Rigorous Phase Equilibrium Calculation Methods for Strong Electrolyte Solutions: The Isothermal Flash

<p dir="ltr">New algorithms for vapor – liquid (VLE) and liquid - liquid (LLE) equilibrium calculations at constant temperature, pressure and feed phase composition (PT flash), with application to mixtures containing fully dissociating electrolytes are presented. A new approach is pr...

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Main Author: Ilias K. Nikolaidis (9217172) (author)
Other Authors: Nefeli Novak (6617864) (author), Georgios M. Kontogeorgis (1571419) (author), Ioannis G. Economou (559797) (author)
Published: 2022
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author Ilias K. Nikolaidis (9217172)
author2 Nefeli Novak (6617864)
Georgios M. Kontogeorgis (1571419)
Ioannis G. Economou (559797)
author2_role author
author
author
author_facet Ilias K. Nikolaidis (9217172)
Nefeli Novak (6617864)
Georgios M. Kontogeorgis (1571419)
Ioannis G. Economou (559797)
author_role author
dc.creator.none.fl_str_mv Ilias K. Nikolaidis (9217172)
Nefeli Novak (6617864)
Georgios M. Kontogeorgis (1571419)
Ioannis G. Economou (559797)
dc.date.none.fl_str_mv 2022-07-01T06:00:00Z
dc.identifier.none.fl_str_mv 10.1016/j.fluid.2022.113441
dc.relation.none.fl_str_mv https://figshare.com/articles/journal_contribution/Rigorous_Phase_Equilibrium_Calculation_Methods_for_Strong_Electrolyte_Solutions_The_Isothermal_Flash/24501178
dc.rights.none.fl_str_mv CC BY 4.0
info:eu-repo/semantics/openAccess
dc.subject.none.fl_str_mv Engineering
Biomedical engineering
Chemical engineering
Nanotechnology
phase equilibria algorithm
electrolytes
mixed salts
mixed solvents
dc.title.none.fl_str_mv Rigorous Phase Equilibrium Calculation Methods for Strong Electrolyte Solutions: The Isothermal Flash
dc.type.none.fl_str_mv Text
Journal contribution
info:eu-repo/semantics/publishedVersion
text
contribution to journal
description <p dir="ltr">New algorithms for vapor – liquid (VLE) and liquid - liquid (LLE) equilibrium calculations at constant temperature, pressure and feed phase composition (PT flash), with application to mixtures containing fully dissociating electrolytes are presented. A new approach is proposed and is rigorously derived by treating phase equilibrium as a minimization problem of the Gibbs free energy, while utilizing the electro-neutrality condition as a constraint. In this way, an augmented function (Lagrange function) is formulated which serves as the basis for the equations that govern phase equilibrium. It is shown that the Lagrange multiplier which corresponds to the electro-neutrality constraint has theoretical meaning and direct relation to the electrostatic potential difference between inhomogeneous phases. Based on the new approach, named Electrochemical Ionic Approach (EIA), two new numerical methods are presented; a successive substitution method similar to the classical Rachford-Rice method and a second-order one, which is based on Newton's method. The new algorithms are general and can be readily applied to mixtures of multiple solvents and one or multiple salts without any modifications. Finally, the Mean Ionic Approach (MIA) for mixtures with multiple solvents and only one salt is discussed in detail and a successive substitution and a second-order method are formulated. Moreover, the MIA is formally extended and presented for mixtures of multiple solvents and multiple salts. All the resulting methods are applied to mixtures with multiple solvents and one or multiple strongly dissociating electrolytes. The performance and technical details of each method are discussed and compared. The calculations are performed with the electrolyte Statistical Associating Fluid Theory with the Mie potential of variable range (eSAFT-VR Mie) equation of state but the proposed methods are general and could be used with any other thermodynamic model.</p><h2>Other Information</h2><p dir="ltr">Published in: Fluid Phase Equilibria<br>License: <a href="http://creativecommons.org/licenses/by/4.0/" target="_blank">http://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1016/j.fluid.2022.113441" target="_blank">https://dx.doi.org/10.1016/j.fluid.2022.113441</a></p>
eu_rights_str_mv openAccess
id Manara2_b88b4239bd634fcd1c454ef6ed81cdb0
identifier_str_mv 10.1016/j.fluid.2022.113441
network_acronym_str Manara2
network_name_str Manara2
oai_identifier_str oai:figshare.com:article/24501178
publishDate 2022
repository.mail.fl_str_mv
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rights_invalid_str_mv CC BY 4.0
spelling Rigorous Phase Equilibrium Calculation Methods for Strong Electrolyte Solutions: The Isothermal FlashIlias K. Nikolaidis (9217172)Nefeli Novak (6617864)Georgios M. Kontogeorgis (1571419)Ioannis G. Economou (559797)EngineeringBiomedical engineeringChemical engineeringNanotechnologyphase equilibria algorithmelectrolytesmixed saltsmixed solvents<p dir="ltr">New algorithms for vapor – liquid (VLE) and liquid - liquid (LLE) equilibrium calculations at constant temperature, pressure and feed phase composition (PT flash), with application to mixtures containing fully dissociating electrolytes are presented. A new approach is proposed and is rigorously derived by treating phase equilibrium as a minimization problem of the Gibbs free energy, while utilizing the electro-neutrality condition as a constraint. In this way, an augmented function (Lagrange function) is formulated which serves as the basis for the equations that govern phase equilibrium. It is shown that the Lagrange multiplier which corresponds to the electro-neutrality constraint has theoretical meaning and direct relation to the electrostatic potential difference between inhomogeneous phases. Based on the new approach, named Electrochemical Ionic Approach (EIA), two new numerical methods are presented; a successive substitution method similar to the classical Rachford-Rice method and a second-order one, which is based on Newton's method. The new algorithms are general and can be readily applied to mixtures of multiple solvents and one or multiple salts without any modifications. Finally, the Mean Ionic Approach (MIA) for mixtures with multiple solvents and only one salt is discussed in detail and a successive substitution and a second-order method are formulated. Moreover, the MIA is formally extended and presented for mixtures of multiple solvents and multiple salts. All the resulting methods are applied to mixtures with multiple solvents and one or multiple strongly dissociating electrolytes. The performance and technical details of each method are discussed and compared. The calculations are performed with the electrolyte Statistical Associating Fluid Theory with the Mie potential of variable range (eSAFT-VR Mie) equation of state but the proposed methods are general and could be used with any other thermodynamic model.</p><h2>Other Information</h2><p dir="ltr">Published in: Fluid Phase Equilibria<br>License: <a href="http://creativecommons.org/licenses/by/4.0/" target="_blank">http://creativecommons.org/licenses/by/4.0/</a><br>See article on publisher's website: <a href="https://dx.doi.org/10.1016/j.fluid.2022.113441" target="_blank">https://dx.doi.org/10.1016/j.fluid.2022.113441</a></p>2022-07-01T06:00:00ZTextJournal contributioninfo:eu-repo/semantics/publishedVersiontextcontribution to journal10.1016/j.fluid.2022.113441https://figshare.com/articles/journal_contribution/Rigorous_Phase_Equilibrium_Calculation_Methods_for_Strong_Electrolyte_Solutions_The_Isothermal_Flash/24501178CC BY 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/245011782022-07-01T06:00:00Z
spellingShingle Rigorous Phase Equilibrium Calculation Methods for Strong Electrolyte Solutions: The Isothermal Flash
Ilias K. Nikolaidis (9217172)
Engineering
Biomedical engineering
Chemical engineering
Nanotechnology
phase equilibria algorithm
electrolytes
mixed salts
mixed solvents
status_str publishedVersion
title Rigorous Phase Equilibrium Calculation Methods for Strong Electrolyte Solutions: The Isothermal Flash
title_full Rigorous Phase Equilibrium Calculation Methods for Strong Electrolyte Solutions: The Isothermal Flash
title_fullStr Rigorous Phase Equilibrium Calculation Methods for Strong Electrolyte Solutions: The Isothermal Flash
title_full_unstemmed Rigorous Phase Equilibrium Calculation Methods for Strong Electrolyte Solutions: The Isothermal Flash
title_short Rigorous Phase Equilibrium Calculation Methods for Strong Electrolyte Solutions: The Isothermal Flash
title_sort Rigorous Phase Equilibrium Calculation Methods for Strong Electrolyte Solutions: The Isothermal Flash
topic Engineering
Biomedical engineering
Chemical engineering
Nanotechnology
phase equilibria algorithm
electrolytes
mixed salts
mixed solvents