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Hydrogen radical additions to unsaturated hydrocarbons and the reverse β-scission reactions: modeling of activation energies and pre-exponential factors

Maarten Sabbe UGent, Marie-Françoise Reyniers UGent, Michel Waroquier UGent and Guy Marin UGent (2010) CHEMPHYSCHEM. 11(1). p.195-210
abstract
The group additivity method for Arrhenius parameters is applied to. hydrogen-addition to alkenes and alkynes and the reverse beta-scission reactions, an important famliy of reactions in thermal processes based on radical chemistry. A consistent set of group additive values for 33 groups is derived to calculate the activation energy and pre-exponential factor for a broad range of hydrogen addition reactions. Thee;group additive values are determined from CBS-QB3 ab-initio-calculated rate coefficients. A mean factor of deviation of only two between CBS-QB3 and experimental rate coefficients for seven reactions in the range 300-1000 K is found. Tunneling. coefficients for these reactions were found to be significant;below 400 K and a correlation accounting for tunneling is presented. Application of the obtained group additive values to predict the kinetics for a set of 11 additions and beta-scissions yields rate coefficients within a factor of 3.5 of the CBS-QB3 results except for two beta-scissions with severe steric effects. The mean factor of deviation with respect to experimental rate coefficients of 2.0 shows that the group additive method with tunneling corrections can accurately predict the kinetics and is at least as accurate as the most commonly used density functional methods. The constructed group additive model can hence be applied to predict the kinetics of hydrogen radical additions for a broad range of unsaturated compounds.
Please use this url to cite or link to this publication:
author
organization
alternative title
Hydrogen radical additions to unsaturated hydrocarbons and the reverse beta-scission reactions : modeling of activation energies and pre-exponential factors
year
type
journalArticle (original)
publication status
published
subject
keyword
COMPUTER-GENERATION, GROUP ADDITIVITY, COMBUSTION CHEMISTRY, ABSTRACTION REACTIONS, THERMAL-CRACKING, AB-INITIO, EVALUATED KINETIC-DATA, REACTION-RATE PREDICTION, DENSITY-FUNCTIONAL THEORY, TRANSITION-STATE THEORY, kinetics, radical reactions, group aditivity methods, gas-phase reactions, ab initio calculations
journal title
CHEMPHYSCHEM
ChemPhysChem
volume
11
issue
1
pages
195 - 210
Web of Science type
Article
Web of Science id
000274265300027
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
3.339 (2010)
JCR rank
5/31 (2010)
JCR quartile
1 (2010)
ISSN
1439-4235
DOI
10.1002/cphc.200900509
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
869538
handle
http://hdl.handle.net/1854/LU-869538
date created
2010-02-19 10:43:18
date last changed
2010-03-02 15:08:42
@article{869538,
  abstract     = {The group additivity method for Arrhenius parameters is applied to. hydrogen-addition to alkenes and alkynes and the reverse beta-scission reactions, an important famliy of reactions in thermal processes based on radical chemistry. A consistent set of group additive values for 33 groups is derived to calculate the activation energy and pre-exponential factor for a broad range of hydrogen addition reactions. Thee;group additive values are determined from CBS-QB3 ab-initio-calculated rate coefficients. A mean factor of deviation of only two between CBS-QB3 and experimental rate coefficients for seven reactions in the range 300-1000 K is found. Tunneling. coefficients for these reactions were found to be significant;below 400 K and a correlation accounting for tunneling is presented. Application of the obtained group additive values to predict the kinetics for a set of 11 additions and beta-scissions yields rate coefficients within a factor of 3.5 of the CBS-QB3 results except for two beta-scissions with severe steric effects. The mean factor of deviation with respect to experimental rate coefficients of 2.0 shows that the group additive method with tunneling corrections can accurately predict the kinetics and is at least as accurate as the most commonly used density functional methods. The constructed group additive model can hence be applied to predict the kinetics of hydrogen radical additions for a broad range of unsaturated compounds.},
  author       = {Sabbe, Maarten and Reyniers, Marie-Fran\c{c}oise and Waroquier, Michel and Marin, Guy},
  issn         = {1439-4235},
  journal      = {CHEMPHYSCHEM},
  keyword      = {COMPUTER-GENERATION,GROUP ADDITIVITY,COMBUSTION CHEMISTRY,ABSTRACTION REACTIONS,THERMAL-CRACKING,AB-INITIO,EVALUATED KINETIC-DATA,REACTION-RATE PREDICTION,DENSITY-FUNCTIONAL THEORY,TRANSITION-STATE THEORY,kinetics,radical reactions,group aditivity methods,gas-phase reactions,ab initio calculations},
  language     = {eng},
  number       = {1},
  pages        = {195--210},
  title        = {Hydrogen radical additions to unsaturated hydrocarbons and the reverse \ensuremath{\beta}-scission reactions: modeling of activation energies and pre-exponential factors},
  url          = {http://dx.doi.org/10.1002/cphc.200900509},
  volume       = {11},
  year         = {2010},
}

Chicago
Sabbe, Maarten, Marie-Françoise Reyniers, Michel Waroquier, and Guy Marin. 2010. “Hydrogen Radical Additions to Unsaturated Hydrocarbons and the Reverse Β-scission Reactions: Modeling of Activation Energies and Pre-exponential Factors.” Chemphyschem 11 (1): 195–210.
APA
Sabbe, M., Reyniers, M.-F., Waroquier, M., & Marin, G. (2010). Hydrogen radical additions to unsaturated hydrocarbons and the reverse β-scission reactions: modeling of activation energies and pre-exponential factors. CHEMPHYSCHEM, 11(1), 195–210.
Vancouver
1.
Sabbe M, Reyniers M-F, Waroquier M, Marin G. Hydrogen radical additions to unsaturated hydrocarbons and the reverse β-scission reactions: modeling of activation energies and pre-exponential factors. CHEMPHYSCHEM. 2010;11(1):195–210.
MLA
Sabbe, Maarten, Marie-Françoise Reyniers, Michel Waroquier, et al. “Hydrogen Radical Additions to Unsaturated Hydrocarbons and the Reverse Β-scission Reactions: Modeling of Activation Energies and Pre-exponential Factors.” CHEMPHYSCHEM 11.1 (2010): 195–210. Print.