Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles

Autores
Soulé, Ezequiel Rodolfo; Hoppe, Cristina Elena; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A thermodynamic model for a mixture of alkanethiol-coated nanoparticles (NPs) and low-molecular-weight (nonpolymeric) solvent is developed, and calculations of liquid−liquid phase equilibria for different values of NP core radius, alkanethiol chain length, solvent molar volume, and alkanethiol−solvent interaction parameter, are presented. The model takes into account the swelling of the organic coronas and the dispersion of particles with swollen coronas in the solvent. The energetic interaction between alkyl chains and solvent is considered, both within the corona and between the outer alkyl segments and free solvent. Swelling involves mixing of alkanethiol chains and solvent in the corona and stretching of the organic chains. Dispersion considers an entropic contribution based on the Carnahan−Starling equation of state and an enthalpic term calculated considering the surface contacts between alkyl segments placed in the external boundary of the corona and the molecules of free solvent. Two different kinds of phase equilibrium are found. One of them, observed at high values of the interaction parameter, is the typical liquid−liquid equilibrium for compact NPs in a poor solvent where a complete phase separation is observed when cooling (increasing the interaction parameter). The second liquid−liquid equilibrium is observed at low values of the interaction parameter, where swelling of coronas is favored. In this region two different phases coexist: one more concentrated in NPs that exhibit relatively compact coronas and the other one more diluted in NPs with extended coronas. In diluted solutions of NPs the deswelling of the fully extended coronas takes place abruptly in a very small temperature range, leading to a solution of compact NPs. This critical transition might find practical applications similar to those found for the abrupt shrinkage of hydrogels at a critical temperature.
Fil: Soulé, Ezequiel Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
Fil: Hoppe, Cristina Elena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
Fil: Borrajo Fernandez, Julio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
Fil: Williams, Roberto Juan Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
Materia
Nanoparticles
Thermodynamics
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:11336/23006
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/23006
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticlesSoulé, Ezequiel RodolfoHoppe, Cristina ElenaBorrajo Fernandez, JulioWilliams, Roberto Juan JoseNanoparticlesThermodynamicshttps://purl.org/becyt/ford/2.10https://purl.org/becyt/ford/2https://purl.org/becyt/ford/2.5https://purl.org/becyt/ford/2A thermodynamic model for a mixture of alkanethiol-coated nanoparticles (NPs) and low-molecular-weight (nonpolymeric) solvent is developed, and calculations of liquid−liquid phase equilibria for different values of NP core radius, alkanethiol chain length, solvent molar volume, and alkanethiol−solvent interaction parameter, are presented. The model takes into account the swelling of the organic coronas and the dispersion of particles with swollen coronas in the solvent. The energetic interaction between alkyl chains and solvent is considered, both within the corona and between the outer alkyl segments and free solvent. Swelling involves mixing of alkanethiol chains and solvent in the corona and stretching of the organic chains. Dispersion considers an entropic contribution based on the Carnahan−Starling equation of state and an enthalpic term calculated considering the surface contacts between alkyl segments placed in the external boundary of the corona and the molecules of free solvent. Two different kinds of phase equilibrium are found. One of them, observed at high values of the interaction parameter, is the typical liquid−liquid equilibrium for compact NPs in a poor solvent where a complete phase separation is observed when cooling (increasing the interaction parameter). The second liquid−liquid equilibrium is observed at low values of the interaction parameter, where swelling of coronas is favored. In this region two different phases coexist: one more concentrated in NPs that exhibit relatively compact coronas and the other one more diluted in NPs with extended coronas. In diluted solutions of NPs the deswelling of the fully extended coronas takes place abruptly in a very small temperature range, leading to a solution of compact NPs. This critical transition might find practical applications similar to those found for the abrupt shrinkage of hydrogels at a critical temperature.Fil: Soulé, Ezequiel Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Hoppe, Cristina Elena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Borrajo Fernandez, Julio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Williams, Roberto Juan Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaAmerican Chemical Society2010-03-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/23006Soulé, Ezequiel Rodolfo; Hoppe, Cristina Elena; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose; Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles; American Chemical Society; Industrial & Engineering Chemical Research; 49; 15; 3-3-2010; 7008-70160888-5885CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ie901784rinfo:eu-repo/semantics/altIdentifier/doi/10.1021/ie901784rinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:25:03Zoai:ri.conicet.gov.ar:11336/23006instacron: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 10:25:03.407CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles
title Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles
spellingShingle Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles
Soulé, Ezequiel Rodolfo
Nanoparticles
Thermodynamics
title_short Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles
title_full Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles
title_fullStr Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles
title_full_unstemmed Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles
title_sort Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles
dc.creator.none.fl_str_mv Soulé, Ezequiel Rodolfo
Hoppe, Cristina Elena
Borrajo Fernandez, Julio
Williams, Roberto Juan Jose
author Soulé, Ezequiel Rodolfo
author_facet Soulé, Ezequiel Rodolfo
Hoppe, Cristina Elena
Borrajo Fernandez, Julio
Williams, Roberto Juan Jose
author_role author
author2 Hoppe, Cristina Elena
Borrajo Fernandez, Julio
Williams, Roberto Juan Jose
author2_role author
author
author
dc.subject.none.fl_str_mv Nanoparticles
Thermodynamics
topic Nanoparticles
Thermodynamics
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.10
https://purl.org/becyt/ford/2
https://purl.org/becyt/ford/2.5
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv A thermodynamic model for a mixture of alkanethiol-coated nanoparticles (NPs) and low-molecular-weight (nonpolymeric) solvent is developed, and calculations of liquid−liquid phase equilibria for different values of NP core radius, alkanethiol chain length, solvent molar volume, and alkanethiol−solvent interaction parameter, are presented. The model takes into account the swelling of the organic coronas and the dispersion of particles with swollen coronas in the solvent. The energetic interaction between alkyl chains and solvent is considered, both within the corona and between the outer alkyl segments and free solvent. Swelling involves mixing of alkanethiol chains and solvent in the corona and stretching of the organic chains. Dispersion considers an entropic contribution based on the Carnahan−Starling equation of state and an enthalpic term calculated considering the surface contacts between alkyl segments placed in the external boundary of the corona and the molecules of free solvent. Two different kinds of phase equilibrium are found. One of them, observed at high values of the interaction parameter, is the typical liquid−liquid equilibrium for compact NPs in a poor solvent where a complete phase separation is observed when cooling (increasing the interaction parameter). The second liquid−liquid equilibrium is observed at low values of the interaction parameter, where swelling of coronas is favored. In this region two different phases coexist: one more concentrated in NPs that exhibit relatively compact coronas and the other one more diluted in NPs with extended coronas. In diluted solutions of NPs the deswelling of the fully extended coronas takes place abruptly in a very small temperature range, leading to a solution of compact NPs. This critical transition might find practical applications similar to those found for the abrupt shrinkage of hydrogels at a critical temperature.
Fil: Soulé, Ezequiel Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
Fil: Hoppe, Cristina Elena. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
Fil: Borrajo Fernandez, Julio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
Fil: Williams, Roberto Juan Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina
description A thermodynamic model for a mixture of alkanethiol-coated nanoparticles (NPs) and low-molecular-weight (nonpolymeric) solvent is developed, and calculations of liquid−liquid phase equilibria for different values of NP core radius, alkanethiol chain length, solvent molar volume, and alkanethiol−solvent interaction parameter, are presented. The model takes into account the swelling of the organic coronas and the dispersion of particles with swollen coronas in the solvent. The energetic interaction between alkyl chains and solvent is considered, both within the corona and between the outer alkyl segments and free solvent. Swelling involves mixing of alkanethiol chains and solvent in the corona and stretching of the organic chains. Dispersion considers an entropic contribution based on the Carnahan−Starling equation of state and an enthalpic term calculated considering the surface contacts between alkyl segments placed in the external boundary of the corona and the molecules of free solvent. Two different kinds of phase equilibrium are found. One of them, observed at high values of the interaction parameter, is the typical liquid−liquid equilibrium for compact NPs in a poor solvent where a complete phase separation is observed when cooling (increasing the interaction parameter). The second liquid−liquid equilibrium is observed at low values of the interaction parameter, where swelling of coronas is favored. In this region two different phases coexist: one more concentrated in NPs that exhibit relatively compact coronas and the other one more diluted in NPs with extended coronas. In diluted solutions of NPs the deswelling of the fully extended coronas takes place abruptly in a very small temperature range, leading to a solution of compact NPs. This critical transition might find practical applications similar to those found for the abrupt shrinkage of hydrogels at a critical temperature.
publishDate 2010
dc.date.none.fl_str_mv 2010-03-03
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/11336/23006
Soulé, Ezequiel Rodolfo; Hoppe, Cristina Elena; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose; Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles; American Chemical Society; Industrial & Engineering Chemical Research; 49; 15; 3-3-2010; 7008-7016
0888-5885
CONICET Digital
CONICET
url http://hdl.handle.net/11336/23006
identifier_str_mv Soulé, Ezequiel Rodolfo; Hoppe, Cristina Elena; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose; Thermodynamic model of liquid-liquid phase equilibrium in solutions of alkanethiol-coated nanoparticles; American Chemical Society; Industrial & Engineering Chemical Research; 49; 15; 3-3-2010; 7008-7016
0888-5885
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.acs.org/doi/abs/10.1021/ie901784r
info:eu-repo/semantics/altIdentifier/doi/10.1021/ie901784r
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
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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 13.070432

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