New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides
We present new reaction pathways relevant to low-temperature oxidation in gaseous and condensed phases. The new pathways originate from γ-ketohydroperoxides (KHP), which are well-known products in low-temperature oxidation and are assumed to react only via homolytic O–O dissociation in existing kine...
| Main Authors: | , , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2017
|
| Online Access: | http://hdl.handle.net/1721.1/106967 |
| _version_ | 1826217685000650752 |
|---|---|
| author | Meana-Pañeda, Rubén Yang, Ke R. Truhlar, Donald G. Jalan, Amrit Alecu, Ionut M Aguilera Iparraguirre, Jorge Merchant, Shamel S. Green, William H |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Meana-Pañeda, Rubén Yang, Ke R. Truhlar, Donald G. Jalan, Amrit Alecu, Ionut M Aguilera Iparraguirre, Jorge Merchant, Shamel S. Green, William H |
| author_sort | Meana-Pañeda, Rubén |
| collection | MIT |
| description | We present new reaction pathways relevant to low-temperature oxidation in gaseous and condensed phases. The new pathways originate from γ-ketohydroperoxides (KHP), which are well-known products in low-temperature oxidation and are assumed to react only via homolytic O–O dissociation in existing kinetic models. Our ab initio calculations identify new exothermic reactions of KHP forming a cyclic peroxide isomer, which decomposes via novel concerted reactions into carbonyl and carboxylic acid products. Geometries and frequencies of all stationary points are obtained using the M06-2X/MG3S DFT model chemistry, and energies are refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. Thermal rate coefficients are computed using variational transition-state theory (VTST) calculations with multidimensional tunneling contributions based on small-curvature tunneling (SCT). These are combined with multistructural partition functions (Q[superscript MS–T]) to obtain direct dynamics multipath (MP-VTST/SCT) gas-phase rate coefficients. For comparison with liquid-phase measurements, solvent effects are included using continuum dielectric solvation models. The predicted rate coefficients are found to be in excellent agreement with experiment when due consideration is made for acid-catalyzed isomerization. This work provides theoretical confirmation of the 30-year-old hypothesis of Korcek and co-workers that KHPs are precursors to carboxylic acid formation, resolving an open problem in the kinetics of liquid-phase autoxidation. The significance of the new pathways in atmospheric chemistry, low-temperature combustion, and oxidation of biological lipids are discussed. |
| first_indexed | 2024-09-23T17:07:31Z |
| format | Article |
| id | mit-1721.1/106967 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T17:07:31Z |
| publishDate | 2017 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1069672022-09-29T23:50:54Z New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides Meana-Pañeda, Rubén Yang, Ke R. Truhlar, Donald G. Jalan, Amrit Alecu, Ionut M Aguilera Iparraguirre, Jorge Merchant, Shamel S. Green, William H Massachusetts Institute of Technology. Department of Chemical Engineering Jalan, Amrit Alecu, Ionut M Aguilera Iparraguirre, Jorge Merchant, Shamel S. Green, William H We present new reaction pathways relevant to low-temperature oxidation in gaseous and condensed phases. The new pathways originate from γ-ketohydroperoxides (KHP), which are well-known products in low-temperature oxidation and are assumed to react only via homolytic O–O dissociation in existing kinetic models. Our ab initio calculations identify new exothermic reactions of KHP forming a cyclic peroxide isomer, which decomposes via novel concerted reactions into carbonyl and carboxylic acid products. Geometries and frequencies of all stationary points are obtained using the M06-2X/MG3S DFT model chemistry, and energies are refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. Thermal rate coefficients are computed using variational transition-state theory (VTST) calculations with multidimensional tunneling contributions based on small-curvature tunneling (SCT). These are combined with multistructural partition functions (Q[superscript MS–T]) to obtain direct dynamics multipath (MP-VTST/SCT) gas-phase rate coefficients. For comparison with liquid-phase measurements, solvent effects are included using continuum dielectric solvation models. The predicted rate coefficients are found to be in excellent agreement with experiment when due consideration is made for acid-catalyzed isomerization. This work provides theoretical confirmation of the 30-year-old hypothesis of Korcek and co-workers that KHPs are precursors to carboxylic acid formation, resolving an open problem in the kinetics of liquid-phase autoxidation. The significance of the new pathways in atmospheric chemistry, low-temperature combustion, and oxidation of biological lipids are discussed. United States. Dept. of Energy. Office of Basic Energy Sciences (Energy Frontier Research Center for Combustion Science. Grant DE-SC0001198) University of Minnesota. Supercomputer Institute Pacific Northwest National Laboratory (U.S.) Molecular Science Computing Facility 2017-02-16T16:57:22Z 2017-02-16T16:57:22Z 2013-07 2013-04 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/106967 Jalan, Amrit et al. “New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides.” Journal of the American Chemical Society 135.30 (2013): 11100–11114. © 2013 American Chemical Society en_US http://dx.doi.org/10.1021/ja4034439 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Meana-Pañeda, Rubén Yang, Ke R. Truhlar, Donald G. Jalan, Amrit Alecu, Ionut M Aguilera Iparraguirre, Jorge Merchant, Shamel S. Green, William H New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides |
| title | New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides |
| title_full | New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides |
| title_fullStr | New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides |
| title_full_unstemmed | New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides |
| title_short | New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of γ-Ketohydroperoxides |
| title_sort | new pathways for formation of acids and carbonyl products in low temperature oxidation the korcek decomposition of γ ketohydroperoxides |
| url | http://hdl.handle.net/1721.1/106967 |
| work_keys_str_mv | AT meanapanedaruben newpathwaysforformationofacidsandcarbonylproductsinlowtemperatureoxidationthekorcekdecompositionofgketohydroperoxides AT yangker newpathwaysforformationofacidsandcarbonylproductsinlowtemperatureoxidationthekorcekdecompositionofgketohydroperoxides AT truhlardonaldg newpathwaysforformationofacidsandcarbonylproductsinlowtemperatureoxidationthekorcekdecompositionofgketohydroperoxides AT jalanamrit newpathwaysforformationofacidsandcarbonylproductsinlowtemperatureoxidationthekorcekdecompositionofgketohydroperoxides AT alecuionutm newpathwaysforformationofacidsandcarbonylproductsinlowtemperatureoxidationthekorcekdecompositionofgketohydroperoxides AT aguileraiparraguirrejorge newpathwaysforformationofacidsandcarbonylproductsinlowtemperatureoxidationthekorcekdecompositionofgketohydroperoxides AT merchantshamels newpathwaysforformationofacidsandcarbonylproductsinlowtemperatureoxidationthekorcekdecompositionofgketohydroperoxides AT greenwilliamh newpathwaysforformationofacidsandcarbonylproductsinlowtemperatureoxidationthekorcekdecompositionofgketohydroperoxides |