Theoretical Study on the Unimolecular Pyrolysis of Thiophene and Modeling.

Thiophenic sulfur is the most stable and abundant organic sulfur species in petroleum. Removal of thiophenes has profound significance in environmental protection. In this work, we investigate the unimolecular pyrolysis of thiophene from a kinetic perspective. High-level ab initio methods have been employed to deduce the potential energy surface. Rate coefficients of the elementary reactions are computed using variational transition-state theory at the CCSD(T)/CBS level to develop a kinetic model. By comparison with preceding experimental results, the kinetic model shows good performance in calculating the thiophene pyrolysis rate. The Arrhenius expression for thiophene unimolecular pyrolysis has been redetermined as k = 1.21 × 10(13) × exp[(78.96 kcal/mol)/(RT)]. The unimolecular pyrolysis of thiophene is mainly initiated by the ring-H migrations, whereas the C-S bond rupture has limited contribution to the overall pyrolysis rate. Thioketene (SC(2)H(2)) and ethyne (C(2)H(2)) are the major pyrolysis products at all temperatures. Significant amounts of the thioformyl (HCS) radical and CS could also be yielded. By contrast, atomic sulfur and H(2)S are difficult to be directly produced. Possible secondary reactions in the products have also been discussed.