Shock tube pyrolysis of thiophene

Abstract

The kinetics of the thermal decomposition of thiophene diluted in argon have been studied behind reflected shock waves in a single pulse shock tube over the temperature range 1598-2022 K and pressures between 2.5 and 3.44 bar. Product yields and composition were determined using capillary column gas chromatography with flame ionization detection and flame photometric sulphur selective detection. The principal hydrocarbon product at all temperatures was ethyne. Ethanethiol was found to be the major sulphur product together with H2S formed in significant concentrations at lower temperatures. Carbon disulphide was also formed at higher temperatures. Additional reaction products were CH4, C2H4, C3H4, C4H3, C4H6, C4H4, C6H6 and C4H2 with some traces were found of C5 and C6H5 species. It was concluded that pyrolysis of thiophene is initiated by C-S bond fission to form the C4H4S radical which reacts to give C4H3 + SH together with the reaction giving C3H4 + CS. The rate expression obtained for the pyrolysis reaction was k (C4H4S)=2.2 × 1011 exp (270 kJ mol-1) s-1. Copyright © 2002 John Wiley and Sons, Ltd.