Kinetics of OH reactions with aliphatic thiols

The kinetics of OH reactions with 1–4 carbon aliphatic thiols have been investigated over the temperature range 252–430 K. OH radicals were produced by flash photolysis of water vapor at λ > 165 nm and detected by time‐resolved resonance fluorescence spectroscopy. All thiols investigated react with OH at nearly the same rate; k (298 K) = 3.2–4.6 × 10 −11 cm 3 molecule −1 s −1 , ‐ E act = 0.6–1.0 kcal/mol, A = 0.6–1.2 × 10 −11 cm 3 molecule −1 s −1 . CH 3 SH and CH 3 SD react with OH at identical rates over the entire temperature range investigated. We conclude that the dominant reaction pathway is addition to the sulfur atom.