Pressure-dependent competition among reaction pathways from first- and second-O2 additions in the low-temperature oxidation of tetrahydrofuran

Antonov, Ivan O.; Zador, Judit; Rotavera, Brandon; Papajak, Ewa; Osborn, David L.; Taatjes, Craig A.; Sheps, Leonid

doi:10.1021/acs.jpca.6b05411

Pressure-dependent competition among reaction pathways from first- and second-O₂ additions in the low-temperature oxidation of tetrahydrofuran

Journal Article · Thu Jul 21 00:00:00 EDT 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.6b05411· OSTI ID:1328120

Antonov, Ivan O. ^[1]; Zador, Judit ^[1]; Rotavera, Brandon ^[1]; Papajak, Ewa ^[1]; Osborn, David L. ^[1]; Taatjes, Craig A. ^[1]; Sheps, Leonid ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1328120

Report Number(s):: SAND--2016-6674J; 644989

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 33 Vol. 120; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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