Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide
Name
Green_Automatic mechanism.pdf
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1.47 MB
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Checksum (MD5)
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Author(s)
Class, Caleb Andrew
Liu, Mengjie
Vandeputte, Aaron
Green, William H
Date Issued
July 2016
Journal
Physical Chemistry Chemical Physics
Publisher
Royal Society of Chemistry, The
Citation
Class, Caleb A. et al. “Automatic Mechanism Generation for Pyrolysis of Di-Tert-Butyl Sulfide.” Physical Chemistry Chemical Physics 18, 31 (2016): 21651–21658 © 2016 Royal Society of Chemistry
Version
Author's final manuscript
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
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Creative Commons Attribution-Noncommercial-Share Alike
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DOI of Published Version
https://doi.org/10.1039/C6CP02202B
