Rate constants for the reaction of H atoms with the alkyl iodides iodomethane (1), deuterated iodomethane (1d), iodoethane (2), 2-iodopropane (3), and 2-iodo-2-methyl propane (4) have been measured using the flash-photolysis resonance fluorescence technique. The results are k 1 ) (6.3 ( 0.6) × 10 -11 exp [((-5(T ) 295 K) and k 4 ) 2.0 × 10 -11 (T ) 294 K) cm 3 molecule -1 s -1 . The transition state for the substitution reaction H + CH 3 I f I + CH 4 was characterized at the Gaussian-2 level of ab initio theory, and the process was shown to be slow. Evidence is presented showing that H-atom abstraction is also slow, and that the dominant pathway for the reactions of H atoms with iodoalkanes is I-atom abstraction.

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