%0 Journal Article
%A Yang, Xueliang
%A Goldsmith, C. Franklin
%A Tranter, Robert S.
%D 2009
%T Decomposition and Vibrational Relaxation in CH3I and Self-Reaction of CH3 Radicals
%U https://acs.figshare.com/articles/journal_contribution/Decomposition_and_Vibrational_Relaxation_in_CH_sub_3_sub_I_and_Self_Reaction_of_CH_sub_3_sub_Radicals/2841625
%R 10.1021/jp903336u.s001
%2 https://acs.figshare.com/ndownloader/files/4539358
%K dissociation
%K CH 3I show
%K CH 3 RadicalsVibrational relaxation
%K coefficient
%K cm
%K vibrational relaxation experiments
%K diaphragmless shock tube
%K RRKM
%K CH 3I
%K laser schlieren densitometry
%K incident shock waves
%K methyl radicals
%X Vibrational relaxation and dissociation of CH3I, 2−20% in krypton, have been investigated behind incident shock waves in a diaphragmless shock tube at 20, 66, 148, and 280 Torr and 630−2200 K by laser schlieren densitometry. The effective collision energy obtained from the vibrational relaxation experiments has a small, positive temperature dependence, ⟨ΔE⟩down = 63 × (T/298)0.56 cm−1. First-order rate coefficients for dissociation of CH3I show a strong pressure dependence and are close to the low-pressure limit. Restricted-rotor Gorin model RRKM calculations fit the experimental results very well with ⟨ΔE⟩down = 378 × (T/298)0.457 cm−1. The secondary chemistry of this reaction system is dominated by reactions of methyl radicals and the reaction of the H atom with CH3I. The results of the decomposition experiments are very well simulated with a model that incorporates methyl recombination and reactions of methylene. Second-order rate coefficients for ethane dissociation to two methyl radicals were derived from the experiments and yield k = (4.50 ± 0.50) × 1017 exp(−32709/T) cm3 mol−1 s−1, in good agreement with previous measurements. Rate coefficients for H + CH3I were also obtained and give k = (7.50 ± 1.0) × 1013 exp(−601/T) cm3 mol−1 s−1, in reasonable agreement with a previous experimental value.
%I ACS Publications