Rate constants and vibrational distributions for water‐forming reactions of OH and OD radicals with thioacetic acid, 1,2‐ethanedithiol and tert‐butanethiol

Reactions of OH and OD radicals with CH 3 C(O)SH, HSCH 2 CH 2 SH, and (CH 3 ) 3 CSH were studied at 298 K in a fast‐flow reactor by infrared emission spectroscopy of the water product molecules. The rate constants (1.3 ± 0.2) × 10 −11 cm 3 molecule −1 s −1 for the OD + CH 3 C(O)SH reaction and (3.8 ± 0.7) × 10 −11 cm 3 molecule −1 s −1 for the OD + HSCH 2 CH 2 SH reaction were determined by comparing the HOD emission intensity to that from the OD reaction with H 2 S, and this is the first measurement of these rate constants. In the same manner, using the OD + (C 2 H 5 ) 2 S reference reaction, the rate constant for the OD + (CH 3 ) 3 CSH reaction was estimated to be (3.6 ± 0.7) × 10 −11 cm 3 molecule −1 s −1 . Vibrational distributions of the H 2 O and HOD molecules from the title reactions are typical for H‐atom abstraction reactions by OH radicals with release of about 50% of the available energy as vibrational energy to the water molecule in a 2:1 ratio of stretch and bend modes.