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

(2014) JOURNAL OF PHYSICAL CHEMISTRY A. 118(40). p.9296-9309
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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.
Keywords
HIGH-TEMPERATURE PYROLYSIS, TRANSITION-STATE THEORY, GAS-PHASE REACTION, DIMETHYL ETHER, ACTIVATION-ENERGIES, SHOCK-TUBE, THERMAL-CRACKING, RATE CONSTANTS, REACTION-RATES, THERMOCHEMISTRY

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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.
@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},
}

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