A kinetic and thermochemical database for organic sulfur and oxygen compounds
Potential energy surfaces and reaction kinetics were calculated for 40 reactions involving sulfur and oxygen. This includes 11 H[subscript 2]O addition, 8 H[subscript 2]S addition, 11 hydrogen abstraction, 7 beta scission, and 3 elementary tautomerization reactions, which are potentially relevant in...
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| Format: | Article |
| Language: | en_US |
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Royal Society of Chemistry
2016
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| Online Access: | http://hdl.handle.net/1721.1/102378 |
| _version_ | 1826191797302329344 |
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| author | Class, Caleb A. Aguilera-Iparraguirre, Jorge Green, William H. |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Class, Caleb A. Aguilera-Iparraguirre, Jorge Green, William H. |
| author_sort | Class, Caleb A. |
| collection | MIT |
| description | Potential energy surfaces and reaction kinetics were calculated for 40 reactions involving sulfur and oxygen. This includes 11 H[subscript 2]O addition, 8 H[subscript 2]S addition, 11 hydrogen abstraction, 7 beta scission, and 3 elementary tautomerization reactions, which are potentially relevant in the combustion and desulfurization of sulfur compounds found in various fuel sources. Geometry optimizations and frequencies were calculated for reactants and transition states using B3LYP/CBSB7, and potential energies were calculated using CBS-QB3 and CCSD(T)-F12a/VTZ-F12. Rate coefficients were calculated using conventional transition state theory, with corrections for internal rotations and tunneling. Additionally, thermochemical parameters were calculated for each of the compounds involved in these reactions. With few exceptions, rate parameters calculated using the two potential energy methods agreed reasonably, with calculated activation energies differing by less than 5 kJ mol[superscript −1]. The computed rate coefficients and thermochemical parameters are expected to be useful for kinetic modeling. |
| first_indexed | 2024-09-23T09:01:27Z |
| format | Article |
| id | mit-1721.1/102378 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T09:01:27Z |
| publishDate | 2016 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | mit-1721.1/1023782022-09-26T09:56:28Z A kinetic and thermochemical database for organic sulfur and oxygen compounds Class, Caleb A. Aguilera-Iparraguirre, Jorge Green, William H. Massachusetts Institute of Technology. Department of Chemical Engineering Green, William H. Class, Caleb A. Aguilera-Iparraguirre, Jorge Green, William H. Potential energy surfaces and reaction kinetics were calculated for 40 reactions involving sulfur and oxygen. This includes 11 H[subscript 2]O addition, 8 H[subscript 2]S addition, 11 hydrogen abstraction, 7 beta scission, and 3 elementary tautomerization reactions, which are potentially relevant in the combustion and desulfurization of sulfur compounds found in various fuel sources. Geometry optimizations and frequencies were calculated for reactants and transition states using B3LYP/CBSB7, and potential energies were calculated using CBS-QB3 and CCSD(T)-F12a/VTZ-F12. Rate coefficients were calculated using conventional transition state theory, with corrections for internal rotations and tunneling. Additionally, thermochemical parameters were calculated for each of the compounds involved in these reactions. With few exceptions, rate parameters calculated using the two potential energy methods agreed reasonably, with calculated activation energies differing by less than 5 kJ mol[superscript −1]. The computed rate coefficients and thermochemical parameters are expected to be useful for kinetic modeling. Saudi Aramco (Contract 6600023444) 2016-05-03T13:52:50Z 2016-05-03T13:52:50Z 2015-04 2014-12 Article http://purl.org/eprint/type/JournalArticle 1463-9076 1463-9084 http://hdl.handle.net/1721.1/102378 Class, Caleb A., Jorge Aguilera-Iparraguirre, and William H. Green. “A Kinetic and Thermochemical Database for Organic Sulfur and Oxygen Compounds.” Phys. Chem. Chem. Phys. 17, no. 20 (2015): 13625–13639. en_US http://dx.doi.org/10.1039/c4cp05631k 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 Prof. Green via Erja Kajosalo |
| spellingShingle | Class, Caleb A. Aguilera-Iparraguirre, Jorge Green, William H. A kinetic and thermochemical database for organic sulfur and oxygen compounds |
| title | A kinetic and thermochemical database for organic sulfur and oxygen compounds |
| title_full | A kinetic and thermochemical database for organic sulfur and oxygen compounds |
| title_fullStr | A kinetic and thermochemical database for organic sulfur and oxygen compounds |
| title_full_unstemmed | A kinetic and thermochemical database for organic sulfur and oxygen compounds |
| title_short | A kinetic and thermochemical database for organic sulfur and oxygen compounds |
| title_sort | kinetic and thermochemical database for organic sulfur and oxygen compounds |
| url | http://hdl.handle.net/1721.1/102378 |
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