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

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
Maarten K SabbeGuy B Marin

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 family 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. The 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...Continue Reading

References

Dec 3, 2005·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Mark SaeysGuy B Marin
Jul 13, 2006·The Journal of Physical Chemistry. a·Judit ZádorAndrea Saltelli
Jul 13, 2006·The Journal of Physical Chemistry. a·Stephen J Klippenstein, James A Miller
Jul 13, 2006·The Journal of Physical Chemistry. a·Maarten K SabbeMichel Waroquier
Mar 29, 2007·The Journal of Physical Chemistry. a·Lam K HuynhThanh N Truong
Aug 7, 2007·The Journal of Physical Chemistry. a·Maarten K SabbeGuy B Marin
Oct 31, 2007·The Journal of Physical Chemistry. a·Aäron G VandeputteGuy B Marin
Jan 5, 2008·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Maarten K SabbeGuy B Marin

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Citations

Dec 2, 2011·The Journal of Physical Chemistry. a·Artur Ratkiewicz, Barbara Bankiewicz
May 23, 2012·The Journal of Physical Chemistry. a·Artur Ratkiewicz, Thanh N Truong
Jul 23, 2011·Physical Chemistry Chemical Physics : PCCP·Artur Ratkiewicz
Aug 3, 2012·Physical Chemistry Chemical Physics : PCCP·Aäron G VandeputteGuy B Marin
May 16, 2014·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Paschalis D ParaskevasGuy B Marin
Nov 26, 2014·Journal of Computational Chemistry·Nick M VandewieleGuy B Marin
Dec 7, 2018·The Journal of Chemical Physics·Jay C Amicangelo, Yuan-Pern Lee
Sep 12, 2014·The Journal of Physical Chemistry. a·Paschalis D ParaskevasGuy B Marin

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