NDLI: Ab initio study on alkyl radical decomposition and alkyl radical addition to olefins

Content Provider	Springer Nature Link
Author	Viskolcz, Béla Seres, László
Copyright Year	2009
Abstract	The β bond dissociation of alkyl radicals and their reverse reactions, the addition of alkyl radicals to olefins were studied by G3MP2 level of theory to obtain a consistent kinetic data set. Both reaction families can be classified depending on the type of radical formed by β bond scission, namely the CH$_{3}$, primary, secondary tertiary radical formed. The kinetics of the reaction classes were described by only a limited number of Arrhenius parameters. The unified A factor of 10$^{13.7}$ s$^{−1}$ was found for all β bond dissociations. The Arrhenius activation energies are 125, 121, 113 and 103 kJ mol$^{−1}$, for methyl, primary, secondary, and tertiary radicals, respectively. The activation energies of 32, 25 and 18 kJ mol$^{−1}$ are calculated for the terminal addition of primary (including methyl), secondary, and tertiary radicals to olefins, respectively. The biologically important nonterminal radical additions to olefins have higher barriers of 37, 31 and 35 kJ mol$^{−1}$, respectively. At room temperature both strongly exothermic additions can compete with H-atom abstraction.New groups for Benson’s group additivity rules were defined to describe activation parameters for the β bond dissociation reactions. The group values were calculated by using the ab initio heats of formation of transition state structures.
Starting Page	245
Ending Page	262
Page Count	18
File Format	PDF
ISSN	01331736
Journal	Reaction Kinetics and Catalysis Letters
Volume Number	96
Issue Number	2
e-ISSN	15882837
Language	English
Publisher	Springer Netherlands
Publisher Date	2009-04-30
Publisher Place	Dordrecht
Access Restriction	Subscribed
Subject Keyword	β-bond dissociation thermochemistry activation energy activation entropy Industrial Chemistry/Chemical Engineering Physical Chemistry Catalysis
Content Type	Text
Resource Type	Article
Subject	Physical and Theoretical Chemistry Catalysis

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