Premium
Kinetics of C 6 H 5 radical reactions with 2‐methylpropane, 2,3‐dimethylbutane and 2,3,4‐trimethylpentane
Author(s) -
Park J.,
Gheyas S. I.,
Lin M. C.
Publication year - 1999
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1999)31:9<645::aid-kin6>3.0.co;2-q
Subject(s) - chemistry , reaction rate constant , alkyl , mass spectrometry , kinetics , medicinal chemistry , analytical chemistry (journal) , atmospheric temperature range , photodissociation , photochemistry , organic chemistry , chromatography , thermodynamics , physics , quantum mechanics
The absolute bimolecular rate constants for the reactions of C 6 H 5 with 2‐methylpropane, 2,3‐dimethylbutane and 2,3,4‐trimethylpentane have been measured by cavity ringdown spectrometry at temperatures between 290 and 500 K. For 2‐methylpropane, additional measurements were performed with the pulsed laser photolysis/mass spectrometry, extending the temperature range to 972 K. The reactions were found to be dominated by the abstraction of a tertiary CH bond from the molecular reactant, resulting in the production of a tertiary alkyl radical: C 6 H 5 + CH(CH 3 ) 3 → C 6 H 6 + t ‐C 4 H 9 (1) C 6 H 5 + (CH 3 ) 2 CHCH(CH 3 ) 2 → C 6 H 6 + t ‐C 6 H 13 (2) C 6 H 5 + (CH 3 ) 2 CHCH(CH 3 )CH(CH 3 ) 2 → C 6 H 6 + t ‐C 8 H 17 (3) with the following rate constants given in units of cm 3 mol −1 s −1 : k 1 = 10 (11.45 ± 0.18) e −(1512 ± 44)/Tk 2 = 10 (11.72 ± 0.15) e −(1007 ± 124)/Tk 3 = 10 (11.83 ± 0.13) e −(428 ± 108)/T © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 645–653, 1999