Modeling phase equilibria of ternary systems (water + formic acid + ester or alcohol) through UNIFAC-original, SERLAS, NRTL, NRTL-modified, and three-suffix Margules

Parameter estimation using genetic algorithm

Aynur Senol, Mehmet Bilgin, Burcu Baslioglu, Gholamreza Vakili-Nezhaad

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Ternary liquid-liquid equilibrium (LLE) systems composed of (water + formic acid + ester or alcohol), exhibiting experimental phase diagrams of type 1, have been studied at T = (298.2 ± 0.1) K and P = (101.3 ± 0.7) kPa. The equilibrium distribution of formic acid onto (water + solvent) two-phase system is better for dibasic ester (diethyl sebacate, diethyl succinate) as compared to monobasic ester (ethyl caprylate, ethyl valerate) and isoamyl alcohol. The thermodynamic models SERLAS, UNIFAC-original, NRTL, NRTL-modified and three-suffix Margules have been deeply tested for consistency in simulating the ternary LLE behavior. An immediate goal is to estimate the interaction parameters of molecular models from ternary data only using a genetic algorithm. The genetic algorithm identifies globally optimal values by producing a population of candidate solutions from given upper and lower bounds of the interaction parameters. The reliability of existing models has been analyzed statistically with respect to three physical extraction factors. Essentially, SERLAS, UNIFAC-original, NRTL, NRTL-modified and three-suffix Margules yield mean errors of 3.4%, 19.4%, 4.2%, 4.4% and 8.6%, respectively, enabling the ternary phase behavior to be simulated satisfactorily. The UNIFAC-original prediction is moderately precise. NRTL is especially effective in correlating both the two-phase envelope size and the tie line slope. While SERLAS has proven reasonably successful in reproducing the physical extraction factors, yielding about equally accurately estimates for each ternary system.

Original languageEnglish
Pages (from-to)254-265
Number of pages12
JournalFluid Phase Equilibria
Volume429
DOIs
Publication statusPublished - Dec 15 2016

Fingerprint

Formic Acid Esters
Formic acid
formic acid
Ternary systems
ternary systems
genetic algorithms
Phase equilibria
Parameter estimation
esters
Esters
alcohols
Alcohols
Genetic algorithms
Water
Liquids
liquids
water
Valerates
binary systems (materials)
Phase behavior

Keywords

  • Ester
  • Formic acid
  • Genetic algorithm
  • Liquid-liquid equilibria
  • Modeling

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

@article{b79672cdddac4915aee849340f2984d5,
title = "Modeling phase equilibria of ternary systems (water + formic acid + ester or alcohol) through UNIFAC-original, SERLAS, NRTL, NRTL-modified, and three-suffix Margules: Parameter estimation using genetic algorithm",
abstract = "Ternary liquid-liquid equilibrium (LLE) systems composed of (water + formic acid + ester or alcohol), exhibiting experimental phase diagrams of type 1, have been studied at T = (298.2 ± 0.1) K and P = (101.3 ± 0.7) kPa. The equilibrium distribution of formic acid onto (water + solvent) two-phase system is better for dibasic ester (diethyl sebacate, diethyl succinate) as compared to monobasic ester (ethyl caprylate, ethyl valerate) and isoamyl alcohol. The thermodynamic models SERLAS, UNIFAC-original, NRTL, NRTL-modified and three-suffix Margules have been deeply tested for consistency in simulating the ternary LLE behavior. An immediate goal is to estimate the interaction parameters of molecular models from ternary data only using a genetic algorithm. The genetic algorithm identifies globally optimal values by producing a population of candidate solutions from given upper and lower bounds of the interaction parameters. The reliability of existing models has been analyzed statistically with respect to three physical extraction factors. Essentially, SERLAS, UNIFAC-original, NRTL, NRTL-modified and three-suffix Margules yield mean errors of 3.4{\%}, 19.4{\%}, 4.2{\%}, 4.4{\%} and 8.6{\%}, respectively, enabling the ternary phase behavior to be simulated satisfactorily. The UNIFAC-original prediction is moderately precise. NRTL is especially effective in correlating both the two-phase envelope size and the tie line slope. While SERLAS has proven reasonably successful in reproducing the physical extraction factors, yielding about equally accurately estimates for each ternary system.",
keywords = "Ester, Formic acid, Genetic algorithm, Liquid-liquid equilibria, Modeling",
author = "Aynur Senol and Mehmet Bilgin and Burcu Baslioglu and Gholamreza Vakili-Nezhaad",
year = "2016",
month = "12",
day = "15",
doi = "10.1016/j.fluid.2016.08.041",
language = "English",
volume = "429",
pages = "254--265",
journal = "Fluid Phase Equilibria",
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publisher = "Elsevier",

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TY - JOUR

T1 - Modeling phase equilibria of ternary systems (water + formic acid + ester or alcohol) through UNIFAC-original, SERLAS, NRTL, NRTL-modified, and three-suffix Margules

T2 - Parameter estimation using genetic algorithm

AU - Senol, Aynur

AU - Bilgin, Mehmet

AU - Baslioglu, Burcu

AU - Vakili-Nezhaad, Gholamreza

PY - 2016/12/15

Y1 - 2016/12/15

N2 - Ternary liquid-liquid equilibrium (LLE) systems composed of (water + formic acid + ester or alcohol), exhibiting experimental phase diagrams of type 1, have been studied at T = (298.2 ± 0.1) K and P = (101.3 ± 0.7) kPa. The equilibrium distribution of formic acid onto (water + solvent) two-phase system is better for dibasic ester (diethyl sebacate, diethyl succinate) as compared to monobasic ester (ethyl caprylate, ethyl valerate) and isoamyl alcohol. The thermodynamic models SERLAS, UNIFAC-original, NRTL, NRTL-modified and three-suffix Margules have been deeply tested for consistency in simulating the ternary LLE behavior. An immediate goal is to estimate the interaction parameters of molecular models from ternary data only using a genetic algorithm. The genetic algorithm identifies globally optimal values by producing a population of candidate solutions from given upper and lower bounds of the interaction parameters. The reliability of existing models has been analyzed statistically with respect to three physical extraction factors. Essentially, SERLAS, UNIFAC-original, NRTL, NRTL-modified and three-suffix Margules yield mean errors of 3.4%, 19.4%, 4.2%, 4.4% and 8.6%, respectively, enabling the ternary phase behavior to be simulated satisfactorily. The UNIFAC-original prediction is moderately precise. NRTL is especially effective in correlating both the two-phase envelope size and the tie line slope. While SERLAS has proven reasonably successful in reproducing the physical extraction factors, yielding about equally accurately estimates for each ternary system.

AB - Ternary liquid-liquid equilibrium (LLE) systems composed of (water + formic acid + ester or alcohol), exhibiting experimental phase diagrams of type 1, have been studied at T = (298.2 ± 0.1) K and P = (101.3 ± 0.7) kPa. The equilibrium distribution of formic acid onto (water + solvent) two-phase system is better for dibasic ester (diethyl sebacate, diethyl succinate) as compared to monobasic ester (ethyl caprylate, ethyl valerate) and isoamyl alcohol. The thermodynamic models SERLAS, UNIFAC-original, NRTL, NRTL-modified and three-suffix Margules have been deeply tested for consistency in simulating the ternary LLE behavior. An immediate goal is to estimate the interaction parameters of molecular models from ternary data only using a genetic algorithm. The genetic algorithm identifies globally optimal values by producing a population of candidate solutions from given upper and lower bounds of the interaction parameters. The reliability of existing models has been analyzed statistically with respect to three physical extraction factors. Essentially, SERLAS, UNIFAC-original, NRTL, NRTL-modified and three-suffix Margules yield mean errors of 3.4%, 19.4%, 4.2%, 4.4% and 8.6%, respectively, enabling the ternary phase behavior to be simulated satisfactorily. The UNIFAC-original prediction is moderately precise. NRTL is especially effective in correlating both the two-phase envelope size and the tie line slope. While SERLAS has proven reasonably successful in reproducing the physical extraction factors, yielding about equally accurately estimates for each ternary system.

KW - Ester

KW - Formic acid

KW - Genetic algorithm

KW - Liquid-liquid equilibria

KW - Modeling

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U2 - 10.1016/j.fluid.2016.08.041

DO - 10.1016/j.fluid.2016.08.041

M3 - Article

VL - 429

SP - 254

EP - 265

JO - Fluid Phase Equilibria

JF - Fluid Phase Equilibria

SN - 0378-3812

ER -