Mechanism and Kinetics of the Hydrogen Abstraction Reaction of C&lt;sub&gt;2&lt;/sub&gt;H&lt;sub&gt;3&lt;/sub&gt; with CH&lt;sub&gt;3&lt;/sub&gt;F

This paper presents an application of the reaction class transition state theory (RC-TST) to predict thermal rate constants for hydrogen abstraction reactions at alkane by the ÁC 2 H 5 radical on-the-fly. The linear energy relationship (LER), developed for acyclic alkanes, was also proven to hold for cyclic alkanes. We have derived all RC-TST parameters from rate constants of 19 representative reactions, coupling with LER and the barrier height grouping (BHG) approach. Both the RC-TST/LER, where only reaction energy is needed, and the RC-TST/BHG, where no other information is needed, can predict rate constants for any reaction in this reaction class with satisfactory accuracy for combustion modeling. Our analysis indicates that less than 50 % systematic errors on the average exist in the predicted rate constants using either the RC-TST/LER or RC-TST/BHG method, while in comparison with explicit rate calculations, the differences are within a factor of 2 on the average. The results also show that the RC-TST method is not sensitive to the choice of density functional theory used.

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Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

Ratkiewicz

Huynh

Pham

et al. 2013

Theor Chem Acc

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Direct dynamics study on the hydrogen abstraction reaction of fluoromethanes with vinyl radical

Feng

Jia

Wang

et al. 2013

Computational and Theoretical Chemistry

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First-principles kinetics of n-octyl radicals

Ratkiewicz

2013

Progress in Reaction Kinetics and Mechanism

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Kinetics of the isomerisation and unimolecular degradation of n-octyl radicals have been studied with the reaction class transition state theory (RC-TST) method. To explore the kinetics of the 1,7-H migration reactions family, the accurate high-pressure limits of the rate constants for the reference reaction of this class (1-heptyl → 1-heptyl) have been calculated. Finally, both the achievements reported in this paper and previous developments are employed to obtain theoretical branching ratios of intramolecular H-transfers and unimolecular degradations of all possible n-octyl radicals; the results are in satisfactory agreement when compared to experiment. The application of the rates obtained to the simulation of a simple reactor is also reported.

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Mechanism and Kinetics of the Hydrogen Abstraction Reaction of C<sub>2</sub>H<sub>3</sub> with CH<sub>3</sub>F

Cited by 3 publications

References 18 publications

Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

Kinetics of the hydrogen abstraction ·C2H5 + alkane → C2H6 + alkyl reaction class: an application of the reaction class transition state theory

Direct dynamics study on the hydrogen abstraction reaction of fluoromethanes with vinyl radical

First-principles kinetics of n-octyl radicals

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