TY - JOUR
T1 - On the high-temperature unimolecular decomposition of ethyl levulinate
AU - AlAbbad, Mohammed A.
AU - Giri, Binod
AU - Szőri, Milán
AU - Farooq, Aamir
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Research reported in this publication was funded by King Abdullah University of Science and Technology (KAUST), and by the scientific fund of Faculty of Education at University of Szeged (CS-009/2015). Experimental work was carried out at the Chemical Kinetics and Laser Sensors Laboratory at KAUST. Milán Szőri was a Magyary Zoltán fellow in the framework of TÁMOP 4.2.4.A/2-11-1-2012-0001 (A2-MZPD-12-0139) and currently a János Bolyai Research Scholar of the Hungarian Academy of Sciences(BO/00113/15/7).
PY - 2016/9/20
Y1 - 2016/9/20
N2 - The pyrolysis of ethyl levulinate (EL) was studied behind reflected shock waves over the temperature range of 1015-1325K and pressures of 750-1650Torr. The reaction progress was followed by measuring ethylene mole fraction using CO2 gas laser absorption near 10.532 μm. The rate coefficients for the unimolecular dissociation of EL were extracted from the initial slope method and further ascertained by using a complete kinetic model. Our data exhibited no discernible pressure dependence under the current experimental conditions. To rationalize our results further, high-level quantum chemical and master equation calculations were employed to calculate the pressure- and temperature-dependence of the reaction. Our calculations revealed that unimolecular dissociation of EL involves simultaneous 1,5-hydrogen shift of the β-hydrogen to the carbonyl group, rupture of the O-C ester bond and formation of the π-bond (C α -C β ). Our results present evidences that the C2H4 elimination from EL occurs in a concerted manner. To our knowledge, this work represents the first experimental and theoretical study of the thermal unimolecular dissociation of ethyl levulinate. © 2016 The Combustion Institute.
AB - The pyrolysis of ethyl levulinate (EL) was studied behind reflected shock waves over the temperature range of 1015-1325K and pressures of 750-1650Torr. The reaction progress was followed by measuring ethylene mole fraction using CO2 gas laser absorption near 10.532 μm. The rate coefficients for the unimolecular dissociation of EL were extracted from the initial slope method and further ascertained by using a complete kinetic model. Our data exhibited no discernible pressure dependence under the current experimental conditions. To rationalize our results further, high-level quantum chemical and master equation calculations were employed to calculate the pressure- and temperature-dependence of the reaction. Our calculations revealed that unimolecular dissociation of EL involves simultaneous 1,5-hydrogen shift of the β-hydrogen to the carbonyl group, rupture of the O-C ester bond and formation of the π-bond (C α -C β ). Our results present evidences that the C2H4 elimination from EL occurs in a concerted manner. To our knowledge, this work represents the first experimental and theoretical study of the thermal unimolecular dissociation of ethyl levulinate. © 2016 The Combustion Institute.
UR - http://hdl.handle.net/10754/622324
UR - http://www.sciencedirect.com/science/article/pii/S154074891630092X
UR - http://www.scopus.com/inward/record.url?scp=84994705284&partnerID=8YFLogxK
U2 - 10.1016/j.proci.2016.06.034
DO - 10.1016/j.proci.2016.06.034
M3 - Article
SN - 1540-7489
VL - 36
SP - 187
EP - 193
JO - Proceedings of the Combustion Institute
JF - Proceedings of the Combustion Institute
IS - 1
ER -