Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide
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 a...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | en_US |
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Royal Society of Chemistry, The
2017
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| Online Access: | http://hdl.handle.net/1721.1/110982 https://orcid.org/0000-0003-2414-1986 |
| _version_ | 1826215298158559232 |
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| author | Class, Caleb Andrew Liu, Mengjie Vandeputte, Aaron Green, William H |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Class, Caleb Andrew Liu, Mengjie Vandeputte, Aaron Green, William H |
| author_sort | Class, Caleb Andrew |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T16:22:29Z |
| format | Article |
| id | mit-1721.1/110982 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T16:22:29Z |
| publishDate | 2017 |
| publisher | Royal Society of Chemistry, The |
| record_format | dspace |
| spelling | mit-1721.1/1109822022-09-29T19:43:54Z Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide Class, Caleb Andrew Liu, Mengjie Vandeputte, Aaron Green, William H Massachusetts Institute of Technology. Department of Chemical Engineering Green, William H Class, Caleb Andrew Liu, Mengjie Vandeputte, Aaron Green, William H 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. 2017-08-18T15:54:39Z 2017-08-18T15:54:39Z 2016-07 2016-04 Article http://purl.org/eprint/type/JournalArticle 1463-9076 1463-9084 http://hdl.handle.net/1721.1/110982 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 https://orcid.org/0000-0003-2414-1986 en_US http://dx.doi.org/10.1039/C6CP02202B Physical Chemistry Chemical Physics Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Royal Society of Chemistry, The Prof. Green via Erja Kasjosalo |
| spellingShingle | Class, Caleb Andrew Liu, Mengjie Vandeputte, Aaron Green, William H Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide |
| title | Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide |
| title_full | Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide |
| title_fullStr | Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide |
| title_full_unstemmed | Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide |
| title_short | Automatic mechanism generation for pyrolysis of di-tert-butyl sulfide |
| title_sort | automatic mechanism generation for pyrolysis of di tert butyl sulfide |
| url | http://hdl.handle.net/1721.1/110982 https://orcid.org/0000-0003-2414-1986 |
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