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Kinetic modeling of a-hydrogen abstractions from unsaturated and saturated oxygenate compounds by hydrogen atoms

Paschalis Paraskevas, Maarten Sabbe UGent, Marie-Françoise Reyniers UGent, N Papayannakos and Guy Marin UGent (2014) JOURNAL OF PHYSICAL CHEMISTRY A. 118(40). p.9296-9309
abstract
Hydrogen-abstraction reactions play a significant role in thermal biomass conversion processes, as well as regular gasification, pyrolysis, or combustion. In this work, a group additivity model is constructed that allows prediction of reaction rates and Arrhenius parameters of hydrogen abstractions by hydrogen atoms from alcohols, ethers, esters, peroxides, ketones, aldehydes, acids, and diketones in a broad temperature range (300-2000 K). A training set of 60 reactions was developed with rate coefficients and Arrhenius parameters calculated by the CBS-QB3 method in the high-pressure limit with tunneling corrections using Eckart tunneling coefficients. From this set of reactions, 15 group additive values were derived for the forward and the reverse reaction, 4 referring to primary and 11 to secondary contributions. The accuracy of the model is validated upon an ab initio and an experimental validation set of 19 and 21 reaction rates, respectively, showing that reaction rates can be predicted with a mean factor of deviation of 2 for the ab initio and 3 for the experimental values. Hence, this work illustrates that the developed group additive model can be reliably applied for the accurate prediction of kinetics of a-hydrogen abstractions by hydrogen atoms from a broad range of oxygenates.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
HIGH-TEMPERATURE PYROLYSIS, TRANSITION-STATE THEORY, GAS-PHASE REACTION, DIMETHYL ETHER, ACTIVATION-ENERGIES, SHOCK-TUBE, THERMAL-CRACKING, RATE CONSTANTS, REACTION-RATES, THERMOCHEMISTRY
journal title
JOURNAL OF PHYSICAL CHEMISTRY A
volume
118
issue
40
pages
9296 - 9309
Web of Science type
Article
Web of Science id
000343016900002
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
2.693 (2014)
JCR rank
10/34 (2014)
JCR quartile
2 (2014)
ISSN
1089-5639
DOI
10.1021/jp503570e
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
5722182
handle
http://hdl.handle.net/1854/LU-5722182
date created
2014-10-15 09:40:29
date last changed
2017-03-09 12:48:50
@article{5722182,
  abstract     = {Hydrogen-abstraction reactions play a significant role in thermal biomass conversion processes, as well as regular gasification, pyrolysis, or combustion. In this work, a group additivity model is constructed that allows prediction of reaction rates and Arrhenius parameters of hydrogen abstractions by hydrogen atoms from alcohols, ethers, esters, peroxides, ketones, aldehydes, acids, and diketones in a broad temperature range (300-2000 K). A training set of 60 reactions was developed with rate coefficients and Arrhenius parameters calculated by the CBS-QB3 method in the high-pressure limit with tunneling corrections using Eckart tunneling coefficients. From this set of reactions, 15 group additive values were derived for the forward and the reverse reaction, 4 referring to primary and 11 to secondary contributions. The accuracy of the model is validated upon an ab initio and an experimental validation set of 19 and 21 reaction rates, respectively, showing that reaction rates can be predicted with a mean factor of deviation of 2 for the ab initio and 3 for the experimental values. Hence, this work illustrates that the developed group additive model can be reliably applied for the accurate prediction of kinetics of a-hydrogen abstractions by hydrogen atoms from a broad range of oxygenates.},
  author       = {Paraskevas, Paschalis and Sabbe, Maarten and Reyniers, Marie-Fran\c{c}oise and Papayannakos, N and Marin, Guy},
  issn         = {1089-5639},
  journal      = {JOURNAL OF PHYSICAL CHEMISTRY A},
  keyword      = {HIGH-TEMPERATURE PYROLYSIS,TRANSITION-STATE THEORY,GAS-PHASE REACTION,DIMETHYL ETHER,ACTIVATION-ENERGIES,SHOCK-TUBE,THERMAL-CRACKING,RATE CONSTANTS,REACTION-RATES,THERMOCHEMISTRY},
  language     = {eng},
  number       = {40},
  pages        = {9296--9309},
  title        = {Kinetic modeling of a-hydrogen abstractions from unsaturated and saturated oxygenate compounds by hydrogen atoms},
  url          = {http://dx.doi.org/10.1021/jp503570e},
  volume       = {118},
  year         = {2014},
}

Chicago
Paraskevas, Paschalis, Maarten Sabbe, Marie-Françoise Reyniers, N Papayannakos, and Guy Marin. 2014. “Kinetic Modeling of A-hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Hydrogen Atoms.” Journal of Physical Chemistry A 118 (40): 9296–9309.
APA
Paraskevas, P., Sabbe, M., Reyniers, M.-F., Papayannakos, N., & Marin, G. (2014). Kinetic modeling of a-hydrogen abstractions from unsaturated and saturated oxygenate compounds by hydrogen atoms. JOURNAL OF PHYSICAL CHEMISTRY A, 118(40), 9296–9309.
Vancouver
1.
Paraskevas P, Sabbe M, Reyniers M-F, Papayannakos N, Marin G. Kinetic modeling of a-hydrogen abstractions from unsaturated and saturated oxygenate compounds by hydrogen atoms. JOURNAL OF PHYSICAL CHEMISTRY A. 2014;118(40):9296–309.
MLA
Paraskevas, Paschalis, Maarten Sabbe, Marie-Françoise Reyniers, et al. “Kinetic Modeling of A-hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Hydrogen Atoms.” JOURNAL OF PHYSICAL CHEMISTRY A 118.40 (2014): 9296–9309. Print.