Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reaction

Autores: Arvia, Alejandro Jorge; Triaca, Walter Enrique
Año de publicación: 1966
Idioma: inglés
Tipo de recurso: artículo
Estado: versión publicada
Descripción: The anodic reaction occurring during the electrolysis of molten nitrates on graphite electrodes at temperatures from 230 to 320°C has been studied. The overall reaction is $2 N O_{3}^{-} + C = C O_{2} + 2 N O_{2} + 2 e$ Current/voltage curves in the range 0·5–200 mA/cm² fit a Tafel line with a slope 2RT/F. The decay of anodic overvoltage is logarithmic with time in a region beyond 10 ms, depending on the current density. The decay process indicates a high pseudo-capacitance, which decreases as the anodic overvoltage increases. Results obtained from steady current/voltage curves, decay and build-up of the anodic overvoltage, and the temperature effect can be explained with the aid of known results on the kinetics of thermal oxidation of graphite and on the anodic reaction taking place on platinum electrodes. At high overvoltage a high degree of oxidation caused by the NO 3 intermediate is achieved, and the rate-determining step of the anodic reaction is then $C (O) + N O_{3}^{-} \to N O_{2} + C O_{2} + e$ A stable residual cell formed after the interruption of electrolysis is discussed in terms of the reactions in the proposed reaction path.
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
Materia: Ciencias Exactas
Química
Molten nitrates
Graphite electrodes
Nivel de accesibilidad: acceso abierto
Condiciones de uso: http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
Institución: Universidad Nacional de La Plata
OAI Identificador: oai:sedici.unlp.edu.ar:10915/120668

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repository_id_str	1329
network_name_str	SEDICI (UNLP)
spelling	Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reactionArvia, Alejandro JorgeTriaca, Walter EnriqueCiencias ExactasQuímicaMolten nitratesGraphite electrodesThe anodic reaction occurring during the electrolysis of molten nitrates on graphite electrodes at temperatures from 230 to 320°C has been studied. The overall reaction is <math><mrow is="true"><mn is="true">2</mn><mo is="true">N</mo><msubsup is="true"><mo is="true">O</mo><mn is="true">3</mn><mo is="true">−</mo></msubsup><mo is="true">+</mo><mo is="true">C</mo><mo is="true">=</mo><mo is="true">C</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mn is="true">2</mn><mo is="true">N</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mn is="true">2</mn><mo is="true">e</mo></mrow></math> Current/voltage curves in the range 0·5–200 mA/cm<sup>2</sup> fit a Tafel line with a slope 2RT/F. The decay of anodic overvoltage is logarithmic with time in a region beyond 10 ms, depending on the current density. The decay process indicates a high pseudo-capacitance, which decreases as the anodic overvoltage increases. Results obtained from steady current/voltage curves, decay and build-up of the anodic overvoltage, and the temperature effect can be explained with the aid of known results on the kinetics of thermal oxidation of graphite and on the anodic reaction taking place on platinum electrodes. At high overvoltage a high degree of oxidation caused by the NO 3 intermediate is achieved, and the rate-determining step of the anodic reaction is then <math><mrow is="true"><mo is="true">C</mo><mo stretchy="false" is="true">(</mo><mo is="true">O</mo><mo stretchy="false" is="true">)</mo><mo is="true">+</mo><mo is="true">N</mo><msubsup is="true"><mo is="true">O</mo><mn is="true">3</mn><mo is="true">−</mo></msubsup><mo is="true">→</mo><mo is="true">N</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mo is="true">C</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mo is="true">e</mo></mrow></math> A stable residual cell formed after the interruption of electrolysis is discussed in terms of the reactions in the proposed reaction path.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas1966info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf975-986http://sedici.unlp.edu.ar/handle/10915/120668enginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/0013468666800361info:eu-repo/semantics/altIdentifier/issn/0013-4686info:eu-repo/semantics/altIdentifier/doi/10.1016/0013-4686(66)80036-1info: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:UNLP2025-09-29T11:28:34Zoai:sedici.unlp.edu.ar:10915/120668Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-29 11:28:34.845SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv	Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reaction
title	Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reaction
spellingShingle	Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reaction Arvia, Alejandro Jorge Ciencias Exactas Química Molten nitrates Graphite electrodes
title_short	Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reaction
title_full	Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reaction
title_fullStr	Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reaction
title_full_unstemmed	Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reaction
title_sort	Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reaction
dc.creator.none.fl_str_mv	Arvia, Alejandro Jorge Triaca, Walter Enrique
author	Arvia, Alejandro Jorge
author_facet	Arvia, Alejandro Jorge Triaca, Walter Enrique
author_role	author
author2	Triaca, Walter Enrique
author2_role	author
dc.subject.none.fl_str_mv	Ciencias Exactas Química Molten nitrates Graphite electrodes
topic	Ciencias Exactas Química Molten nitrates Graphite electrodes
dc.description.none.fl_txt_mv	The anodic reaction occurring during the electrolysis of molten nitrates on graphite electrodes at temperatures from 230 to 320°C has been studied. The overall reaction is <math><mrow is="true"><mn is="true">2</mn><mo is="true">N</mo><msubsup is="true"><mo is="true">O</mo><mn is="true">3</mn><mo is="true">−</mo></msubsup><mo is="true">+</mo><mo is="true">C</mo><mo is="true">=</mo><mo is="true">C</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mn is="true">2</mn><mo is="true">N</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mn is="true">2</mn><mo is="true">e</mo></mrow></math> Current/voltage curves in the range 0·5–200 mA/cm<sup>2</sup> fit a Tafel line with a slope 2RT/F. The decay of anodic overvoltage is logarithmic with time in a region beyond 10 ms, depending on the current density. The decay process indicates a high pseudo-capacitance, which decreases as the anodic overvoltage increases. Results obtained from steady current/voltage curves, decay and build-up of the anodic overvoltage, and the temperature effect can be explained with the aid of known results on the kinetics of thermal oxidation of graphite and on the anodic reaction taking place on platinum electrodes. At high overvoltage a high degree of oxidation caused by the NO 3 intermediate is achieved, and the rate-determining step of the anodic reaction is then <math><mrow is="true"><mo is="true">C</mo><mo stretchy="false" is="true">(</mo><mo is="true">O</mo><mo stretchy="false" is="true">)</mo><mo is="true">+</mo><mo is="true">N</mo><msubsup is="true"><mo is="true">O</mo><mn is="true">3</mn><mo is="true">−</mo></msubsup><mo is="true">→</mo><mo is="true">N</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mo is="true">C</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mo is="true">e</mo></mrow></math> A stable residual cell formed after the interruption of electrolysis is discussed in terms of the reactions in the proposed reaction path. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas
description	The anodic reaction occurring during the electrolysis of molten nitrates on graphite electrodes at temperatures from 230 to 320°C has been studied. The overall reaction is <math><mrow is="true"><mn is="true">2</mn><mo is="true">N</mo><msubsup is="true"><mo is="true">O</mo><mn is="true">3</mn><mo is="true">−</mo></msubsup><mo is="true">+</mo><mo is="true">C</mo><mo is="true">=</mo><mo is="true">C</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mn is="true">2</mn><mo is="true">N</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mn is="true">2</mn><mo is="true">e</mo></mrow></math> Current/voltage curves in the range 0·5–200 mA/cm<sup>2</sup> fit a Tafel line with a slope 2RT/F. The decay of anodic overvoltage is logarithmic with time in a region beyond 10 ms, depending on the current density. The decay process indicates a high pseudo-capacitance, which decreases as the anodic overvoltage increases. Results obtained from steady current/voltage curves, decay and build-up of the anodic overvoltage, and the temperature effect can be explained with the aid of known results on the kinetics of thermal oxidation of graphite and on the anodic reaction taking place on platinum electrodes. At high overvoltage a high degree of oxidation caused by the NO 3 intermediate is achieved, and the rate-determining step of the anodic reaction is then <math><mrow is="true"><mo is="true">C</mo><mo stretchy="false" is="true">(</mo><mo is="true">O</mo><mo stretchy="false" is="true">)</mo><mo is="true">+</mo><mo is="true">N</mo><msubsup is="true"><mo is="true">O</mo><mn is="true">3</mn><mo is="true">−</mo></msubsup><mo is="true">→</mo><mo is="true">N</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mo is="true">C</mo><msub is="true"><mo is="true">O</mo><mn is="true">2</mn></msub><mo is="true">+</mo><mo is="true">e</mo></mrow></math> A stable residual cell formed after the interruption of electrolysis is discussed in terms of the reactions in the proposed reaction path.
publishDate	1966
dc.date.none.fl_str_mv	1966
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/10915/120668
url	http://sedici.unlp.edu.ar/handle/10915/120668
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/abs/pii/0013468666800361 info:eu-repo/semantics/altIdentifier/issn/0013-4686 info:eu-repo/semantics/altIdentifier/doi/10.1016/0013-4686(66)80036-1
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 975-986
dc.source.none.fl_str_mv	reponame:SEDICI (UNLP) instname:Universidad Nacional de La Plata instacron:UNLP
reponame_str	SEDICI (UNLP)
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instname_str	Universidad Nacional de La Plata
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repository.name.fl_str_mv	SEDICI (UNLP) - Universidad Nacional de La Plata
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Electrolysis of molten nitrates on graphite electrodes : Kinetics of the anodic reaction

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