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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/141728
Ver los metadatos del registro completo
id |
CONICETDig_dc58959d9075d9d278467a3bb2e92710 |
---|---|
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 Técnicas2025-09-29T09:42:07Zoai: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:34982025-09-29 09:42:07.42CONICET 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 |
_version_ |
1844613327496413184 |
score |
13.070432 |