An experimental and theoretical study of the reaction of ethanethiol with Cl atoms

Laser photolysis-resonance fluorescence was used for the first time to investigate the reaction of ethanethiol with atmospheric relevant Cl atoms as a function of temperature and pressure. Kinetic data obtained were used to derive an Arrhenius expression. Moreover, a mechanism is proposed on the base of ab initio MP2/6-311G** calculations. Activation energies have been estimated through QCISD(T) molecular energies. Accordingly, our results predict, for the first time, two nearly energy-equivalent channels for H-abstraction from CH3CH2SH under attack by Cl, one showing attack along H-S bond whereas the other exhibits attack along H-Cα bond.

Graphical abstractGas-phase reaction of atmospheric chlorine atoms with ethanethiol was investigated as a function of temperature and pressure by laser photolysis-resonance fluorescence, for the first time. Theoretical calculations on the mechanism of this reaction predict two nearly energy-equivalent channels for H-abstraction by Cl.Download full-size image