Oxidation of hexcacyanoferrate(II) ion by hydrogen peroxide: inhibition by polyalcohols and related compounds

The oxidation of hexacyanoferrate(ll) ion by a large excess of hydrogen peroxide, in slightly acidic aqueous media containing potassium dihydrogen phosphate (pH 5.10 ± 0.05), was followed by monitoring the increase of absorbance at 420 nm as the colorless Fe(ll) complex gradually evolved into the ye...

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Detalles Bibliográficos
Autores: Pérez de Benito, Joaquín F., Prado-Diaz, Pol
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2022
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/200658
Acceso en línea:https://hdl.handle.net/2445/200658
Access Level:acceso abierto
Palabra clave:Oxidació
Aigua oxigenada
Inhibició
Oxidation
Hydrogen peroxide
Inhibition
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spelling Oxidation of hexcacyanoferrate(II) ion by hydrogen peroxide: inhibition by polyalcohols and related compoundsPérez de Benito, Joaquín F.Prado-Diaz, PolOxidacióAigua oxigenadaInhibicióOxidationHydrogen peroxideInhibitionThe oxidation of hexacyanoferrate(ll) ion by a large excess of hydrogen peroxide, in slightly acidic aqueous media containing potassium dihydrogen phosphate (pH 5.10 ± 0.05), was followed by monitoring the increase of absorbance at 420 nm as the colorless Fe(ll) complex gradually evolved into the yellow Fe(lll) complex. The reaction was inhibited by OH-containing organic compounds, either alcohols or carbohydrates, and two different inhibition pathways were observed, an iron(III)-independent pathway (rate constant k1) and an iron(III)-mediated pathway (rate constant k2). A BASIC-language computer program was developed in order to use the fourth-order Runge-Kutta integration method to obtain the concentrations of the Fe(ll)-inhibitor complex and the Fe(lll) reaction product. Rate constant k1, whose value is determined by that of the initial rate, decreased slightly as the concentration of alcohol / carbohydrate increased, and a mechanism involving the formation of hydroxyl radicals in a Fenton-like reaction and its posterior scavenging by the organic antioxidant additive has been proposed. Of the 8 inhibiting agents that were tried, the most potent antioxidant under the experimental conditions of this study was D-mannitol. Rate constant k2, whose value is a measurement of the deviation from a pseudo-first order behavior provoked by the inhibiting agent, increased notably as the concentration of the latter increased, and a mechanism involving the complexation of the Fe(lll) product by the organic inhibitor and its posterior outer-sphere one electron reduction from hexacyanoferrate(ll) ion has also been proposed. This might result in a blockage of the regeneration of pentacyanoaquaferrate(ll) ion, an intermediate believed to be essential for the redox reaction to take place.Akadémiai Kiadó2022info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://hdl.handle.net/2445/200658Articles publicats en revistes (Ciència dels Materials i Química Física)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió postprint del document publicat a: https://doi.org/10.1007/s11144-022-02306-7Reaction Kinetics Mechanisms And Catalysis, 2022, vol. 135, num. 6, p. 2897-2913https://doi.org/10.1007/s11144-022-02306-7(c) Akadémiai Kiadó, 2022info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/2006582026-05-27T06:46:51Z
dc.title.none.fl_str_mv Oxidation of hexcacyanoferrate(II) ion by hydrogen peroxide: inhibition by polyalcohols and related compounds
title Oxidation of hexcacyanoferrate(II) ion by hydrogen peroxide: inhibition by polyalcohols and related compounds
spellingShingle Oxidation of hexcacyanoferrate(II) ion by hydrogen peroxide: inhibition by polyalcohols and related compounds
Pérez de Benito, Joaquín F.
Oxidació
Aigua oxigenada
Inhibició
Oxidation
Hydrogen peroxide
Inhibition
title_short Oxidation of hexcacyanoferrate(II) ion by hydrogen peroxide: inhibition by polyalcohols and related compounds
title_full Oxidation of hexcacyanoferrate(II) ion by hydrogen peroxide: inhibition by polyalcohols and related compounds
title_fullStr Oxidation of hexcacyanoferrate(II) ion by hydrogen peroxide: inhibition by polyalcohols and related compounds
title_full_unstemmed Oxidation of hexcacyanoferrate(II) ion by hydrogen peroxide: inhibition by polyalcohols and related compounds
title_sort Oxidation of hexcacyanoferrate(II) ion by hydrogen peroxide: inhibition by polyalcohols and related compounds
dc.creator.none.fl_str_mv Pérez de Benito, Joaquín F.
Prado-Diaz, Pol
author Pérez de Benito, Joaquín F.
author_facet Pérez de Benito, Joaquín F.
Prado-Diaz, Pol
author_role author
author2 Prado-Diaz, Pol
author2_role author
dc.subject.none.fl_str_mv Oxidació
Aigua oxigenada
Inhibició
Oxidation
Hydrogen peroxide
Inhibition
topic Oxidació
Aigua oxigenada
Inhibició
Oxidation
Hydrogen peroxide
Inhibition
description The oxidation of hexacyanoferrate(ll) ion by a large excess of hydrogen peroxide, in slightly acidic aqueous media containing potassium dihydrogen phosphate (pH 5.10 ± 0.05), was followed by monitoring the increase of absorbance at 420 nm as the colorless Fe(ll) complex gradually evolved into the yellow Fe(lll) complex. The reaction was inhibited by OH-containing organic compounds, either alcohols or carbohydrates, and two different inhibition pathways were observed, an iron(III)-independent pathway (rate constant k1) and an iron(III)-mediated pathway (rate constant k2). A BASIC-language computer program was developed in order to use the fourth-order Runge-Kutta integration method to obtain the concentrations of the Fe(ll)-inhibitor complex and the Fe(lll) reaction product. Rate constant k1, whose value is determined by that of the initial rate, decreased slightly as the concentration of alcohol / carbohydrate increased, and a mechanism involving the formation of hydroxyl radicals in a Fenton-like reaction and its posterior scavenging by the organic antioxidant additive has been proposed. Of the 8 inhibiting agents that were tried, the most potent antioxidant under the experimental conditions of this study was D-mannitol. Rate constant k2, whose value is a measurement of the deviation from a pseudo-first order behavior provoked by the inhibiting agent, increased notably as the concentration of the latter increased, and a mechanism involving the complexation of the Fe(lll) product by the organic inhibitor and its posterior outer-sphere one electron reduction from hexacyanoferrate(ll) ion has also been proposed. This might result in a blockage of the regeneration of pentacyanoaquaferrate(ll) ion, an intermediate believed to be essential for the redox reaction to take place.
publishDate 2022
dc.date.none.fl_str_mv 2022
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/200658
url https://hdl.handle.net/2445/200658
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió postprint del document publicat a: https://doi.org/10.1007/s11144-022-02306-7
Reaction Kinetics Mechanisms And Catalysis, 2022, vol. 135, num. 6, p. 2897-2913
https://doi.org/10.1007/s11144-022-02306-7
dc.rights.none.fl_str_mv (c) Akadémiai Kiadó, 2022
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) Akadémiai Kiadó, 2022
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Akadémiai Kiadó
publisher.none.fl_str_mv Akadémiai Kiadó
dc.source.none.fl_str_mv Articles publicats en revistes (Ciència dels Materials i Química Física)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,298079

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