Caleb A. Class

Document Type

Article

Publication Date

2016

Publication Title

Physical Chemistry Chemical Physics

First Page

21658

Last Page

21658

DOI

10.1039/C6CP02202B

Additional Publication URL

https://pubs.rsc.org/en/content/articlelanding/2016/CP/C6CP02202B#!divAbstract

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.

Rights

This is a pre-print version of this article. The version of record is available at Physical Chemistry Chemical Physics. NOTE: this version of the article is pending revision and may not reflect the changes made in the final, peer-reviewed version.

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