Kinetics of CH(X 2Π) radical reactions with propane, isobutane and neopentane

Abstract

Rate constants over the temperature range 298–689 K are reported for the reaction of CH(X 2Π) radicals with C 3H 8, i-C 4H 10 and neo-C 5H 12. The CH radical was generated by multiphoton laser photolysis of CHBr 3 and its disappearance monitored by laser-induced fluorescence (LIF) at 429.8 nm. Absolute rate constants were determined as a function of temperature and total pressure. The following Arrhenius parameters were derived: k = (1.85 ± 0.13) × 10 −10 exp[(240±30)/ T] cm 3/s for CH+propane; k = (2.03±0.19)×10 −10 exp[(240±40)/ T] cm 3/s for CH+isobutane; k = (1.61±0.10)×10 −10 exp[(340±30)/ T] cm 3/s for CH+neopentane, all independent of total pressure. The negative temperature dependences along with the energetics and lack of pressure effects lead to the conclusion that the reactions proceed by CH insertion into the alkane. The activated adduct thus formed rapidly decomposes via many energetically accessible channels. An analysis of CH reactions with C 1 to C 5 alkanes shows an increase in the room temperature rate constants in going from C 1 to C 4 irrespective of the nature of CH bonds. The rate constant then begins to level off near ≈ 5 × 10 −10 cm/s for C 4 and C 5 alkanes.