Theoretical and Ftir Study of the Atmospheric Reaction of Methyl Dichloroacetate with •Oh and Cl• Radicals: Kinetics, Products and Mechanism
This is a preprint article, it offers immediate access but has not been peer reviewed.
| Main Authors: | , , , , , |
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| Format: | info:eu-repo/semantics/publishedVersion |
| Language: | eng |
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2024
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| Online Access: | http://hdl.handle.net/11086/552451 https://papers.ssrn.com/sol3/papers.cfm?abstract_id=4796935 http://dx.doi.org/10.2139/ssrn.4796935 |
| _version_ | 1806012308877475840 |
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| author | Straccia C., Vianni G. Cardona, Alejandro L. Blanco, María B. Rivela, Cynthia B. Teruel, Mariano A. Ventura, Oscar N. |
| author2 | https://orcid.org/0000-0003-2656-1597 |
| author_facet | https://orcid.org/0000-0003-2656-1597 Straccia C., Vianni G. Cardona, Alejandro L. Blanco, María B. Rivela, Cynthia B. Teruel, Mariano A. Ventura, Oscar N. |
| author_sort | Straccia C., Vianni G. |
| collection | Repositorio Digital Universitario |
| description | This is a preprint article, it offers immediate access but has not been peer reviewed. |
| format | info:eu-repo/semantics/publishedVersion |
| id | rdu-unc.552451 |
| institution | Universidad Nacional de Cordoba |
| language | eng |
| publishDate | 2024 |
| record_format | dspace |
| spelling | rdu-unc.5524512024-06-30T06:24:15Z Theoretical and Ftir Study of the Atmospheric Reaction of Methyl Dichloroacetate with •Oh and Cl• Radicals: Kinetics, Products and Mechanism Straccia C., Vianni G. Cardona, Alejandro L. Blanco, María B. Rivela, Cynthia B. Teruel, Mariano A. Ventura, Oscar N. https://orcid.org/0000-0003-2656-1597 https://orcid.org/0000-0003-4790-4579 https://orcid.org/0000-0002-5001-3200 https://orcid.org/0000-0001-5474-0061 Methyl dichloroacetate Fourier transform infrared Potential-Energy Surface Volatile Organic Compounds Atmospheric oxidants https://orcid.org/0000-0003-2846-6948 This is a preprint article, it offers immediate access but has not been peer reviewed. info:eu-repo/semantics/publishedVersion Fil: Straccia C., Vianni G. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica, Argentina. Fil: Straccia C., Vianni G. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigaciones en Físico-Química de Córdoba. Laboratorio Universitario de Química y Contaminación del Aire, Argentina. Fil: Cardona, Alejandro L. Universidad de la República. Facultad de Química. Computational Chemistry and Biology Group, Montevideo, Uruguay. Fil: Blanco, María B. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica, Argentina. Fil: Blanco, María B. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigaciones en Físico-Química de Córdoba. Laboratorio Universitario de Química y Contaminación del Aire, Argentina. Fil: Blanco, María B. University of Wuppertal. Institute for Atmospheric and Environmental Research, Wuppertal, Germany. Fil: Rivela, Cynthia B. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica, Argentina. Fil: Rivela, Cynthia B. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigaciones en Físico-Química de Córdoba. Laboratorio Universitario de Química y Contaminación del Aire, Argentina. Fil: Teruel, Mariano A. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica, Argentina. Fil: Teruel, Mariano A. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigaciones en Físico-Química de Córdoba. Laboratorio Universitario de Química y Contaminación del Aire, Argentina. Fil: Ventura, Oscar N. Universidad de la República. Facultad de Química. Computational Chemistry and Biology Group, Montevideo, Uruguay. The atmospheric degradation of methyl dichloroacetate initiated by •OH and Cl• radicals can occur via H-atom abstraction from the alkyl groups, (Cl2HC– or –CH3). The product yields for the gas phase reaction with •OH were determined experimentally in a 480 L Pyrex glass atmospheric-simulation reactor coupled to an in-situ Fourier transform infrared (FTIR) spectrometer. In addition to those results, we present in this paper a complete degradation mechanism, based on thermodynamic data obtained by identifying all critical points on the potential-energy surface for said reactions, employing density functional calculations with the M06-2X and MN15 hybrid exchange-correlation functionals and the aug-cc-pVTZ basis sets. A conformational search for reactants and transition states was performed. The energies of these conformers were later corrected at the CCSD(T,Full)-F12/CBS level using the SVECV-f12 composite method. The corrected energies were then used to obtain the theoretical rate coefficients in a multi-conformer approach. The products and their yields for the reaction with •OH were Cl2CHCOOH (44±3%), COCl2 (43±3%), and CO (41±6%). The analysis of the mechanism suggests that formation of P1 (Cl2CO, phosgene) occurs mainly by abstraction from the Cl2HC– group, since the formation of P4 (Cl2CHC(O)OH, dichloroacetic acid) and P5 (CO, carbon monoxide) are more favorable in the path for abstraction from the –OCH3 group. The multi-conformer calculated rate constants values were compared with the values obtained employing only the low-lying TS’s and with our own previous experimental studies. Branching ratios for the reaction with •Cl were compared with the experimental yields of products. info:eu-repo/semantics/publishedVersion Fil: Straccia C., Vianni G. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica, Argentina. Fil: Straccia C., Vianni G. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigaciones en Físico-Química de Córdoba. Laboratorio Universitario de Química y Contaminación del Aire, Argentina. Fil: Cardona, Alejandro L. Universidad de la República. Facultad de Química. Computational Chemistry and Biology Group, Montevideo, Uruguay. Fil: Blanco, María B. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica, Argentina. Fil: Blanco, María B. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigaciones en Físico-Química de Córdoba. Laboratorio Universitario de Química y Contaminación del Aire, Argentina. Fil: Blanco, María B. University of Wuppertal. Institute for Atmospheric and Environmental Research, Wuppertal, Germany. Fil: Rivela, Cynthia B. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica, Argentina. Fil: Rivela, Cynthia B. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigaciones en Físico-Química de Córdoba. Laboratorio Universitario de Química y Contaminación del Aire, Argentina. Fil: Teruel, Mariano A. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica, Argentina. Fil: Teruel, Mariano A. Consejo Nacional de Investigaciones Científicas y Técnicas. Instituto de Investigaciones en Físico-Química de Córdoba. Laboratorio Universitario de Química y Contaminación del Aire, Argentina. Fil: Ventura, Oscar N. Universidad de la República. Facultad de Química. Computational Chemistry and Biology Group, Montevideo, Uruguay. 2024-06-29T14:43:32Z 2024-06-29T14:43:32Z 2024-04-17 article Cardona, Alejandro L. and Blanco, María B. and Rivela, Cynthia B. and Teruel, Mariano and Ventura, Oscar N., Theoretical and Ftir Study of the Atmospheric Reaction of Methyl Dichloroacetate with •Oh and Cl• Radicals: Kinetics, Products and Mechanism. Available at SSRN: https://ssrn.com/abstract=4796935 or http://dx.doi.org/10.2139/ssrn.4796935 http://hdl.handle.net/11086/552451 1556-5068 https://papers.ssrn.com/sol3/papers.cfm?abstract_id=4796935 http://dx.doi.org/10.2139/ssrn.4796935 eng Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
| spellingShingle | Methyl dichloroacetate Fourier transform infrared Potential-Energy Surface Volatile Organic Compounds Atmospheric oxidants https://orcid.org/0000-0003-2846-6948 Straccia C., Vianni G. Cardona, Alejandro L. Blanco, María B. Rivela, Cynthia B. Teruel, Mariano A. Ventura, Oscar N. Theoretical and Ftir Study of the Atmospheric Reaction of Methyl Dichloroacetate with •Oh and Cl• Radicals: Kinetics, Products and Mechanism |
| title | Theoretical and Ftir Study of the Atmospheric Reaction of Methyl Dichloroacetate with •Oh and Cl• Radicals: Kinetics, Products and Mechanism |
| title_full | Theoretical and Ftir Study of the Atmospheric Reaction of Methyl Dichloroacetate with •Oh and Cl• Radicals: Kinetics, Products and Mechanism |
| title_fullStr | Theoretical and Ftir Study of the Atmospheric Reaction of Methyl Dichloroacetate with •Oh and Cl• Radicals: Kinetics, Products and Mechanism |
| title_full_unstemmed | Theoretical and Ftir Study of the Atmospheric Reaction of Methyl Dichloroacetate with •Oh and Cl• Radicals: Kinetics, Products and Mechanism |
| title_short | Theoretical and Ftir Study of the Atmospheric Reaction of Methyl Dichloroacetate with •Oh and Cl• Radicals: Kinetics, Products and Mechanism |
| title_sort | theoretical and ftir study of the atmospheric reaction of methyl dichloroacetate with •oh and cl• radicals kinetics products and mechanism |
| topic | Methyl dichloroacetate Fourier transform infrared Potential-Energy Surface Volatile Organic Compounds Atmospheric oxidants https://orcid.org/0000-0003-2846-6948 |
| url | http://hdl.handle.net/11086/552451 https://papers.ssrn.com/sol3/papers.cfm?abstract_id=4796935 http://dx.doi.org/10.2139/ssrn.4796935 |
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