Kinetics of the hydrogen abstraction C2H3* + alkane --> C2H4 + alkyl radical reaction class

Marta Muszyńska; Artur Ratkiewicz; Lam K Huynh; Thanh N Truong

doi:10.1021/jp903762x

Kinetics of the hydrogen abstraction C2H3* + alkane --> C2H4 + alkyl radical reaction class

J Phys Chem A. 2009 Jul 23;113(29):8327-36. doi: 10.1021/jp903762x.

Authors

Marta Muszyńska¹, Artur Ratkiewicz, Lam K Huynh, Thanh N Truong

Affiliation

¹ Chemistry Institute, University of Bialystok, Hurtowa 1 15-399 Bialystok, Poland.

PMID: 19569659
DOI: 10.1021/jp903762x

Abstract

This paper presents an application of the reaction class transition state theory (RC-TST) to predict thermal rate constants for hydrogen abstraction reactions of the type C(2)H(3) + alkane --> C(2)H(4) + alkyl radical. The linear energy relationship (LER) was proven to hold for both noncyclic and cyclic hydrocarbons. We have derived all parameters for the RC-TST method 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 90% systematic errors on the average exist in the predicted rate constants using the RC-TST/LER or RC-TST/BHG method, while in comparison to explicit rate calculations, the differences are within a factor of 2 on the average.