Jump to main content
Jump to site search

Issue 31, 2016
Previous Article Next Article

Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide

Author affiliations

Abstract

The automated Reaction Mechanism Generator (RMG), using rate parameters derived from ab initio CCSD(T) calculations, is used to build reaction networks for the thermal decomposition of di-tert-butyl sulfide. Simulation results were compared with data from pyrolysis experiments with and without the addition of a cyclohexene inhibitor. Purely free-radical chemistry did not properly explain the reactivity of di-tert-butyl sulfide, as the previous experimental work showed that the sulfide decomposed via first-order kinetics in the presence and absence of the radical inhibitor. The concerted unimolecular decomposition of di-tert-butyl sulfide to form isobutene and tert-butyl thiol was found to be a key reaction in both cases, as it explained the first-order sulfide decomposition. The computer-generated kinetic model predictions quantitatively match most of the experimental data, but the model is apparently missing pathways for radical-induced decomposition of thiols to form elemental sulfur. Cyclohexene has a significant effect on the composition of the radical pool, and this led to dramatic changes in the resulting product distribution.

Graphical abstract: Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide

Back to tab navigation

Supplementary files

Publication details

The article was received on 03 Apr 2016, accepted on 11 Jul 2016 and first published on 12 Jul 2016


Article type: Paper
DOI: 10.1039/C6CP02202B
Author version available: Download Author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2016,18, 21651-21658
  •   Request permissions

    Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide

    C. A. Class, M. Liu, A. G. Vandeputte and W. H. Green, Phys. Chem. Chem. Phys., 2016, 18, 21651
    DOI: 10.1039/C6CP02202B

Search articles by author

Spotlight

Advertisements