Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline

Autores
Marmisollé, Waldemar Alejandro; Florit, Maria Ines; Posadas, Dionisio
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
In this work it is investigated the coupling between the redox potential and the extent of proton binding in electrochemically active polymers, for the particular case of Polyaniline (Pani). To this purpose, the degree of oxidation of the polymer was measured by spectrophotometry changing the external potential applied to Pani films, in solutions of different pH values. The knowledge of the oxidation degree for the different applied potentials allows determining the apparent formal redox potential. For Pani, in the hypothetical case of absence of interactions between the redox centres, the apparent formal redox potential should be independent of the oxidation degree and it should decrease linearly with the pH with a slope of 0.059 V, at room temperature. The values of the apparent formal redox potential, experimentally obtained, show that the pH dependence is not as expected from the redox equation. This fact implies interactions between the redox centres and some sort of coupling between the redox potential and the state of binding of the polymer. By employing a simple statistical mechanic model is possible to evaluate the interaction energy between the redox centres and also the acid dissociation constants of both, the oxidized and reduced forms. The values obtained for both dissociation constants agree with some reported in the literature. The application of the model also allows explaining the observed relationship between the apparent formal redox potential and the electrolyte pH.
Fil: Marmisollé, Waldemar Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Florit, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Posadas, Dionisio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
Conducting Polymers
Coupling
Polyaniline
Proton Binding
Redox Potential Distribution
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/81879
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/81879
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of PolyanilineMarmisollé, Waldemar AlejandroFlorit, Maria InesPosadas, DionisioConducting PolymersCouplingPolyanilineProton BindingRedox Potential Distributionhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1In this work it is investigated the coupling between the redox potential and the extent of proton binding in electrochemically active polymers, for the particular case of Polyaniline (Pani). To this purpose, the degree of oxidation of the polymer was measured by spectrophotometry changing the external potential applied to Pani films, in solutions of different pH values. The knowledge of the oxidation degree for the different applied potentials allows determining the apparent formal redox potential. For Pani, in the hypothetical case of absence of interactions between the redox centres, the apparent formal redox potential should be independent of the oxidation degree and it should decrease linearly with the pH with a slope of 0.059 V, at room temperature. The values of the apparent formal redox potential, experimentally obtained, show that the pH dependence is not as expected from the redox equation. This fact implies interactions between the redox centres and some sort of coupling between the redox potential and the state of binding of the polymer. By employing a simple statistical mechanic model is possible to evaluate the interaction energy between the redox centres and also the acid dissociation constants of both, the oxidized and reduced forms. The values obtained for both dissociation constants agree with some reported in the literature. The application of the model also allows explaining the observed relationship between the apparent formal redox potential and the electrolyte pH.Fil: Marmisollé, Waldemar Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Florit, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Posadas, Dionisio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaElsevier Science Sa2013-10-15info: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/11336/81879Marmisollé, Waldemar Alejandro; Florit, Maria Ines; Posadas, Dionisio; Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline; Elsevier Science Sa; Journal of Electroanalytical Chemistry; 707; 15-10-2013; 43-510022-0728CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S1572665713003627info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jelechem.2013.08.012info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:28:28Zoai:ri.conicet.gov.ar:11336/81879instacron: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:34982025-09-29 10:28:28.796CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline
title Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline
spellingShingle Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline
Marmisollé, Waldemar Alejandro
Conducting Polymers
Coupling
Polyaniline
Proton Binding
Redox Potential Distribution
title_short Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline
title_full Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline
title_fullStr Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline
title_full_unstemmed Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline
title_sort Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline
dc.creator.none.fl_str_mv Marmisollé, Waldemar Alejandro
Florit, Maria Ines
Posadas, Dionisio
author Marmisollé, Waldemar Alejandro
author_facet Marmisollé, Waldemar Alejandro
Florit, Maria Ines
Posadas, Dionisio
author_role author
author2 Florit, Maria Ines
Posadas, Dionisio
author2_role author
author
dc.subject.none.fl_str_mv Conducting Polymers
Coupling
Polyaniline
Proton Binding
Redox Potential Distribution
topic Conducting Polymers
Coupling
Polyaniline
Proton Binding
Redox Potential Distribution
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv In this work it is investigated the coupling between the redox potential and the extent of proton binding in electrochemically active polymers, for the particular case of Polyaniline (Pani). To this purpose, the degree of oxidation of the polymer was measured by spectrophotometry changing the external potential applied to Pani films, in solutions of different pH values. The knowledge of the oxidation degree for the different applied potentials allows determining the apparent formal redox potential. For Pani, in the hypothetical case of absence of interactions between the redox centres, the apparent formal redox potential should be independent of the oxidation degree and it should decrease linearly with the pH with a slope of 0.059 V, at room temperature. The values of the apparent formal redox potential, experimentally obtained, show that the pH dependence is not as expected from the redox equation. This fact implies interactions between the redox centres and some sort of coupling between the redox potential and the state of binding of the polymer. By employing a simple statistical mechanic model is possible to evaluate the interaction energy between the redox centres and also the acid dissociation constants of both, the oxidized and reduced forms. The values obtained for both dissociation constants agree with some reported in the literature. The application of the model also allows explaining the observed relationship between the apparent formal redox potential and the electrolyte pH.
Fil: Marmisollé, Waldemar Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Florit, Maria Ines. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: Posadas, Dionisio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description In this work it is investigated the coupling between the redox potential and the extent of proton binding in electrochemically active polymers, for the particular case of Polyaniline (Pani). To this purpose, the degree of oxidation of the polymer was measured by spectrophotometry changing the external potential applied to Pani films, in solutions of different pH values. The knowledge of the oxidation degree for the different applied potentials allows determining the apparent formal redox potential. For Pani, in the hypothetical case of absence of interactions between the redox centres, the apparent formal redox potential should be independent of the oxidation degree and it should decrease linearly with the pH with a slope of 0.059 V, at room temperature. The values of the apparent formal redox potential, experimentally obtained, show that the pH dependence is not as expected from the redox equation. This fact implies interactions between the redox centres and some sort of coupling between the redox potential and the state of binding of the polymer. By employing a simple statistical mechanic model is possible to evaluate the interaction energy between the redox centres and also the acid dissociation constants of both, the oxidized and reduced forms. The values obtained for both dissociation constants agree with some reported in the literature. The application of the model also allows explaining the observed relationship between the apparent formal redox potential and the electrolyte pH.
publishDate 2013
dc.date.none.fl_str_mv 2013-10-15
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/11336/81879
Marmisollé, Waldemar Alejandro; Florit, Maria Ines; Posadas, Dionisio; Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline; Elsevier Science Sa; Journal of Electroanalytical Chemistry; 707; 15-10-2013; 43-51
0022-0728
CONICET Digital
CONICET
url http://hdl.handle.net/11336/81879
identifier_str_mv Marmisollé, Waldemar Alejandro; Florit, Maria Ines; Posadas, Dionisio; Coupling between proton binding and redox potential in electrochemically active macromolecules. the example of Polyaniline; Elsevier Science Sa; Journal of Electroanalytical Chemistry; 707; 15-10-2013; 43-51
0022-0728
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S1572665713003627
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jelechem.2013.08.012
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science Sa
publisher.none.fl_str_mv Elsevier Science Sa
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
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score 13.070432

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