A Signature of Roaming Dynamics in the Thermal Decomposition of Ethyl Nitrite: Chirped-Pulse Rotational Spectroscopy and Kinetic Modeling
Author(s)Prozument, Kirill; Suleimanov, Yury V.; Buesser, Beat; Oldham, James M.; Green, William H.; Suits, Arthur G.; Field, Robert W.; ... Show more Show less
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Chirped-pulse (CP) Fourier transform rotational spectroscopy is uniquely suited for near-universal quantitative detection and structural characterization of mixtures that contain multiple molecular and radical species. In this work, we employ CP spectroscopy to measure product branching and extract information about the reaction mechanism, guided by kinetic modeling. Pyrolysis of ethyl nitrite, CH[subscript 3]CH[subscript 2]ONO, is studied in a Chen type flash pyrolysis reactor at temperatures of 1000–1800 K. The branching between HNO, CH[subscript 2]O, and CH[subscript 3]CHO products is measured and compared to the kinetic models generated by the Reaction Mechanism Generator software. We find that roaming CH[subscript 3]CH[subscript 2]ONO → CH[subscript 3]CHO + HNO plays an important role in the thermal decomposition of ethyl nitrite, with its rate, at 1000 K, comparable to that of the radical elimination channel CH[subscript 3]CH[subscript 2]ONO → CH[subscript 3]CH[subscript 2]O + NO. HNO is a signature of roaming in this system.
DepartmentMassachusetts Institute of Technology. Department of Chemical Engineering; Massachusetts Institute of Technology. Department of Chemistry
The Journal of Physical Chemistry Letters
American Chemical Society (ACS)
Prozument, Kirill, Yury V. Suleimanov, Beat Buesser, James M. Oldham, William H. Green, Arthur G. Suits, and Robert W. Field. “A Signature of Roaming Dynamics in the Thermal Decomposition of Ethyl Nitrite: Chirped-Pulse Rotational Spectroscopy and Kinetic Modeling.” The Journal of Physical Chemistry Letters 5, no. 21 (November 6, 2014): 3641–48.
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