J.A. Labarta

03/20/2024: Thanks a lot for all the interest shown. This paper has been one of the most downloaded* during its first 12 months of publication in AIChE Journal (*Among work published in an issue between 1 January 2022 – 31 December 2022).

06/28/2022: A new research paper has been published regarding the possibilities and limitations of the nonrandom two-liquids (NRTL) model for reproducing different kinds of fluid phase equilibria (AIChE Journal. 2022, 68(10), e17805. DOI: 10.1002/aic.17805).

This paper references 3 graphical user interfaces (GUIs), publicly available online, to help researchers that have to deal with experimental LL and LV data correlation (using the NRTL, UNIQUAC or any alternative model):

1. GMcal_TieLinesLL: Graphical User Interface (GUI) for the Topological Analysis of Calculated GM Surfaces and Curves, including Tie-Lines, Hessian Matrix, Spinodal Curve, Critical Point Location, Miscibility Boundaries, etc. for Binary and Ternary LLE Data. Institutional Repository of the University of Alicante (RUA). 2015-2022. Publicly available at: http://hdl.handle.net/10045/51725.

2. GMcal_TieLinesLV: Graphical User Interface (GUI) for the Topological Analysis of GM Functions for Binary and Ternary (isobaric or isothermal) Vapor-Liquid Equilibrium (VLE) data (including Tie-Lines, Derivatives, Distillation Boundaries, LL Critical Points Location, etc.). Institutional Repository of the University of Alicante (RUA). 2022. Publicly available at: http://hdl.handle.net/10045/122857.

3. Boundaries_LL_NRTL: Graphical User Interface (GUI) for the Characterization of the NRTL Model: Binary Spinodal Surfaces (in the ti,j-tj,i-xi space), LLE Maps and Miscibility Boundaries. Institutional Repository of the University of Alicante (RUA). 2022. Publicly available at: http://hdl.handle.net/10045/121471.

Related references:

*Should we trust all the published LLE correlation parameters in phase equilibria? Necessity of their Assessment Prior to Publication. Fluid Phase Equilibria. 2017, 433, 243-252 (http://dx.doi.org/10.1016/j.fluid.2016.11.009). RUA: http://hdl.handle.net/10045/66521.

*GE Models and Algorithms for Condensed Phase Equilibrium Data Regression in Ternary Systems: Limitations and Proposals. The Open Thermodynamics Journal. 2011, 5, (Suppl 1-M5) 48-62 (http://dx.doi.org/10.2174/1874396X01105010048).

* Checking Liquid-Liquid Critical Point Conditions and their Application in Ternary Systems. Industrial & Engineering Chemistry Research. 2012, 51(13), 5098-5102 (http://dx.doi.org/10.1021/ie202793r).

*LLE data correlation using NRTL model for different types of binary systems: UCST, LCST and closed miscibility loops. Industrial & Engineering Chemistry Research. 2020, 59(17), 8469-8479 (https://doi.org/10.1021/acs.iecr.0c00141).

* Procedure for the correlation of normal appearance VLE data, where the classical models dramatically fail with no apparent reason. Fluid Phase Equilibria. 2019, 493, 88-101. DOI: https://doi.org/10.1016/j.fluid.2019.04.001.

* The unavoidable necessity of considering temperature dependence of the liquid Gibbs energy of mixing for certain VLE data correlations. Fluid Phase Equilibria. 2018, 473, 17-31. DOI: https://doi.org/10.1016/j.fluid.2018.05.025.

* Approximate Calculation of Distillation Boundaries for Ternary Azeotropic Systems. Ind. Eng. Chem. Res. 2011, 50 (12), 7462-7466. DOI: http://dx.doi.org/10.1021/ie101873.

* Numerical Determination of Distillation Boundaries for Multicomponent Homogeneous and Heterogeneous Azeotropic Systems. Computer Aided Chemical Engineering. 2010, 28(C), 643-648. DOI: http://dx.doi.org/10.1016/S1570-7946(10)28108-7.

* Procedure to Qualitatively Represent Residue Curve Maps and Analyze the Possible Existence of Distillation Boundaries. RUA, 2023: http://hdl.handle.net/10045/131058.

* Liquid-Liquid Equilibrium Data Correlation: Predicting A Robust and Consistent Set of Initial NRTL Parameters. RUA, 2023: http://hdl.handle.net/10045/134753.

* ParamIni_LL_NRTL: Graphical User Interface (GUI) for the Selection of NRTL Initial Parameters for the Correlation of Ternary Liquid-Liquid Equilibrium Data (Type I, II, III and 0 (LL island), i.e. with 1, 2, 3 or 0 binary pairs partially miscible). RUA, 2023: http://hdl.handle.net/10045/130017.

The analysis of residue curve maps is essential to know the VLE behavior of a ternary mixture, the possible existence of distillation boundaries and therefore different distillation regions in the ternary composition diagram, and the corresponding areas where the different distillation products are located. All this knowledge is necessary for the correct design of distillation column sequences especially when azeotropic distillation columns are included.

As a first step, it is possible to represent qualitative residue curve maps just by knowing the equilibrium temperature of all the characteristic points (nodes) of the ternary system, i.e. pure components, and binary and ternary azeotropes (if they exist). Here you can find a simple guide (RUA, 2023): http://hdl.handle.net/10045/131058.

More information about distillation boundaries and residue curves maps definition and calculation:

• Labarta, J.A.; Olaya, M.M.; Marcilla, A. GMcal_TieLinesVL: Graphical User Interface (GUI) for the Topological Analysis of Experimental and Calculated G^M Functions for Binary and Ternary (isobaric or isothermal) Vapor-Liquid Equilibrium (VLE) data (including Tie-Lines, Derivatives, Distillation Boundaries, LL Critical Points Location, etc.). Institutional Repository of the University of Alicante (RUA). 2022. Publicly available online at: http://hdl.handle.net/10045/122857.

• Labarta, J.A.; Serrano, M.D.; Velasco, R.; Olaya, M.M.; Marcilla, A. Approximate Calculation of Distillation Boundaries for Ternary Azeotropic Systems. Eng. Chem. Res. 2011, 50 (12), 7462-7466. DOI: http://dx.doi.org/10.1021/ie101873.
• Labarta, J.A.; Caballero, J.A.; Marcilla, A. Numerical Determination of Distillation Boundaries for Multicomponent Homogeneous and Heterogeneous Azeotropic Systems. Computer Aided Chemical Engineering. 2010, 28(C), 643-648. DOI: http://dx.doi.org/10.1016/S1570-7946(10)28108-7. Institutional Repository (RUA): http://hdl.handle.net/10045/14202.
• Gómez, A.; Ruiz, F.; Marcilla, A.; Labarta, J.A.; Menargues, S. Diseño de la separación de mezclas ternarias (I). Conceptos gráficos del equilibrio entre fases. Ingeniería Química. 2001, 377, 219-229. Institutional Repository (RUA): http://hdl.handle.net/10045/24715.
• Gómez, A.; Ruiz, F.; Marcilla, A.; Labarta, J.A.; Menargues, S. Diseño de la separación de mezclas ternarias (II). Aplicación de conceptos gráficos a la separación de mezclas azeotrópicas. Ingeniería Química. 2001, 379, 253-262. Institutional Repository (RUA): http://hdl.handle.net/10045/24716.

Similar to previous MatLab Graphical User Interfaces (GUI’s) developed to systematically check the consistency of LLE data correlation results, GMcal_TieLinesLL (v.2.3), or Boundaries_LL_NRTL for the analysis of the miscibility boundaries that the NRTL model present, this GUI, GMcal_TieLinesVL (new version v.2.3 RUA 2022: http://hdl.handle.net/10045/122857), allows the analysis of experimental and calculated (isobaric or isothermal) vapor-liquid equilibrium data for binary and ternary systems, in the sense presented in the following papers, to detect the necessity of considering larger dependences (of temperature or pressure, respectively) in the binary interaction parameters of the model used (e.g. NRTL model) and also to check the consistency of VLE data correlation results through the topological information contained in the Gibbs energy of mixing function:

• Procedure for the correlation of normal appearance VLE data, where the classical models dramatically fail with no apparent reason. Fluid Phase Equilibria. 2019, 493, 88-101. DOI: https://doi.org/10.1016/j.fluid.2019.04.001.
• The unavoidable necessity of considering temperature dependence of the liquid Gibbs energy of mixing for certain VLE data correlations. Fluid Phase Equilibria. 2018, 473, 17-31. DOI: https://doi.org/10.1016/j.fluid.2018.05.025.
• Should we trust all the published LLE correlation parameters in phase equilibria? Necessity of their Assessment Prior to Publication. Fluid Phase Equilibria. 2017, 433, 243-252 (http://dx.doi.org/10.1016/j.fluid.2016.11.009). RUA: http://hdl.handle.net/10045/66521.

This analysis allows researchers involved in the correlation of experimental vapor-liquid equilibrium data, to visualize the  experimental data’s  behavior and also the consistency and quality of the results obtained in the correlation process.

This new version of the GMcal_TieLinesVL (v.2.3) is also useful to analyze the predictions of the model used (when only the parameters of the corresponding models are known) regarding the possibilities of LLE, analyzing possible critical solution points, in the case of binary systems or the Hessian Matrix, Spinodal Curve and possible Plait Point Location in ternary systems in the corresponding range of experimental (isobaric or isothermal) data, and/or to the existence of distillation boundaries.

Related references:

Marcilla, A.; Labarta, J.A.; Olaya, M.M. Should we trust all the published LLE correlation parameters in phase equilibria? Necessity of their Assessment Prior to Publication. Fluid Phase Equilibria. 2017, 433, 243-252 (http://dx.doi.org/10.1016/j.fluid.2016.11.009). The 4^th most cited article published in Fluid Phase Equilibria in 2017-2020 (extracted from Scopus 11/2020). Research Gate. RUA: http://hdl.handle.net/10045/66521.

Labarta, J.A.; Olaya, M.M.; Marcilla, A. What does the NRTL model look like? Determination of boundaries for different fluid phase equilibrium regions. AIChE Journal. 2022, 68(10), e17805 (https://dx.doi.org/10.1002/aic.17805)

Labarta, J.A.; Olaya, M.M.; Marcilla, A. GMcal_TieLinesLL v.2.2. Graphical User Interface (GUI) for the representation of GM surfaces and curves (for binary and ternary systems), including tie-lines, Hessian Matrix analysis, Critical Point Location, Miscibility Boundaries, etc.  Institutional Repository of the University of Alicante (RUA) 2015-2022. (http://hdl.handle.net/10045/51725). (Including a Thermodynamic Review).

Marcilla, A.; Labarta, J.A.; Serrano M.D.; Olaya, M.M. GE Models and Algorithms for Condensed Phase Equilibrium Data Regression in Ternary Systems: Limitations and Proposals. The Open Thermodynamics Journal. 2011, 5, (Suppl 1-M5) 48-62 (http://dx.doi.org/10.2174/1874396X01105010048).

Labarta, J.A.; Olaya, M.M.; Marcilla, A. Boundaries_LL_NRTL Graphical User Interface (GUI) for the characterization of the NRTL model: Binary Spinodal Surfaces (in the τ_i,j-τ_j,i-x_i space), LLE maps and Miscibility Boundaries. Institutional Repository of the University of Alicante (RUA) 2022. (http://hdl.handle.net/10045/121471).

Marcilla, A.; Serrano, M.D.; Labarta. J.A.; Olaya, M.M. Checking Liquid-Liquid Critical Plait Conditions and their Application in Ternary Systems. Industrial & Engineering Chemistry Research. 2012, 51(13), 5098-5102. http://dx.doi.org/10.1021/ie202793r.

Olaya, M.M.; Carbonell-Hermida, P.; Trives, M.; Labarta, J.A.; Marcilla, A. LLE data correlation using NRTL model for different types of binary systems: UCST, LCST and closed miscibility loops. Industrial & Engineering Chemistry Research. 2020, 59(17), 8469-8479. https://doi.org/10.1021/acs.iecr.0c00141.

Labarta, J.A.; Serrano, M.D.; Velasco, R.; Olaya, M.M.; Marcilla, A. Approximate Calculation of Distillation Boundaries for Ternary Azeotropic Systems. Ind. Eng. Chem. Res. 2011, 50 (12), 7462-7466. DOI: http://dx.doi.org/10.1021/ie101873.

Labarta, J.A.; Caballero, J.A.; Marcilla, A. Numerical Determination of Distillation Boundaries for Multicomponent Homogeneous and Heterogeneous Azeotropic Systems. Computer Aided Chemical Engineering. 2010, 28(C), 643-648. DOI: http://dx.doi.org/10.1016/S1570-7946(10)28108-7.

In this link: http://rua.ua.es/dspace/handle/10045/51725, it is possible to acces to a very easy to use Graphical User Interface (GMcal_TieLinesLL v.2.3) based on the topological information contained in the Gibbs energy of mixing function, that has been developed for binary and ternary LLE systems, as a friendly tool to check the coherence of the parameters obtained in a correlation data procedure (the NRTL and UNIQUAC models are included by defect, however any other G^Excess(L)/RT model could be easily implemented).

The analysis of the G^M(L)/RT surface in the whole range of composition, the G^M(L)/RT for the binaries subsystems and the G^M(L)/RT curves in planes containing the liquid-liquid tie lines should be necessary to validate the obtained parameters for the different models for correlating phase equlibrium data. This simple analysis could be used by authors and journals in order to guarantee the adequate prediction of equilibrium. In addition, restrictions on NRTL binary parameters have been used in the correlation procedure to guarantee the adequate prediction of the total or partial miscibility behavior of the binary subsystems.

The NEW VERSION 2.3 of this friendly tool also allows the analysis of the Hessian Matrix determinant (σ), the spinodal curve (σ=0) and the Plait Point location for LLE ternary systems, using additionally the δ and δ* matrix determinants, which have to be also equal to zero and additionally the miscibility boundaries (for α_ij values different from 0.2). The analysis of LLE binary systems at different temperatures is also possible, including the location, if there exits, of the Critical Solution Temperature (UCST, LCST or Closed Misciblity Loops).

To follow updates and comments:   LinkedIn    Research Gate    Facebook

** After using this GUI: GMcal_TieLinesLL, please complete the following quick inquiry to know your opinion about the graphical user interface developed: English version // Spanish version.

Related references:

Marcilla, A.; Labarta, J.A.; Olaya, M.M. Should we trust all the published LLE correlation parameters in phase equilibria? Necessity of their Assessment Prior to Publication. Fluid Phase Equilibria. 2017, 433, 243-252 (http://dx.doi.org/10.1016/j.fluid.2016.11.009). The 4^th most cited article published in Fluid Phase Equilibria in 2017-2020 (extracted from Scopus 11/2020). Research Gate. RUA: http://hdl.handle.net/10045/66521.

Labarta, J.A.; Olaya, M.M.; Marcilla, A. What does the NRTL model look like? Determination of boundaries for different fluid phase equilibrium regions. AIChE Journal. 2022, 68(10), e17805 (https://dx.doi.org/10.1002/aic.17805).

Marcilla, A.; Labarta, J.A.; Serrano M.D.; Olaya, M.M. GE Models and Algorithms for Condensed Phase Equilibrium Data Regression in Ternary Systems: Limitations and Proposals. The Open Thermodynamics Journal. 2011, 5, (Suppl 1-M5) 48-62 (http://dx.doi.org/10.2174/1874396X01105010048).

Marcilla, A.; Serrano, M.D.; Labarta. J.A.; Olaya, M.M. Checking Liquid-Liquid Critical Point Conditions and their Application in Ternary Systems. Industrial & Engineering Chemistry Research. 2012, 51(13), 5098-5102 (http://dx.doi.org/10.1021/ie202793r).

Olaya, M.M.; Carbonell-Hermida, P.; Trives, M.; Labarta, J.A.; Marcilla, A. LLE data correlation using NRTL model for different types of binary systems: UCST, LCST and closed miscibility loops. Industrial & Engineering Chemistry Research. 2020, 59(17), 8469-8479 (https://doi.org/10.1021/acs.iecr.0c00141).

Vicente-Martínez, M.; Labarta, J.A. Análisis topológico del modelo NRTL en sistemas binarios y ternarios para caracterizar la tipología de los sistemas líquido-líquido que predice en función de los valores de los parámetros de interacción binaria. Institutional Repository of the University of Alicante (RUA) 2021. (http://hdl.handle.net/10045/117665).

Labarta, J.A.; Olaya, M.M.; Marcilla, A. Boundaries_LL_NRTL Graphical User Interface (GUI) for the characterization of the NRTL model: Binary Spinodal Surfaces (in the τ_i,j-τ_j,i-x_i space), LLE maps and Miscibility Boundaries. Institutional Repository of the University of Alicante (RUA) 2022. (http://hdl.handle.net/10045/121471).

Labarta, J.A.; Olaya, M.M.; Marcilla, A. GMcal_TieLinesVL: Graphical User Interface (GUI) for the Topological Analysis of Experimental and Calculated G^M Functions for Binary and Ternary (isobaric or isothermal) Vapor-Liquid Equilibrium (VLE) data (including Tie-Lines, Derivatives, Distillation Boundaries, LL Critical Points Location, etc.). Institutional Repository of the University of Alicante (RUA). 2022. Publicly available online at: http://hdl.handle.net/10045/122857.

A. Marcilla | J. A. Labarta | M. M. Olaya
Chemical Engineering Department & Institute of Chemical Process Engineering, University of Alicante, Apdo. 99, Alicante, 03080, Spain.

Supplementary material: GRAPHICAL USER INTERFACE (GUI) FOR THE TOPOLOGICAL ANALYSIS OF CALCULATED GM SURFACES AND CURVES, INCLUDING TIE-LINES, HESSIAN MATRIX, ETC. FOR BINARY AND TERNARY LLE SYSTEMS (GMcal_TieLinesLL v.2.2)  (RUA 2015/22): http://hdl.handle.net/10045/51725.

The 4^th most cited article published in Fluid Phase Equilibria in 2017-2020 (extracted from Scopus 11/2020).

In the following link you can find a Thermodynamic introduction about the topology of the Gibbs Energy of Mixing function, and its relevance in the phase equilibrium calculations:

http://rua.ua.es/dspace/handle/10045/51725