Kinetic Studies of Atomic Carbon, C[2p2 (3PJ)], with Thiols by Time-Resolved Atomic Resonance Absorption Spectroscopy in the Vacuum Ultraviolet

Reaction rates of atomic carbon in its electronic ground state, C[2p2 (3PJ)], with a range of large sulfur-containing molecules have been investigated using time-resolved atomic spectroscopy in the vacuum ultraviolet following pulsed irradiation. Absolute rate data for the collisional removal at 300 K of C(23PJ) by the gases 1-propanethiol, 1-butanethiol, 1-pentanethiol, 2-propanethiol, 2-methyl-1-propanethiol, 2-methyl-2-propanethiol and dimethyl sulfide are reported. All processes proceed at rates of the order of the collision numbers, supporting an overall mechanism of C-atom insertion into the S–H bond following initial addition, which is energetically favourable, a mechanism demonstrated analogously hitherto with H2S and where H-atom abstraction would also be endothermic.