy surfaces. On the basis of our results, we propose a simplified THF oxidation mechanism below 700 K, which involves the competition among unimolecular decomposition and oxidation pathways of QOOH.
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Publication Date:
Report Number(s):
SAND-2016-6674J
Journal ID: ISSN 1089-5639; 644989
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 33; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Research Org:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1328120

Antonov, Ivan O., Zador, Judit, Rotavera, Brandon, Papajak, Ewa, Osborn, David L., Taatjes, Craig A., and Sheps, Leonid. Pressure-dependent competition among reaction pathways from first- and second-O2 additions in the low-temperature oxidation of tetrahydrofuran. United States: N. p., Web. doi:10.1021/acs.jpca.6b05411.
Antonov, Ivan O., Zador, Judit, Rotavera, Brandon, Papajak, Ewa, Osborn, David L., Taatjes, Craig A., & Sheps, Leonid. Pressure-dependent competition among reaction pathways from first- and second-O2 additions in the low-temperature oxidation of tetrahydrofuran. United States. doi:10.1021/acs.jpca.6b05411.
Antonov, Ivan O., Zador, Judit, Rotavera, Brandon, Papajak, Ewa, Osborn, David L., Taatjes, Craig A., and Sheps, Leonid. 2016. "Pressure-dependent competition among reaction pathways from first- and second-O2 additions in the low-temperature oxidation of tetrahydrofuran". United States. doi:10.1021/acs.jpca.6b05411. https://www.osti.gov/servlets/purl/1328120.
@article{osti_1328120,
title = {Pressure-dependent competition among reaction pathways from first- and second-O2 additions in the low-temperature oxidation of tetrahydrofuran},
author = {Antonov, Ivan O. and Zador, Judit and Rotavera, Brandon and Papajak, Ewa and Osborn, David L. and Taatjes, Craig A. and Sheps, Leonid},
abstractNote = {Here, we report a combined experimental and quantum chemistry study of the initial reactions in low-temperature oxidation of tetrahydrofuran (THF). Using synchrotron-based time-resolved VUV photoionization mass spectrometry, we probe numerous transient intermediates and products at P = 10–2000 Torr and T = 400–700 K. A key reaction sequence, revealed by our experiments, is the conversion of THF-yl peroxy to hydroperoxy-THF-yl radicals (QOOH), followed by a second O2 addition and subsequent decomposition to dihydrofuranyl hydroperoxide + HO2 or to γ-butyrolactone hydroperoxide + OH. The competition between these two pathways affects the degree of radical chain-branching and is likely of central importance in modeling the autoignition of THF. We interpret our data with the aid of quantum chemical calculations of the THF-yl + O2 and QOOH + O2 potential energy surfaces. On the basis of our results, we propose a simplified THF oxidation mechanism below 700 K, which involves the competition among unimolecular decomposition and oxidation pathways of QOOH.},
doi = {10.1021/acs.jpca.6b05411},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 33,
volume = 120,
place = {United States},
year = {2016},
month = {7}
}