Fluid–solid equilibria of flexible and linear rigid tangent chains from Wertheim’s thermodynamic perturbation theory

An extension of Wertheim’s first-order thermodynamic perturbation theory is proposed to describe the global phase behavior of linear rigid tangent hard sphere chains. The extension is based on a scaling proposed recently by Vega and McBride [Phys. Rev. E 65, 052501 (2002)] for the equation of state...

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Autores: Jiménez Blas, Felipe, Sanz, Eduardo, Vega, C., Galindo, Amparo
Formato: artículo
Fecha de publicación:2003
País:España
Recursos:Universidad de Huelva (UHU)
Repositorio:Arias Montano. Repositorio Institucional de la Universidad de Huelva
Idioma:inglés
OAI Identifier:oai:ariasmontano.uhu.es:10272/17337
Acesso em linha:http://hdl.handle.net/10272/17337
Access Level:acceso abierto
Palavra-chave:Phase equilibria
Lennard-Jones chains
Wertheim&apos
s theory
Solid phase
Molecular simulation
Monte Carlo
Free energy
Flexible tangent chains
Linear rigid tangent chains
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spelling Fluid–solid equilibria of flexible and linear rigid tangent chains from Wertheim’s thermodynamic perturbation theoryJiménez Blas, FelipeSanz, EduardoVega, C.Galindo, AmparoPhase equilibriaLennard-Jones chainsWertheim&aposs theorySolid phaseMolecular simulationMonte CarloFree energyFlexible tangent chainsLinear rigid tangent chainsAn extension of Wertheim’s first-order thermodynamic perturbation theory is proposed to describe the global phase behavior of linear rigid tangent hard sphere chains. The extension is based on a scaling proposed recently by Vega and McBride [Phys. Rev. E 65, 052501 (2002)] for the equation of state of linear chains in the solid phase. We have used the Einstein-crystal methodology, the Rahman–Parrinello technique, and the thermodynamic integration method for calculating the free energy and equation of state of linear rigid hard sphere chains with different chain lengths, including the solid–fluid phase equilibria. Agreement between the simulation data and theoretical predictions is excellent in all cases. Once it is confirmed that the proposed theory can be used to describe correctly the equation of state, free energy, and solid–fluid phase transitions of linear rigid molecules, a simple mean-field approximation at the level of van der Waals is included to account for segment–segment attractive interactions. The approach is used to determine the global phase behavior of fully flexible and linear rigid chains of varying chain lengths. The main effect of increasing the chain length in the case of linear rigid chains is to decrease the fluid densities at freezing, so that the triple-point temperatures increase. As a consequence, the range of temperatures where vapor–liquid equilibria exist decreases considerably with chain length. This behavior is a direct result of the stabilization of the solid phase with respect to the liquid phase as the chain length is increased. The vapor–liquid equilibria are seen to disappear for linear rigid chains formed by more than 11 hard sphere segments that interact through an attractive van der Waals mean-field contribution; in other words, long linear rigid chains exhibit solid–vapor phase behavior only. In the case of flexible chains, the fluid–solid equilibrium is hardly affected by the chain length, so that the triple-point temperature reaches quickly an asymptotic value. In contrast to linear rigid chains, flexible chains present quite a broad range of temperatures where vapor–liquid equilibria exist. Although the vapor–liquid equilibria of flexible and linear rigid chain molecules are similar, the differences in the type of stable solid they form and, more importantly, the differences in the scaling of thermodynamic properties with chain length bring dramatic differences to the appearance of their phase diagrams.AIP Publishing20032003-01-0120032003-01-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10272/17337reponame: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:10272/173372026-06-02T14:58:11Z
dc.title.none.fl_str_mv Fluid–solid equilibria of flexible and linear rigid tangent chains from Wertheim’s thermodynamic perturbation theory
title Fluid–solid equilibria of flexible and linear rigid tangent chains from Wertheim’s thermodynamic perturbation theory
spellingShingle Fluid–solid equilibria of flexible and linear rigid tangent chains from Wertheim’s thermodynamic perturbation theory
Jiménez Blas, Felipe
Phase equilibria
Lennard-Jones chains
Wertheim&apos
s theory
Solid phase
Molecular simulation
Monte Carlo
Free energy
Flexible tangent chains
Linear rigid tangent chains
title_short Fluid–solid equilibria of flexible and linear rigid tangent chains from Wertheim’s thermodynamic perturbation theory
title_full Fluid–solid equilibria of flexible and linear rigid tangent chains from Wertheim’s thermodynamic perturbation theory
title_fullStr Fluid–solid equilibria of flexible and linear rigid tangent chains from Wertheim’s thermodynamic perturbation theory
title_full_unstemmed Fluid–solid equilibria of flexible and linear rigid tangent chains from Wertheim’s thermodynamic perturbation theory
title_sort Fluid–solid equilibria of flexible and linear rigid tangent chains from Wertheim’s thermodynamic perturbation theory
dc.creator.none.fl_str_mv Jiménez Blas, Felipe
Sanz, Eduardo
Vega, C.
Galindo, Amparo
author Jiménez Blas, Felipe
author_facet Jiménez Blas, Felipe
Sanz, Eduardo
Vega, C.
Galindo, Amparo
author_role author
author2 Sanz, Eduardo
Vega, C.
Galindo, Amparo
author2_role author
author
author
dc.contributor.none.fl_str_mv
dc.subject.none.fl_str_mv Phase equilibria
Lennard-Jones chains
Wertheim&apos
s theory
Solid phase
Molecular simulation
Monte Carlo
Free energy
Flexible tangent chains
Linear rigid tangent chains
topic Phase equilibria
Lennard-Jones chains
Wertheim&apos
s theory
Solid phase
Molecular simulation
Monte Carlo
Free energy
Flexible tangent chains
Linear rigid tangent chains
description An extension of Wertheim’s first-order thermodynamic perturbation theory is proposed to describe the global phase behavior of linear rigid tangent hard sphere chains. The extension is based on a scaling proposed recently by Vega and McBride [Phys. Rev. E 65, 052501 (2002)] for the equation of state of linear chains in the solid phase. We have used the Einstein-crystal methodology, the Rahman–Parrinello technique, and the thermodynamic integration method for calculating the free energy and equation of state of linear rigid hard sphere chains with different chain lengths, including the solid–fluid phase equilibria. Agreement between the simulation data and theoretical predictions is excellent in all cases. Once it is confirmed that the proposed theory can be used to describe correctly the equation of state, free energy, and solid–fluid phase transitions of linear rigid molecules, a simple mean-field approximation at the level of van der Waals is included to account for segment–segment attractive interactions. The approach is used to determine the global phase behavior of fully flexible and linear rigid chains of varying chain lengths. The main effect of increasing the chain length in the case of linear rigid chains is to decrease the fluid densities at freezing, so that the triple-point temperatures increase. As a consequence, the range of temperatures where vapor–liquid equilibria exist decreases considerably with chain length. This behavior is a direct result of the stabilization of the solid phase with respect to the liquid phase as the chain length is increased. The vapor–liquid equilibria are seen to disappear for linear rigid chains formed by more than 11 hard sphere segments that interact through an attractive van der Waals mean-field contribution; in other words, long linear rigid chains exhibit solid–vapor phase behavior only. In the case of flexible chains, the fluid–solid equilibrium is hardly affected by the chain length, so that the triple-point temperature reaches quickly an asymptotic value. In contrast to linear rigid chains, flexible chains present quite a broad range of temperatures where vapor–liquid equilibria exist. Although the vapor–liquid equilibria of flexible and linear rigid chain molecules are similar, the differences in the type of stable solid they form and, more importantly, the differences in the scaling of thermodynamic properties with chain length bring dramatic differences to the appearance of their phase diagrams.
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
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10272/17337
url http://hdl.handle.net/10272/17337
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 AIP Publishing
publisher.none.fl_str_mv AIP Publishing
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
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score 15,812429

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