Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate

Autores
Arroyave Rodriguez, Jeison Manuel; Avena, Marcelo Javier
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
One of the most common approaches in the adsorption kinetic literature is to compare the fitting performance of several empirical or non-empirical equations (pseudo-first order, pseudo-second order, Elovich, parabolic diffusion, etc.) with the aim of selecting the equation that best describes the experimental data. This is normally a futile fitting exercise that leads to the determination of ambiguous rate parameters, without providing insights into the behaviour of the studied system. A more realistic approach is to treat it as a combination of mass transport and chemical reaction under controlled conditions, and thus actual adsorption-desorption rate parameters are readily estimated. This article applies a simple and realistic physicochemical model to describe and understand the adsorption-desorption kinetics of ions at the solid/water interface. The model is applied to an ATR-FTIR study of phosphate adsorption-desorption on goethite, which is a very well-known and reference system, ideal for testing the performance of a physicochemical treatment that combines transport and reaction. Always the same phosphate species (monodentate mononuclear protonated) was present at the goethite surface during adsorption-desorption. There was an excellent agreement between theory and experiments at a variety of phosphate concentration and surface coverages for adsorption kinetics, desorption kinetics and equilibrium situations, employing just one set of rate coefficients. The use of rate vs adsorption curves permitted easily to detect conditions of transport- and reaction-controlled kinetics. The phosphate-goethite system is a fast-adsorbing/slow-desorbing system, with an adsorption rate constant k_a^o=1.26×103 s-1 and a desorption rate constant k_d=1.66×10-5 s-1. Therefore, adsorption was transport-controlled and desorption was reaction-controlled. The half-life of the desorption reaction is 41700 s (11.6 h) but for adsorption it would take only a few seconds in absence of transport control. For this kind of systems, which are ubiquitous in nature and technological processes, it is easier to determine rate constants from desorption than from adsorption experiments.
Fil: Arroyave Rodriguez, Jeison Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Avena, Marcelo Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Materia
ADSORPTION KINETICS
OXIDE-WATER INTERFACE
SURFACE COMPLEXES
PHOSPHATE DESORPTION
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:11336/141728
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/141728
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rateArroyave Rodriguez, Jeison ManuelAvena, Marcelo JavierADSORPTION KINETICSOXIDE-WATER INTERFACESURFACE COMPLEXESPHOSPHATE DESORPTIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1One of the most common approaches in the adsorption kinetic literature is to compare the fitting performance of several empirical or non-empirical equations (pseudo-first order, pseudo-second order, Elovich, parabolic diffusion, etc.) with the aim of selecting the equation that best describes the experimental data. This is normally a futile fitting exercise that leads to the determination of ambiguous rate parameters, without providing insights into the behaviour of the studied system. A more realistic approach is to treat it as a combination of mass transport and chemical reaction under controlled conditions, and thus actual adsorption-desorption rate parameters are readily estimated. This article applies a simple and realistic physicochemical model to describe and understand the adsorption-desorption kinetics of ions at the solid/water interface. The model is applied to an ATR-FTIR study of phosphate adsorption-desorption on goethite, which is a very well-known and reference system, ideal for testing the performance of a physicochemical treatment that combines transport and reaction. Always the same phosphate species (monodentate mononuclear protonated) was present at the goethite surface during adsorption-desorption. There was an excellent agreement between theory and experiments at a variety of phosphate concentration and surface coverages for adsorption kinetics, desorption kinetics and equilibrium situations, employing just one set of rate coefficients. The use of rate vs adsorption curves permitted easily to detect conditions of transport- and reaction-controlled kinetics. The phosphate-goethite system is a fast-adsorbing/slow-desorbing system, with an adsorption rate constant k_a^o=1.26×103 s-1 and a desorption rate constant k_d=1.66×10-5 s-1. Therefore, adsorption was transport-controlled and desorption was reaction-controlled. The half-life of the desorption reaction is 41700 s (11.6 h) but for adsorption it would take only a few seconds in absence of transport control. For this kind of systems, which are ubiquitous in nature and technological processes, it is easier to determine rate constants from desorption than from adsorption experiments.Fil: Arroyave Rodriguez, Jeison Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Avena, Marcelo Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaRoyal Society of Chemistry2020-04-23info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/141728Arroyave Rodriguez, Jeison Manuel; Avena, Marcelo Javier; Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 20; 23-4-2020; 1-231463-9076CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2020/CP/D0CP00993Hinfo:eu-repo/semantics/altIdentifier/doi/10.1039/D0CP00993Hinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:34:08Zoai:ri.conicet.gov.ar:11336/141728instacron: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:34982025-10-15 14:34:08.386CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate
title Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate
spellingShingle Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate
Arroyave Rodriguez, Jeison Manuel
ADSORPTION KINETICS
OXIDE-WATER INTERFACE
SURFACE COMPLEXES
PHOSPHATE DESORPTION
title_short Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate
title_full Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate
title_fullStr Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate
title_full_unstemmed Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate
title_sort Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate
dc.creator.none.fl_str_mv Arroyave Rodriguez, Jeison Manuel
Avena, Marcelo Javier
author Arroyave Rodriguez, Jeison Manuel
author_facet Arroyave Rodriguez, Jeison Manuel
Avena, Marcelo Javier
author_role author
author2 Avena, Marcelo Javier
author2_role author
dc.subject.none.fl_str_mv ADSORPTION KINETICS
OXIDE-WATER INTERFACE
SURFACE COMPLEXES
PHOSPHATE DESORPTION
topic ADSORPTION KINETICS
OXIDE-WATER INTERFACE
SURFACE COMPLEXES
PHOSPHATE DESORPTION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv One of the most common approaches in the adsorption kinetic literature is to compare the fitting performance of several empirical or non-empirical equations (pseudo-first order, pseudo-second order, Elovich, parabolic diffusion, etc.) with the aim of selecting the equation that best describes the experimental data. This is normally a futile fitting exercise that leads to the determination of ambiguous rate parameters, without providing insights into the behaviour of the studied system. A more realistic approach is to treat it as a combination of mass transport and chemical reaction under controlled conditions, and thus actual adsorption-desorption rate parameters are readily estimated. This article applies a simple and realistic physicochemical model to describe and understand the adsorption-desorption kinetics of ions at the solid/water interface. The model is applied to an ATR-FTIR study of phosphate adsorption-desorption on goethite, which is a very well-known and reference system, ideal for testing the performance of a physicochemical treatment that combines transport and reaction. Always the same phosphate species (monodentate mononuclear protonated) was present at the goethite surface during adsorption-desorption. There was an excellent agreement between theory and experiments at a variety of phosphate concentration and surface coverages for adsorption kinetics, desorption kinetics and equilibrium situations, employing just one set of rate coefficients. The use of rate vs adsorption curves permitted easily to detect conditions of transport- and reaction-controlled kinetics. The phosphate-goethite system is a fast-adsorbing/slow-desorbing system, with an adsorption rate constant k_a^o=1.26×103 s-1 and a desorption rate constant k_d=1.66×10-5 s-1. Therefore, adsorption was transport-controlled and desorption was reaction-controlled. The half-life of the desorption reaction is 41700 s (11.6 h) but for adsorption it would take only a few seconds in absence of transport control. For this kind of systems, which are ubiquitous in nature and technological processes, it is easier to determine rate constants from desorption than from adsorption experiments.
Fil: Arroyave Rodriguez, Jeison Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
Fil: Avena, Marcelo Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina
description One of the most common approaches in the adsorption kinetic literature is to compare the fitting performance of several empirical or non-empirical equations (pseudo-first order, pseudo-second order, Elovich, parabolic diffusion, etc.) with the aim of selecting the equation that best describes the experimental data. This is normally a futile fitting exercise that leads to the determination of ambiguous rate parameters, without providing insights into the behaviour of the studied system. A more realistic approach is to treat it as a combination of mass transport and chemical reaction under controlled conditions, and thus actual adsorption-desorption rate parameters are readily estimated. This article applies a simple and realistic physicochemical model to describe and understand the adsorption-desorption kinetics of ions at the solid/water interface. The model is applied to an ATR-FTIR study of phosphate adsorption-desorption on goethite, which is a very well-known and reference system, ideal for testing the performance of a physicochemical treatment that combines transport and reaction. Always the same phosphate species (monodentate mononuclear protonated) was present at the goethite surface during adsorption-desorption. There was an excellent agreement between theory and experiments at a variety of phosphate concentration and surface coverages for adsorption kinetics, desorption kinetics and equilibrium situations, employing just one set of rate coefficients. The use of rate vs adsorption curves permitted easily to detect conditions of transport- and reaction-controlled kinetics. The phosphate-goethite system is a fast-adsorbing/slow-desorbing system, with an adsorption rate constant k_a^o=1.26×103 s-1 and a desorption rate constant k_d=1.66×10-5 s-1. Therefore, adsorption was transport-controlled and desorption was reaction-controlled. The half-life of the desorption reaction is 41700 s (11.6 h) but for adsorption it would take only a few seconds in absence of transport control. For this kind of systems, which are ubiquitous in nature and technological processes, it is easier to determine rate constants from desorption than from adsorption experiments.
publishDate 2020
dc.date.none.fl_str_mv 2020-04-23
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/11336/141728
Arroyave Rodriguez, Jeison Manuel; Avena, Marcelo Javier; Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 20; 23-4-2020; 1-23
1463-9076
CONICET Digital
CONICET
url http://hdl.handle.net/11336/141728
identifier_str_mv Arroyave Rodriguez, Jeison Manuel; Avena, Marcelo Javier; Determining rate coefficients for ion adsorption at the solid/water interface: Better from desorption rate than from adsorption rate; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 20; 23-4-2020; 1-23
1463-9076
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2020/CP/D0CP00993H
info:eu-repo/semantics/altIdentifier/doi/10.1039/D0CP00993H
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
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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 13.22299

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