Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!

Autores
Tassin, Natalia Giselle; Rodriguez Reartes, Sabrina Belen; Cismondi Duarte, Martín
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The idea that cubic EoS's are very primitive and limited models, quite extended at present among researchers working on fluid properties and phase equilibria, has different roots, including some limitations observed specifically for classic and popular equations like Peng-Robinson (PR) or Soave-Redlich-Kwong (SRK). These are two-parameter models, i.e. they have only an attractive and a repulsive parameter to characterize each molecule, while other models like SAFT but also cubic –and still for non-associating molecules-introduce also a third parameter related somehow to the molecular structure or shape. One of the alluded limitations, actually a very clear one, is the complete failure in describing the non-ideality in nearly athermal mixtures, like those composed of n-alkanes with different chain lengths: SRK and PR predict positive deviations from ideality, which increase with the system asymmetry, while experimental measurements show exactly the opposite, i.e. increasing negative deviations from ideality. This provides an excellent opportunity to try to clarify whether such failure is due to the cubic nature of these classic models or to their two-parameter character and/or to the classic van der Waals one-fluid (vdW1f) mixing rules typically used. With that motivation, in this work we used models representing three different categories, in a completely predictive way: a two-parameter cubic EoS (PR), a three-parameter cubic EoS (RKPR) and a three-parameter SAFT EoS (PC-SAFT). Their predictions of infinite dilution activity coefficients were analyzed and compared, in contrast to available data for different mixtures of n-butane to n-octane as the lighter compound and paraffins ranging from C16 to C36 as the heavier, in both extremes of dilution. The obtained results, and their analysis, allowed us to extract very clear conclusions which were not present in the literature so far, regarding the importance of a third parameter in any type of EoS.
Fil: Tassin, Natalia Giselle. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; Argentina
Fil: Rodriguez Reartes, Sabrina Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; Argentina
Fil: Cismondi Duarte, Martín. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; Argentina. YPF - Tecnología; Argentina
Materia
EQUATIONS OF STATE
ACTIVITY COEFFICIENTS
LIMITATIONS OF TWO PARAMETER EOS
THREE-PARAMETER EOS
N-ALKANE MIXTURES
Nivel de accesibilidad
acceso embargado
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/126830

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network_name_str CONICET Digital (CONICET)
spelling Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!Tassin, Natalia GiselleRodriguez Reartes, Sabrina BelenCismondi Duarte, MartínEQUATIONS OF STATEACTIVITY COEFFICIENTSLIMITATIONS OF TWO PARAMETER EOSTHREE-PARAMETER EOSN-ALKANE MIXTUREShttps://purl.org/becyt/ford/2.4https://purl.org/becyt/ford/2The idea that cubic EoS's are very primitive and limited models, quite extended at present among researchers working on fluid properties and phase equilibria, has different roots, including some limitations observed specifically for classic and popular equations like Peng-Robinson (PR) or Soave-Redlich-Kwong (SRK). These are two-parameter models, i.e. they have only an attractive and a repulsive parameter to characterize each molecule, while other models like SAFT but also cubic –and still for non-associating molecules-introduce also a third parameter related somehow to the molecular structure or shape. One of the alluded limitations, actually a very clear one, is the complete failure in describing the non-ideality in nearly athermal mixtures, like those composed of n-alkanes with different chain lengths: SRK and PR predict positive deviations from ideality, which increase with the system asymmetry, while experimental measurements show exactly the opposite, i.e. increasing negative deviations from ideality. This provides an excellent opportunity to try to clarify whether such failure is due to the cubic nature of these classic models or to their two-parameter character and/or to the classic van der Waals one-fluid (vdW1f) mixing rules typically used. With that motivation, in this work we used models representing three different categories, in a completely predictive way: a two-parameter cubic EoS (PR), a three-parameter cubic EoS (RKPR) and a three-parameter SAFT EoS (PC-SAFT). Their predictions of infinite dilution activity coefficients were analyzed and compared, in contrast to available data for different mixtures of n-butane to n-octane as the lighter compound and paraffins ranging from C16 to C36 as the heavier, in both extremes of dilution. The obtained results, and their analysis, allowed us to extract very clear conclusions which were not present in the literature so far, regarding the importance of a third parameter in any type of EoS.Fil: Tassin, Natalia Giselle. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; ArgentinaFil: Rodriguez Reartes, Sabrina Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Cismondi Duarte, Martín. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; Argentina. YPF - Tecnología; ArgentinaElsevier Science2020-11info:eu-repo/date/embargoEnd/2021-04-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/126830Tassin, Natalia Giselle; Rodriguez Reartes, Sabrina Belen; Cismondi Duarte, Martín; Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!; Elsevier Science; Fluid Phase Equilibria; 522; 11-2020; 1-31; 1127530378-3812CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0378381220303010info:eu-repo/semantics/altIdentifier/doi/10.1016/j.fluid.2020.112753info:eu-repo/semantics/embargoedAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:10:30Zoai:ri.conicet.gov.ar:11336/126830instacron: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 10:10:30.942CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!
title Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!
spellingShingle Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!
Tassin, Natalia Giselle
EQUATIONS OF STATE
ACTIVITY COEFFICIENTS
LIMITATIONS OF TWO PARAMETER EOS
THREE-PARAMETER EOS
N-ALKANE MIXTURES
title_short Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!
title_full Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!
title_fullStr Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!
title_full_unstemmed Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!
title_sort Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!
dc.creator.none.fl_str_mv Tassin, Natalia Giselle
Rodriguez Reartes, Sabrina Belen
Cismondi Duarte, Martín
author Tassin, Natalia Giselle
author_facet Tassin, Natalia Giselle
Rodriguez Reartes, Sabrina Belen
Cismondi Duarte, Martín
author_role author
author2 Rodriguez Reartes, Sabrina Belen
Cismondi Duarte, Martín
author2_role author
author
dc.subject.none.fl_str_mv EQUATIONS OF STATE
ACTIVITY COEFFICIENTS
LIMITATIONS OF TWO PARAMETER EOS
THREE-PARAMETER EOS
N-ALKANE MIXTURES
topic EQUATIONS OF STATE
ACTIVITY COEFFICIENTS
LIMITATIONS OF TWO PARAMETER EOS
THREE-PARAMETER EOS
N-ALKANE MIXTURES
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.4
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv The idea that cubic EoS's are very primitive and limited models, quite extended at present among researchers working on fluid properties and phase equilibria, has different roots, including some limitations observed specifically for classic and popular equations like Peng-Robinson (PR) or Soave-Redlich-Kwong (SRK). These are two-parameter models, i.e. they have only an attractive and a repulsive parameter to characterize each molecule, while other models like SAFT but also cubic –and still for non-associating molecules-introduce also a third parameter related somehow to the molecular structure or shape. One of the alluded limitations, actually a very clear one, is the complete failure in describing the non-ideality in nearly athermal mixtures, like those composed of n-alkanes with different chain lengths: SRK and PR predict positive deviations from ideality, which increase with the system asymmetry, while experimental measurements show exactly the opposite, i.e. increasing negative deviations from ideality. This provides an excellent opportunity to try to clarify whether such failure is due to the cubic nature of these classic models or to their two-parameter character and/or to the classic van der Waals one-fluid (vdW1f) mixing rules typically used. With that motivation, in this work we used models representing three different categories, in a completely predictive way: a two-parameter cubic EoS (PR), a three-parameter cubic EoS (RKPR) and a three-parameter SAFT EoS (PC-SAFT). Their predictions of infinite dilution activity coefficients were analyzed and compared, in contrast to available data for different mixtures of n-butane to n-octane as the lighter compound and paraffins ranging from C16 to C36 as the heavier, in both extremes of dilution. The obtained results, and their analysis, allowed us to extract very clear conclusions which were not present in the literature so far, regarding the importance of a third parameter in any type of EoS.
Fil: Tassin, Natalia Giselle. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; Argentina
Fil: Rodriguez Reartes, Sabrina Belen. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; Argentina
Fil: Cismondi Duarte, Martín. Universidad Nacional de Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigación y Desarrollo en Ingeniería de Procesos y Química Aplicada; Argentina. YPF - Tecnología; Argentina
description The idea that cubic EoS's are very primitive and limited models, quite extended at present among researchers working on fluid properties and phase equilibria, has different roots, including some limitations observed specifically for classic and popular equations like Peng-Robinson (PR) or Soave-Redlich-Kwong (SRK). These are two-parameter models, i.e. they have only an attractive and a repulsive parameter to characterize each molecule, while other models like SAFT but also cubic –and still for non-associating molecules-introduce also a third parameter related somehow to the molecular structure or shape. One of the alluded limitations, actually a very clear one, is the complete failure in describing the non-ideality in nearly athermal mixtures, like those composed of n-alkanes with different chain lengths: SRK and PR predict positive deviations from ideality, which increase with the system asymmetry, while experimental measurements show exactly the opposite, i.e. increasing negative deviations from ideality. This provides an excellent opportunity to try to clarify whether such failure is due to the cubic nature of these classic models or to their two-parameter character and/or to the classic van der Waals one-fluid (vdW1f) mixing rules typically used. With that motivation, in this work we used models representing three different categories, in a completely predictive way: a two-parameter cubic EoS (PR), a three-parameter cubic EoS (RKPR) and a three-parameter SAFT EoS (PC-SAFT). Their predictions of infinite dilution activity coefficients were analyzed and compared, in contrast to available data for different mixtures of n-butane to n-octane as the lighter compound and paraffins ranging from C16 to C36 as the heavier, in both extremes of dilution. The obtained results, and their analysis, allowed us to extract very clear conclusions which were not present in the literature so far, regarding the importance of a third parameter in any type of EoS.
publishDate 2020
dc.date.none.fl_str_mv 2020-11
info:eu-repo/date/embargoEnd/2021-04-01
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/11336/126830
Tassin, Natalia Giselle; Rodriguez Reartes, Sabrina Belen; Cismondi Duarte, Martín; Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!; Elsevier Science; Fluid Phase Equilibria; 522; 11-2020; 1-31; 112753
0378-3812
CONICET Digital
CONICET
url http://hdl.handle.net/11336/126830
identifier_str_mv Tassin, Natalia Giselle; Rodriguez Reartes, Sabrina Belen; Cismondi Duarte, Martín; Activity coefficients in nearly athermal mixtures predicted from equations of state: Don't blame the cubic when it is the lack of a third parameter!; Elsevier Science; Fluid Phase Equilibria; 522; 11-2020; 1-31; 112753
0378-3812
CONICET Digital
CONICET
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language eng
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info:eu-repo/semantics/altIdentifier/doi/10.1016/j.fluid.2020.112753
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