A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical

The kinetics of the thermal reaction of FS(O2)OO(O2)SF with SO2 have been theoretically studied. Experimental investigations performed at 293–323 K indicate that the FSO3 radical, in equilibrium with the peroxide FS(O2)OO(O2)SF ¢ 2 FSO3 (1, -1), initially attacks the SO2 forming the FS(O2)OSO2 radic...

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Detalles Bibliográficos
Autores: Badenes, María Paula, Cobos, Carlos Jorge, Croce, Adela Ester
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2018
País:Argentina
Institución:Universidad Nacional de La Plata
Repositorio:SEDICI (UNLP)
Idioma:inglés
OAI Identifier:oai:sedici.unlp.edu.ar:10915/73218
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/73218
Access Level:acceso abierto
Palabra clave:Química
FSO<SUB>3</SUB>, FS(O<SUB>2</SUB>)OSO<SUB>2</SUB>, (FS(O<SUB>2</SUB>)O)<SUB>2</SUB>SO<SUB>2</SUB>, quantum-chemical calculations, transition state theory, statistical adiabatic channel model
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repository_id_str
spelling A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radicalBadenes, María PaulaCobos, Carlos JorgeCroce, Adela EsterQuímicaFSO<SUB>3</SUB>, FS(O<SUB>2</SUB>)OSO<SUB>2</SUB>, (FS(O<SUB>2</SUB>)O)<SUB>2</SUB>SO<SUB>2</SUB>, quantum-chemical calculations, transition state theory, statistical adiabatic channel modelThe kinetics of the thermal reaction of FS(O2)OO(O2)SF with SO2 have been theoretically studied. Experimental investigations performed at 293–323 K indicate that the FSO3 radical, in equilibrium with the peroxide FS(O2)OO(O2)SF ¢ 2 FSO3 (1, -1), initially attacks the SO2 forming the FS(O2)OSO2 radical which afterwards may dissociate back, FSO3 + SO2 ¢FS(O2)OSO2 (2, -2), or recombinewith FSO3 generating the final product, FSO3 + FS(O2)OSO2? (FS(O2)O)2SO2 (3). Several DFT formulations and composite ab initio models were employed to characterize FS(O2)OSO2 molecular properties and to determine relevant potential energy surfaces features of reactions (2), (-2) and (3). Transition state theory calculations lead to the high pressure rate coefficients k1;2 ¼ 9:1 10 14 expð 5:2 kcal mol 1 = RTÞ cm3 molecule 1 s 1 and k1; 2 ¼ 4:9 1015 expð 13:9 kcal mol 1 =RTÞ s 1 while statistical adiabatic channel model (SACM/CT) calculations predict for the barrierless reaction (3) the expression k1;3 ¼ 2:9 10 11ðT=300Þ0:4 cm3 molecule 1 s 1. The experimental phenomenological rate coefficients are very well reproduced by these rate coefficients.Facultad de Ciencias Exactas2018info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf87-95http://sedici.unlp.edu.ar/handle/10915/73218enginfo:eu-repo/semantics/altIdentifier/issn/2210-271Xinfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.comptc.2017.11.002info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2024-05-08T12:50:46Zoai:sedici.unlp.edu.ar:10915/73218Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292024-05-08 12:50:47.162SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
title A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
spellingShingle A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
Badenes, María Paula
Química
FSO<SUB>3</SUB>, FS(O<SUB>2</SUB>)OSO<SUB>2</SUB>, (FS(O<SUB>2</SUB>)O)<SUB>2</SUB>SO<SUB>2</SUB>, quantum-chemical calculations, transition state theory, statistical adiabatic channel model
title_short A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
title_full A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
title_fullStr A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
title_full_unstemmed A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
title_sort A theoretical study of the thermal stability of the FS(O<SUB>2</SUB>)OSO<SUB>2</SUB> radical and the recombination kinetics with the FSO<SUB>3</SUB> radical
dc.creator.none.fl_str_mv Badenes, María Paula
Cobos, Carlos Jorge
Croce, Adela Ester
author Badenes, María Paula
author_facet Badenes, María Paula
Cobos, Carlos Jorge
Croce, Adela Ester
author_role author
author2 Cobos, Carlos Jorge
Croce, Adela Ester
author2_role author
author
dc.subject.none.fl_str_mv Química
FSO<SUB>3</SUB>, FS(O<SUB>2</SUB>)OSO<SUB>2</SUB>, (FS(O<SUB>2</SUB>)O)<SUB>2</SUB>SO<SUB>2</SUB>, quantum-chemical calculations, transition state theory, statistical adiabatic channel model
topic Química
FSO<SUB>3</SUB>, FS(O<SUB>2</SUB>)OSO<SUB>2</SUB>, (FS(O<SUB>2</SUB>)O)<SUB>2</SUB>SO<SUB>2</SUB>, quantum-chemical calculations, transition state theory, statistical adiabatic channel model
description The kinetics of the thermal reaction of FS(O2)OO(O2)SF with SO2 have been theoretically studied. Experimental investigations performed at 293–323 K indicate that the FSO3 radical, in equilibrium with the peroxide FS(O2)OO(O2)SF ¢ 2 FSO3 (1, -1), initially attacks the SO2 forming the FS(O2)OSO2 radical which afterwards may dissociate back, FSO3 + SO2 ¢FS(O2)OSO2 (2, -2), or recombinewith FSO3 generating the final product, FSO3 + FS(O2)OSO2? (FS(O2)O)2SO2 (3). Several DFT formulations and composite ab initio models were employed to characterize FS(O2)OSO2 molecular properties and to determine relevant potential energy surfaces features of reactions (2), (-2) and (3). Transition state theory calculations lead to the high pressure rate coefficients k1;2 ¼ 9:1 10 14 expð 5:2 kcal mol 1 = RTÞ cm3 molecule 1 s 1 and k1; 2 ¼ 4:9 1015 expð 13:9 kcal mol 1 =RTÞ s 1 while statistical adiabatic channel model (SACM/CT) calculations predict for the barrierless reaction (3) the expression k1;3 ¼ 2:9 10 11ðT=300Þ0:4 cm3 molecule 1 s 1. The experimental phenomenological rate coefficients are very well reproduced by these rate coefficients.
publishDate 2018
dc.date.none.fl_str_mv 2018
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://sedici.unlp.edu.ar/handle/10915/73218
url http://sedici.unlp.edu.ar/handle/10915/73218
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/issn/2210-271X
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.comptc.2017.11.002
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
87-95
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
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