期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 120, 期 33, 页码 6582-6595出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.6b05411
关键词
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资金
- Division of Chemical Sciences, Geosciences, and Biosciences, the Office of Basic Energy Sciences, the U.S. Department of Energy
- Argonne Sandia Consortium on High-Pressure Combustion Chemistry
- National Nuclear Security Administration [DE-AC04-94AL85000]
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 02 addition and subsequent decomposition to dihydrofuranyl hydroperoxide + HO2 or to gamma-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.
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