High-temperature unimolecular decomposition of ethyl propionate

[Display omitted] •Unimolecular thermal decomposition of ethyl propionate studied at high temperatures.•Measured rates do not exhibit noticeable fall off over 1–2.5bar.•Decomposition process occurs through six-centered retro-ene elimination of ethylene.•Ab-initio/master equation calculations agreed...

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Bibliographic Details
Published in:Chemical physics letters 2016-11, Vol.664, p.184-190
Main Authors: Giri, Binod Raj, AlAbbad, Mohammed, Farooq, Aamir
Format: Article
Language:English
Subjects:
Ethyl propionate
Retro-ene elimination
Shock tube
Unimolecular decomposition
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Summary:[Display omitted] •Unimolecular thermal decomposition of ethyl propionate studied at high temperatures.•Measured rates do not exhibit noticeable fall off over 1–2.5bar.•Decomposition process occurs through six-centered retro-ene elimination of ethylene.•Ab-initio/master equation calculations agreed very well with experimental rates. This work reports rate coefficients of the thermal unimolecular decomposition reaction of ethyl propionate (EP) behind reflected shock waves over the temperature range of 976–1300K and pressures of 825–1875Torr. The reaction progress was monitored by detecting C2H4 near 10.532μm using CO2 gas laser absorption. In addition, G3//MP2/aug-cc-pVDZ and master equation calculations were performed to assess the pressure- and temperature-dependence of the reaction. Our calculations revealed that C2H4 elimination occurs via a six-centered retro-ene transition state. Our measured rate data are close to the high-pressure limit and showed no discernable temperature fall off.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2016.10.012