Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrum

The concept of conditional stability constant is extended to the competitive binding of small molecules to heterogeneous surfaces or macromolecules via the introduction of the conditional affinity spectrum (CAS). The CAS describes the distribution of effective binding energies experienced by one com...

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Authors: Garcés, Josep Lluís, Mas i Pujadas, Francesc, Puy Llorens, Jaume
Format: article
Status:Published version
Publication Date:2006
Country:España
Institution:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repository:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10459.1/46473
Online Access:https://doi.org/10.1063/1.2162876
http://hdl.handle.net/10459.1/46473
Access Level:Open access
Keyword:Metals
Adsorption
Chemical equilibrium
Binding energy
Integral equations
Equilibri químic
Equacions integrals
Absorció
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spelling Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrumGarcés, Josep LluísMas i Pujadas, FrancescPuy Llorens, JaumeMetalsAdsorptionChemical equilibriumBinding energyIntegral equationsEquilibri químicEquacions integralsAbsorcióThe concept of conditional stability constant is extended to the competitive binding of small molecules to heterogeneous surfaces or macromolecules via the introduction of the conditional affinity spectrum (CAS). The CAS describes the distribution of effective binding energies experienced by one complexing agent at a fixed concentration of the rest. We show that, when the multicomponent system can be described in terms of an underlying affinity spectrum [integral equation (IE) approach], the system can always be characterized by means of a CAS. The thermodynamic properties of the CAS and its dependence on the concentration of the rest of components are discussed. In the context of metal/proton competition, analytical expressions for the mean (conditional average affinity) and the variance (conditional heterogeneity) of the CAS as functions of pH are reported and their physical interpretation discussed. Furthermore, we show that the dependence of the CAS variance on pH allows for the analytical determination of the correlation coefficient between the binding energies of the metal and the proton. Nonideal competitive adsorption isotherm and Frumkin isotherms are used to illustrate the results of this work. Finally, the possibility of using CAS when the IE approach does not apply (for instance, when multidentate binding is present) is explored. © 2006 American Institute of Physics.American Institute of Physics2006info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttps://doi.org/10.1063/1.2162876http://hdl.handle.net/10459.1/46473reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésReproducció del document publicat a: https://doi.org/10.1063/1.2162876Journal of Chemical Physics, 2006, vol. 124, núm. 4, p. 044710-1/14(c) American Institute of Physics, 2006info:eu-repo/semantics/openAccessoai:recercat.cat:10459.1/464732026-05-29T05:05:01Z
dc.title.none.fl_str_mv Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrum
title Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrum
spellingShingle Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrum
Garcés, Josep Lluís
Metals
Adsorption
Chemical equilibrium
Binding energy
Integral equations
Equilibri químic
Equacions integrals
Absorció
title_short Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrum
title_full Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrum
title_fullStr Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrum
title_full_unstemmed Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrum
title_sort Conditional equilibrium constants in multicomponent heterogeneous adsorption: The conditional affinity spectrum
dc.creator.none.fl_str_mv Garcés, Josep Lluís
Mas i Pujadas, Francesc
Puy Llorens, Jaume
author Garcés, Josep Lluís
author_facet Garcés, Josep Lluís
Mas i Pujadas, Francesc
Puy Llorens, Jaume
author_role author
author2 Mas i Pujadas, Francesc
Puy Llorens, Jaume
author2_role author
author
dc.subject.none.fl_str_mv Metals
Adsorption
Chemical equilibrium
Binding energy
Integral equations
Equilibri químic
Equacions integrals
Absorció
topic Metals
Adsorption
Chemical equilibrium
Binding energy
Integral equations
Equilibri químic
Equacions integrals
Absorció
description The concept of conditional stability constant is extended to the competitive binding of small molecules to heterogeneous surfaces or macromolecules via the introduction of the conditional affinity spectrum (CAS). The CAS describes the distribution of effective binding energies experienced by one complexing agent at a fixed concentration of the rest. We show that, when the multicomponent system can be described in terms of an underlying affinity spectrum [integral equation (IE) approach], the system can always be characterized by means of a CAS. The thermodynamic properties of the CAS and its dependence on the concentration of the rest of components are discussed. In the context of metal/proton competition, analytical expressions for the mean (conditional average affinity) and the variance (conditional heterogeneity) of the CAS as functions of pH are reported and their physical interpretation discussed. Furthermore, we show that the dependence of the CAS variance on pH allows for the analytical determination of the correlation coefficient between the binding energies of the metal and the proton. Nonideal competitive adsorption isotherm and Frumkin isotherms are used to illustrate the results of this work. Finally, the possibility of using CAS when the IE approach does not apply (for instance, when multidentate binding is present) is explored. © 2006 American Institute of Physics.
publishDate 2006
dc.date.none.fl_str_mv 2006
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://doi.org/10.1063/1.2162876
http://hdl.handle.net/10459.1/46473
url https://doi.org/10.1063/1.2162876
http://hdl.handle.net/10459.1/46473
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Reproducció del document publicat a: https://doi.org/10.1063/1.2162876
Journal of Chemical Physics, 2006, vol. 124, núm. 4, p. 044710-1/14
dc.rights.none.fl_str_mv (c) American Institute of Physics, 2006
info:eu-repo/semantics/openAccess
rights_invalid_str_mv (c) American Institute of Physics, 2006
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv American Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
dc.source.none.fl_str_mv reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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