Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds

Autores
Garcia Einschlag, Fernando Sebastian; Carlos, Luciano; Capparelli, Alberto Luis
Año de publicación
2003
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The rate constants for hydroxyl radical reaction toward a set of nitroaromatic substrates kS, have been measured at 25ºC using competition experiments in the UV/H2O2 process. For a given pair of substrates S1 and S2, the relative reactivity beta(defined as kS1/kS2) was calculated from the slope of the corresponding double logarithmic plot, i.e., of ln[S1] vs. Ln[S2]. This method is more accurate and remained linear for larger conversions in comparison with the plots of ln[S1] and ln[S2] against time. The rate constants measured ranged from 0.33 to 8.6 109 M-1 s-1. A quantitative structure–reactivity relationship was found using the Hammett equation. Assuming sigma values to be additive, a value of -0.60 was obtained for the reaction constant rho. This value agrees with the high reactivity and the electrophilic nature of HO•.radical.
Fil: Garcia Einschlag, Fernando Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Carlos, Luciano. Universidad Nacional de La Plata; Argentina
Fil: Capparelli, Alberto Luis. Universidad Nacional de La Plata; Argentina
Materia
Advanced Oxidation Processes
Nitroaromatic Compounds
Hydroxyl Radicals
Competitive Kinetics
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/28584
Acceder
id CONICETDig_43ca6998d1ec266cc6ba5c1f5d4dd069
oai_identifier_str oai:ri.conicet.gov.ar:11336/28584
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compoundsGarcia Einschlag, Fernando SebastianCarlos, LucianoCapparelli, Alberto LuisAdvanced Oxidation ProcessesNitroaromatic CompoundsHydroxyl RadicalsCompetitive Kineticshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The rate constants for hydroxyl radical reaction toward a set of nitroaromatic substrates kS, have been measured at 25ºC using competition experiments in the UV/H2O2 process. For a given pair of substrates S1 and S2, the relative reactivity beta(defined as kS1/kS2) was calculated from the slope of the corresponding double logarithmic plot, i.e., of ln[S1] vs. Ln[S2]. This method is more accurate and remained linear for larger conversions in comparison with the plots of ln[S1] and ln[S2] against time. The rate constants measured ranged from 0.33 to 8.6 10<sup>9</sup> M-1 s-1. A quantitative structure–reactivity relationship was found using the Hammett equation. Assuming sigma values to be additive, a value of -0.60 was obtained for the reaction constant rho. This value agrees with the high reactivity and the electrophilic nature of HO•.radical.Fil: Garcia Einschlag, Fernando Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Carlos, Luciano. Universidad Nacional de La Plata; ArgentinaFil: Capparelli, Alberto Luis. Universidad Nacional de La Plata; ArgentinaPergamon-Elsevier Science Ltd.2003-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/28584Garcia Einschlag, Fernando Sebastian; Carlos, Luciano; Capparelli, Alberto Luis; Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds; Pergamon-Elsevier Science Ltd.; Chemosphere; 53; 12-2003; 1-70045-6535CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/S0045-6535(03)00388-6info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-29T12:47:24Zoai:ri.conicet.gov.ar:11336/28584instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-29 12:47:25.12CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds
title Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds
spellingShingle Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds
Garcia Einschlag, Fernando Sebastian
Advanced Oxidation Processes
Nitroaromatic Compounds
Hydroxyl Radicals
Competitive Kinetics
title_short Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds
title_full Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds
title_fullStr Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds
title_full_unstemmed Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds
title_sort Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds
dc.creator.none.fl_str_mv Garcia Einschlag, Fernando Sebastian
Carlos, Luciano
Capparelli, Alberto Luis
author Garcia Einschlag, Fernando Sebastian
author_facet Garcia Einschlag, Fernando Sebastian
Carlos, Luciano
Capparelli, Alberto Luis
author_role author
author2 Carlos, Luciano
Capparelli, Alberto Luis
author2_role author
author
dc.subject.none.fl_str_mv Advanced Oxidation Processes
Nitroaromatic Compounds
Hydroxyl Radicals
Competitive Kinetics
topic Advanced Oxidation Processes
Nitroaromatic Compounds
Hydroxyl Radicals
Competitive Kinetics
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The rate constants for hydroxyl radical reaction toward a set of nitroaromatic substrates kS, have been measured at 25ºC using competition experiments in the UV/H2O2 process. For a given pair of substrates S1 and S2, the relative reactivity beta(defined as kS1/kS2) was calculated from the slope of the corresponding double logarithmic plot, i.e., of ln[S1] vs. Ln[S2]. This method is more accurate and remained linear for larger conversions in comparison with the plots of ln[S1] and ln[S2] against time. The rate constants measured ranged from 0.33 to 8.6 10<sup>9</sup> M-1 s-1. A quantitative structure–reactivity relationship was found using the Hammett equation. Assuming sigma values to be additive, a value of -0.60 was obtained for the reaction constant rho. This value agrees with the high reactivity and the electrophilic nature of HO•.radical.
Fil: Garcia Einschlag, Fernando Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina
Fil: Carlos, Luciano. Universidad Nacional de La Plata; Argentina
Fil: Capparelli, Alberto Luis. Universidad Nacional de La Plata; Argentina
description The rate constants for hydroxyl radical reaction toward a set of nitroaromatic substrates kS, have been measured at 25ºC using competition experiments in the UV/H2O2 process. For a given pair of substrates S1 and S2, the relative reactivity beta(defined as kS1/kS2) was calculated from the slope of the corresponding double logarithmic plot, i.e., of ln[S1] vs. Ln[S2]. This method is more accurate and remained linear for larger conversions in comparison with the plots of ln[S1] and ln[S2] against time. The rate constants measured ranged from 0.33 to 8.6 10<sup>9</sup> M-1 s-1. A quantitative structure–reactivity relationship was found using the Hammett equation. Assuming sigma values to be additive, a value of -0.60 was obtained for the reaction constant rho. This value agrees with the high reactivity and the electrophilic nature of HO•.radical.
publishDate 2003
dc.date.none.fl_str_mv 2003-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
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://hdl.handle.net/11336/28584
Garcia Einschlag, Fernando Sebastian; Carlos, Luciano; Capparelli, Alberto Luis; Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds; Pergamon-Elsevier Science Ltd.; Chemosphere; 53; 12-2003; 1-7
0045-6535
CONICET Digital
CONICET
url http://hdl.handle.net/11336/28584
identifier_str_mv Garcia Einschlag, Fernando Sebastian; Carlos, Luciano; Capparelli, Alberto Luis; Competition kinetics using the UV/H2O2 process: a structure reactivity correlation for the rate constants of hydroxyl radicals toward nitroaromatic compounds; Pergamon-Elsevier Science Ltd.; Chemosphere; 53; 12-2003; 1-7
0045-6535
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/S0045-6535(03)00388-6
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd.
publisher.none.fl_str_mv Pergamon-Elsevier Science Ltd.
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
_version_ 1847427533327302656
score 13.10058

Publicaciones similares