Study of the solid–liquid–vapour phase equilibria of flexible chain molecules using Wertheim’s thermodynamic perturbation theory

The phase diagram of flexible molecules formed by freely-jointed tangent spheres is studied using the first-order thermodynamic perturbation theory of Wertheim for both fluid and solid phases. A mean-field term is added to the free energy of the fluid and solid phase in order to account for attracti...

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Detalles Bibliográficos
Autores: Jiménez Blas, Felipe, Galindo, Amparo, Vega, Carlos
Tipo de recurso: artículo
Fecha de publicación:2003
País:España
Institución:Universidad de Huelva (UHU)
Repositorio:Arias Montano. Repositorio Institucional de la Universidad de Huelva
Idioma:inglés
OAI Identifier:oai:ariasmontano.uhu.es:10272/17636
Acceso en línea:http://hdl.handle.net/10272/17636
Access Level:acceso abierto
Palabra clave:Wertheim&apos
s thermodynamic perturbation theory
Solid-liquid
Solid-vapour
Vapour-liquid
Flexible chain molecules
Phase behaviour
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spelling Study of the solid–liquid–vapour phase equilibria of flexible chain molecules using Wertheim’s thermodynamic perturbation theoryJiménez Blas, FelipeGalindo, AmparoVega, CarlosWertheim&aposs thermodynamic perturbation theorySolid-liquidSolid-vapourVapour-liquidFlexible chain moleculesPhase behaviourThe phase diagram of flexible molecules formed by freely-jointed tangent spheres is studied using the first-order thermodynamic perturbation theory of Wertheim for both fluid and solid phases. A mean-field term is added to the free energy of the fluid and solid phase in order to account for attractive dispersion forces. The approach is used to determine the global (solid– liquid–vapour) phase diagrams and triple points of chain molecules of increasing chain length. It is found that the triple point temperature is not affected strongly by the length of the chain, whereas the gas–liquid critical temperature increases dramatically. The asymptotic limits of the phase diagram for infinitely long chains are discussed. The reduced critical temperature of infinitely long chains as given by the mean-field theory is 2/3, and the reduced triple point temperature is 0.04856, so that an asymptotic value of Tt /Tc = 0.07284 for the ratio of the triple to critical point temperatures is obtained. This indicates that fully-flexible tangent chains present an enormous liquid range. The proposed theory, while being extremely simple, provides a useful insight into the phase behaviour of chain molecules, showing the existence of finite asymptotic limits for the triple and critical point temperatures. However, since n-alkanes present an asymptotic limit of about Tt/Tc = 0.40, the agreement with experiment is not quantitative. This suggests that fully flexible models may not be appropriate to model the solid phases of real chain molecules.Taylor and Francis20032003-01-0120032003-01-01journal articlehttp://purl.org/coar/resource_type/c_6501SMURhttp://purl.org/coar/version/c_71e4c1898caa6e32info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10272/17636reponame:Arias Montano. Repositorio Institucional de la Universidad de Huelvainstname:Universidad de Huelva (UHU)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Atribución-NoComercial-SinDerivadas 3.0 Españahttp://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccessoai:ariasmontano.uhu.es:10272/176362026-06-02T14:58:11Z
dc.title.none.fl_str_mv Study of the solid–liquid–vapour phase equilibria of flexible chain molecules using Wertheim’s thermodynamic perturbation theory
title Study of the solid–liquid–vapour phase equilibria of flexible chain molecules using Wertheim’s thermodynamic perturbation theory
spellingShingle Study of the solid–liquid–vapour phase equilibria of flexible chain molecules using Wertheim’s thermodynamic perturbation theory
Jiménez Blas, Felipe
Wertheim&apos
s thermodynamic perturbation theory
Solid-liquid
Solid-vapour
Vapour-liquid
Flexible chain molecules
Phase behaviour
title_short Study of the solid–liquid–vapour phase equilibria of flexible chain molecules using Wertheim’s thermodynamic perturbation theory
title_full Study of the solid–liquid–vapour phase equilibria of flexible chain molecules using Wertheim’s thermodynamic perturbation theory
title_fullStr Study of the solid–liquid–vapour phase equilibria of flexible chain molecules using Wertheim’s thermodynamic perturbation theory
title_full_unstemmed Study of the solid–liquid–vapour phase equilibria of flexible chain molecules using Wertheim’s thermodynamic perturbation theory
title_sort Study of the solid–liquid–vapour phase equilibria of flexible chain molecules using Wertheim’s thermodynamic perturbation theory
dc.creator.none.fl_str_mv Jiménez Blas, Felipe
Galindo, Amparo
Vega, Carlos
author Jiménez Blas, Felipe
author_facet Jiménez Blas, Felipe
Galindo, Amparo
Vega, Carlos
author_role author
author2 Galindo, Amparo
Vega, Carlos
author2_role author
author
dc.contributor.none.fl_str_mv
dc.subject.none.fl_str_mv Wertheim&apos
s thermodynamic perturbation theory
Solid-liquid
Solid-vapour
Vapour-liquid
Flexible chain molecules
Phase behaviour
topic Wertheim&apos
s thermodynamic perturbation theory
Solid-liquid
Solid-vapour
Vapour-liquid
Flexible chain molecules
Phase behaviour
description The phase diagram of flexible molecules formed by freely-jointed tangent spheres is studied using the first-order thermodynamic perturbation theory of Wertheim for both fluid and solid phases. A mean-field term is added to the free energy of the fluid and solid phase in order to account for attractive dispersion forces. The approach is used to determine the global (solid– liquid–vapour) phase diagrams and triple points of chain molecules of increasing chain length. It is found that the triple point temperature is not affected strongly by the length of the chain, whereas the gas–liquid critical temperature increases dramatically. The asymptotic limits of the phase diagram for infinitely long chains are discussed. The reduced critical temperature of infinitely long chains as given by the mean-field theory is 2/3, and the reduced triple point temperature is 0.04856, so that an asymptotic value of Tt /Tc = 0.07284 for the ratio of the triple to critical point temperatures is obtained. This indicates that fully-flexible tangent chains present an enormous liquid range. The proposed theory, while being extremely simple, provides a useful insight into the phase behaviour of chain molecules, showing the existence of finite asymptotic limits for the triple and critical point temperatures. However, since n-alkanes present an asymptotic limit of about Tt/Tc = 0.40, the agreement with experiment is not quantitative. This suggests that fully flexible models may not be appropriate to model the solid phases of real chain molecules.
publishDate 2003
dc.date.none.fl_str_mv 2003
2003-01-01
2003
2003-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
SMUR
http://purl.org/coar/version/c_71e4c1898caa6e32
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10272/17636
url http://hdl.handle.net/10272/17636
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Atribución-NoComercial-SinDerivadas 3.0 España
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Atribución-NoComercial-SinDerivadas 3.0 España
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Taylor and Francis
publisher.none.fl_str_mv Taylor and Francis
dc.source.none.fl_str_mv reponame:Arias Montano. Repositorio Institucional de la Universidad de Huelva
instname:Universidad de Huelva (UHU)
instname_str Universidad de Huelva (UHU)
reponame_str Arias Montano. Repositorio Institucional de la Universidad de Huelva
collection Arias Montano. Repositorio Institucional de la Universidad de Huelva
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869425271786962944
score 15,81155

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