Pub Date : 2025-09-24DOI: 10.1016/j.fluid.2025.114590
Ariel Hernández , Juan Ortega , Mustapha Maarouf , Manuel Chaar
PC-SAFT has been used as a fitted and predictive approaches for modeling the excess molar properties of 81 binary mixtures composed of methyl alkanoate and 1-alkanol at atmospheric pressure and 298.15 K; whose experimental and correlation data were obtained from the literature. Furthermore, we have compared the VLE obtained with PC-SAFT for 9 binary mixtures of methyl alkanoate (ethanoate to butanoate) + 1-alkanol (ethanol to 1-butanol) with experimental data published in the literature at 101.32 kPa. The binary interaction parameter, known as , was adjusted to correct for London dispersion forces, and excess molar volume and excess molar enthalpy data were used for the fitting. From the calculations, we have obtained a good qualitative agreement between PC-SAFT and literature data for most binary mixtures, which present predominant repulsive forces and an endothermic effect in the mixing process. Finally, it was found that PC-SAFT correctly predicts (without using adjustable parameters) the VLE of the 9 binary mixtures analyzed. The best agreement in the representation of the experimental data of excess molar volume was obtained for the group of mixtures of methyl ethanoate + 1-alkanol (18.11%), while in the case of excess molar enthalpy, the best results were obtained for methyl pentadecanoate + 1-alkanol (7.04%). On the other hand, PC-SAFT was able to correctly represent the experimental data of liquid–vapor equilibrium for 9 binary mixtures from a predictive and quantitative perspective and deviations in boiling point and mole fraction in vapor phase of 0.31% and 2.29% were obtained, respectively.
{"title":"Using the PC-SAFT model to represent the mixing properties of 81 binaries formed by a methyl alkanoate with an alkan-1-ol","authors":"Ariel Hernández , Juan Ortega , Mustapha Maarouf , Manuel Chaar","doi":"10.1016/j.fluid.2025.114590","DOIUrl":"10.1016/j.fluid.2025.114590","url":null,"abstract":"<div><div>PC-SAFT has been used as a fitted and predictive approaches for modeling the excess molar properties of 81 binary mixtures composed of methyl alkanoate and 1-alkanol at atmospheric pressure and 298.15 K; whose experimental and correlation data were obtained from the literature. Furthermore, we have compared the VLE obtained with PC-SAFT for 9 binary mixtures of methyl alkanoate (ethanoate to butanoate) + 1-alkanol (ethanol to 1-butanol) with experimental data published in the literature at 101.32 kPa. The binary interaction parameter, known as <span><math><msub><mrow><mi>k</mi></mrow><mrow><mi>i</mi><mi>j</mi></mrow></msub></math></span>, was adjusted to correct for London dispersion forces, and excess molar volume and excess molar enthalpy data were used for the fitting. From the calculations, we have obtained a good qualitative agreement between PC-SAFT and literature data for most binary mixtures, which present predominant repulsive forces and an endothermic effect in the mixing process. Finally, it was found that PC-SAFT correctly predicts (without using adjustable parameters) the VLE of the 9 binary mixtures analyzed. The best agreement in the representation of the experimental data of excess molar volume was obtained for the group of mixtures of methyl ethanoate + 1-alkanol (18.11%), while in the case of excess molar enthalpy, the best results were obtained for methyl pentadecanoate + 1-alkanol (7.04%). On the other hand, PC-SAFT was able to correctly represent the experimental data of liquid–vapor equilibrium for 9 binary mixtures from a predictive and quantitative perspective and deviations in boiling point and mole fraction in vapor phase of 0.31% and 2.29% were obtained, respectively.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"601 ","pages":"Article 114590"},"PeriodicalIF":2.7,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145155774","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-15DOI: 10.1016/j.fluid.2025.114592
Shaohua Lv , Bo Wang , Yun Hao , Jialun Liu , Yali Su
This study experimentally determined the isobaric specific heat capacity of ethyl octanoate using flow calorimetry across 313.15 to 453.15 K at pressures up to 10 MPa, with measurement uncertainty of 0.095. Deviations from literature data were within 0.43 % at 0.1 MPa and 0.42 % under elevated pressures. By integrating literature data, a computational equation for ethyl octanoate was regressed, exhibiting deviations ≤0.42 %. Utilizing the differential relationship , a predictive model for isobaric specific heat capacity was established. This model extends the prediction of heat capacity to 100 MPa, achieving an average absolute deviation (AAD) of 0.28 % within the experimental range, demonstrating satisfactory accuracy.
{"title":"Study on isobaric specific heat capacity of ethyl octanoate under high pressure across 313-453 K","authors":"Shaohua Lv , Bo Wang , Yun Hao , Jialun Liu , Yali Su","doi":"10.1016/j.fluid.2025.114592","DOIUrl":"10.1016/j.fluid.2025.114592","url":null,"abstract":"<div><div>This study experimentally determined the isobaric specific heat capacity of ethyl octanoate using flow calorimetry across 313.15 to 453.15 K at pressures up to 10 MPa, with measurement uncertainty of 0.095. Deviations from literature data were within 0.43 % at 0.1 MPa and 0.42 % under elevated pressures. By integrating literature data, a computational equation for ethyl octanoate was regressed, exhibiting deviations ≤0.42 %. Utilizing the differential relationship <span><math><mrow><msub><mrow><mo>(</mo><mrow><mrow><mi>∂</mi><msub><mi>c</mi><mi>p</mi></msub></mrow><mo>/</mo><mrow><mi>∂</mi><mi>p</mi></mrow></mrow><mo>)</mo></mrow><mi>T</mi></msub><mo>=</mo><mo>−</mo><mi>T</mi><msub><mrow><mo>(</mo><mrow><mrow><msup><mrow><mi>∂</mi></mrow><mn>2</mn></msup><mi>v</mi></mrow><mo>/</mo><mrow><mi>∂</mi><msup><mrow><mi>T</mi></mrow><mn>2</mn></msup></mrow></mrow><mo>)</mo></mrow><mi>p</mi></msub></mrow></math></span>, a predictive model for isobaric specific heat capacity was established. This model extends the prediction of heat capacity to 100 MPa, achieving an average absolute deviation (AAD) of 0.28 % within the experimental range, demonstrating satisfactory accuracy.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"601 ","pages":"Article 114592"},"PeriodicalIF":2.7,"publicationDate":"2025-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-14DOI: 10.1016/j.fluid.2025.114591
Paula V.de A. Pontes, Ericsem Pereira, Guilherme J. Maximo, Eduardo A.C. Batista
Choline chloride has been extensively used in literature for the formulation of eutectic solvents for the extraction of biocompounds from different raw materials. The formulation of eutectic solvents should be performed through the evaluation of the Solid-Liquid Equilibrium (SLE) of the mixture and identification of its eutectic point. In this case, the eutectic point calculation through thermodynamic modeling could improve the design of solvents for extraction processes. The UNIFAC model is a group-contribution based model that could be used in this case. In this context, this study was aimed at the adjustment of new original UNIFAC interaction parameters pairs (amnand anm) for choline chloride [Ch]Cl (treated in this work as a pseudo-group) and CH3 (CH, CH2 and CH3 subgroups), OH and COOH groups. A databank composed of experimental SLE data from different works in literature were built. The dataset included complete SLE data of 23 mixtures of [Ch]Cl with polyols, polycarboxylic acids, long-chain carboxylic acids (fatty acids) and long chain alcohols (fatty alcohols). Parameters adjusted showed a significant accuracy in describing the SLE profile of the mixtures, especially in the [Ch]Cl rich region, with mean relative deviation varying from 1.32 to 10.79 %. The new UNIFAC enthalpic parameters were also able to predict eutectic temperatures and eutectic compositions of [Ch]Cl mixtures with reasonable accuracy, which is quite interesting considering the design of new eutectic solvents. This study collaborates with the green chemistry literature taking into account the faster screening of new DES and ES composed of choline chloride.
{"title":"UNIFAC parametrization for solid-liquid equilibrium of systems containing choline chloride","authors":"Paula V.de A. Pontes, Ericsem Pereira, Guilherme J. Maximo, Eduardo A.C. Batista","doi":"10.1016/j.fluid.2025.114591","DOIUrl":"10.1016/j.fluid.2025.114591","url":null,"abstract":"<div><div>Choline chloride has been extensively used in literature for the formulation of eutectic solvents for the extraction of biocompounds from different raw materials. The formulation of eutectic solvents should be performed through the evaluation of the Solid-Liquid Equilibrium (SLE) of the mixture and identification of its eutectic point. In this case, the eutectic point calculation through thermodynamic modeling could improve the design of solvents for extraction processes. The UNIFAC model is a group-contribution based model that could be used in this case. In this context, this study was aimed at the adjustment of new original UNIFAC interaction parameters pairs (a<sub>mn</sub>and a<sub>nm</sub>) for choline chloride [Ch]Cl (treated in this work as a pseudo-group) and CH<sub>3</sub> (CH, CH<sub>2</sub> and CH<sub>3</sub> subgroups), OH and COOH groups. A databank composed of experimental SLE data from different works in literature were built. The dataset included complete SLE data of 23 mixtures of [Ch]Cl with polyols, polycarboxylic acids, long-chain carboxylic acids (fatty acids) and long chain alcohols (fatty alcohols). Parameters adjusted showed a significant accuracy in describing the SLE profile of the mixtures, especially in the [Ch]Cl rich region, with mean relative deviation varying from 1.32 to 10.79 %. The new UNIFAC enthalpic parameters were also able to predict eutectic temperatures and eutectic compositions of [Ch]Cl mixtures with reasonable accuracy, which is quite interesting considering the design of new eutectic solvents. This study collaborates with the green chemistry literature taking into account the faster screening of new DES and ES composed of choline chloride.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"601 ","pages":"Article 114591"},"PeriodicalIF":2.7,"publicationDate":"2025-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-12DOI: 10.1016/j.fluid.2025.114589
You Shu , Yang Lei , Yanfen Huang , Xinyan Liu , Yuqiu Chen
The vast diversity of ionic liquids (ILs) necessitates the development of accurate predictive models to support their industrial applications. This study combines machine learning (ML) algorithms with group contribution (GC) methods to model the density and viscosity of IL-IL-H2O ternary mixtures. Three ML algorithms (i.e., ANN, XGBoost, and LightGBM) were employed to develop robust predictive models, which were trained on a large experimental dataset. The effect of dataset partitioning on the prediction results is analyzed, and the generalizability of the models is validated through 5-fold cross-validation. The ANN-GC model performs well in predicting both density and viscosity properties, with a mean absolute error (MAE) of 1.7909 and a correlation coefficient (R2) of 0.9933 for density, and an MAE of 0.0329 and an R² of 0.9813 for viscosity. Furthermore, hyperparameters for the ANN model were optimized using Bayesian optimization, while XGBoost and LightGBM were optimized via grid search. After optimization, the prediction accuracies of all three models improved, with ANN-GC maintaining the highest prediction accuracy. Specifically, the optimized ANN-GC model achieves an MAE of 1.5834 and an R2 of 0.9963 for density prediction, and an MAE of 0.0279 and an R2 of 0.9924 for viscosity prediction. Further insights were obtained through SHAP (SHapley Additive exPlanations) analysis, which clarified the contributions of different features to the model predictions. Additionally, the validity of the density and viscosity prediction models was confirmed by calculating the fluid flow unit process case.
{"title":"Modeling study on the density and viscosity of ionic liquid-ionic liquid-water ternary mixtures","authors":"You Shu , Yang Lei , Yanfen Huang , Xinyan Liu , Yuqiu Chen","doi":"10.1016/j.fluid.2025.114589","DOIUrl":"10.1016/j.fluid.2025.114589","url":null,"abstract":"<div><div>The vast diversity of ionic liquids (ILs) necessitates the development of accurate predictive models to support their industrial applications. This study combines machine learning (ML) algorithms with group contribution (GC) methods to model the density and viscosity of IL-IL-H<sub>2</sub>O ternary mixtures. Three ML algorithms (i.e., ANN, XGBoost, and LightGBM) were employed to develop robust predictive models, which were trained on a large experimental dataset. The effect of dataset partitioning on the prediction results is analyzed, and the generalizability of the models is validated through 5-fold cross-validation. The ANN-GC model performs well in predicting both density and viscosity properties, with a mean absolute error (MAE) of 1.7909 and a correlation coefficient (<em>R</em><sup>2</sup>) of 0.9933 for density, and an MAE of 0.0329 and an <em>R</em>² of 0.9813 for viscosity. Furthermore, hyperparameters for the ANN model were optimized using Bayesian optimization, while XGBoost and LightGBM were optimized via grid search. After optimization, the prediction accuracies of all three models improved, with ANN-GC maintaining the highest prediction accuracy. Specifically, the optimized ANN-GC model achieves an MAE of 1.5834 and an <em>R</em><sup>2</sup> of 0.9963 for density prediction, and an MAE of 0.0279 and an <em>R</em><sup>2</sup> of 0.9924 for viscosity prediction. Further insights were obtained through SHAP (SHapley Additive exPlanations) analysis, which clarified the contributions of different features to the model predictions. Additionally, the validity of the density and viscosity prediction models was confirmed by calculating the fluid flow unit process case.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"601 ","pages":"Article 114589"},"PeriodicalIF":2.7,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-10DOI: 10.1016/j.fluid.2025.114584
Johannes S. Løken, Vegard G. Jervell, Morten Hammer, Bjørn Hafskjold, Thuat T. Trinh, Øivind Wilhelmsen
The Lennard-Jones/spline (LJ/s) potential is truncated and splined such that the potential and its first derivative continuously approach zero at , making it short-ranged. In this work, we present a systematic study of the thermal conductivity, shear viscosity, and self-diffusion coefficient of the LJ/s fluid. Four theories are evaluated by comparing to results from equilibrium and non-equilibrium molecular dynamics simulations for temperatures in the range and densities in the range . After regressing two parameters for each transport property in extended corresponding state theory with argon as reference fluid, the Average Absolute Relative Deviations (AARDs) with respect to the simulation data are 4.7% and 2.8% for the viscosity and thermal conductivity respectively. Using 4-6 regression parameters, residual entropy scaling yields AARDs of 5.7%, 2.6%, and 2.5% for the viscosity, thermal conductivity and self-diffusion coefficient respectively. A new method called corresponding entropic states theory is presented, which combines the concept of entropy scaling with the extended corresponding states formalism. Without any fitting parameters and with argon as reference fluid, the viscosity and thermal conductivity from the method have AARDs of 5.2% and 2.6%. For residual entropy scaling, extended corresponding states, and corresponding entropic states, the largest deviations are for the viscosity near the critical point, which can be explained by inaccuracies in the equation of state. Revised Enskog Theory, which is fully predictive, gives AARDs below 10% for , up to . More work is needed to increase the accuracy of Revised Enskog theory at lower temperatures and higher densities.
{"title":"Viscosity, thermal conductivity and self-diffusion coefficient of the Lennard-Jones spline fluid: Evaluation of theories for a short-ranged potential","authors":"Johannes S. Løken, Vegard G. Jervell, Morten Hammer, Bjørn Hafskjold, Thuat T. Trinh, Øivind Wilhelmsen","doi":"10.1016/j.fluid.2025.114584","DOIUrl":"10.1016/j.fluid.2025.114584","url":null,"abstract":"<div><div>The Lennard-Jones/spline (LJ/s) potential is truncated and splined such that the potential and its first derivative continuously approach zero at <span><math><mrow><mo>≈</mo><mn>1</mn><mo>.</mo><mn>74</mn><mi>σ</mi></mrow></math></span>, making it short-ranged. In this work, we present a systematic study of the thermal conductivity, shear viscosity, and self-diffusion coefficient of the LJ/s fluid. Four theories are evaluated by comparing to results from equilibrium and non-equilibrium molecular dynamics simulations for temperatures in the range <span><math><mrow><mn>0</mn><mo>.</mo><mn>7</mn><mo>≤</mo><msup><mrow><mi>T</mi></mrow><mrow><mo>∗</mo></mrow></msup><mo>≤</mo><mn>10</mn></mrow></math></span> and densities in the range <span><math><mrow><mn>0</mn><mo>.</mo><mn>1</mn><mo>≤</mo><msup><mrow><mi>ρ</mi></mrow><mrow><mo>∗</mo></mrow></msup><mo>≤</mo><mn>0</mn><mo>.</mo><mn>8</mn></mrow></math></span>. After regressing two parameters for each transport property in extended corresponding state theory with argon as reference fluid, the Average Absolute Relative Deviations (AARDs) with respect to the simulation data are 4.7% and 2.8% for the viscosity and thermal conductivity respectively. Using 4-6 regression parameters, residual entropy scaling yields AARDs of 5.7%, 2.6%, and 2.5% for the viscosity, thermal conductivity and self-diffusion coefficient respectively. A new method called corresponding entropic states theory is presented, which combines the concept of entropy scaling with the extended corresponding states formalism. Without any fitting parameters and with argon as reference fluid, the viscosity and thermal conductivity from the method have AARDs of 5.2% and 2.6%. For residual entropy scaling, extended corresponding states, and corresponding entropic states, the largest deviations are for the viscosity near the critical point, which can be explained by inaccuracies in the equation of state. Revised Enskog Theory, which is fully predictive, gives AARDs below 10% for <span><math><mrow><msup><mrow><mi>T</mi></mrow><mrow><mo>∗</mo></mrow></msup><mo>≥</mo><mn>3</mn></mrow></math></span>, up to <span><math><mrow><msup><mrow><mi>ρ</mi></mrow><mrow><mo>∗</mo></mrow></msup><mo>=</mo><mn>0</mn><mo>.</mo><mn>4</mn></mrow></math></span>. More work is needed to increase the accuracy of Revised Enskog theory at lower temperatures and higher densities.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"601 ","pages":"Article 114584"},"PeriodicalIF":2.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-08DOI: 10.1016/j.fluid.2025.114588
Veronica Ianno’, Philippe Espeau
PEGs are often used as plasticizers in filaments formulated for FDM 3D printing. Here, we present the behavior of paracetamol in solid dispersions based on PEG 4000 and 6000 via the determination of binary phase diagrams. It is shown, as was already the case with PEG 1500, that paracetamol is present, almost obviously, in its polymorphic Form II during the second heating. This metastable form remains stable in the presence of PEG, and its solubility appears to be independent of the molar mass of PEG, as is the case for Form I. This work aims to mimic the behavior of paracetamol in the presence of PEG during an extrusion process by HME then coupled with 3D printing by FDM.
{"title":"Influence of the molar mass of PEGs on the miscibility of paracetamol: Study of binary phase diagrams. Application for FDM 3D printing","authors":"Veronica Ianno’, Philippe Espeau","doi":"10.1016/j.fluid.2025.114588","DOIUrl":"10.1016/j.fluid.2025.114588","url":null,"abstract":"<div><div>PEGs are often used as plasticizers in filaments formulated for FDM 3D printing. Here, we present the behavior of paracetamol in solid dispersions based on PEG 4000 and 6000 via the determination of binary phase diagrams. It is shown, as was already the case with PEG 1500, that paracetamol is present, almost obviously, in its polymorphic Form II during the second heating. This metastable form remains stable in the presence of PEG, and its solubility appears to be independent of the molar mass of PEG, as is the case for Form I. This work aims to mimic the behavior of paracetamol in the presence of PEG during an extrusion process by HME then coupled with 3D printing by FDM.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"601 ","pages":"Article 114588"},"PeriodicalIF":2.7,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046870","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-06DOI: 10.1016/j.fluid.2025.114587
Corine Mouton, Cara E. Schwarz
This work presents measured high-pressure phase transition data for mixtures containing 1‑nonanol + n‑hexadecane (solute + solute) with supercritical CO2 (solvent) and thermodynamic modelling of the measured data. The data was measured using the static synthetic visual phase method for four (1‑nonanol + n‑hexadecane) mixtures with CO2 as well as 1‑nonanol + CO2 at temperatures between 308.2 K and 358.2 K and solute mass fractions ranging from 0.008 to 0.65 g·g-1. Solute-solute interactions strongly influence the observed phase behaviour, resulting in complex phenomena such as cosolvency effects and temperature inversions. The measured data revealed distinct cosolvency effects and exhibited temperature inversions at 308.2 K and 318.2 K for solvent-free alcohol compositions of 0 g·g-1, 0.8 g·g-1 and 1 g·g-1.
A modified version of the Soave-Redlich-Kwong (SRK) equation of state implemented in Aspen Plus®, RK‑Aspen, was used to correlate experimental pure component and binary data, and to predict the high-pressure phase transition data for the ternary system. Incorporating polar parameters, solute-solvent binary interaction parameters (BIPs), and solute-solute BIPs in the RK-Aspen model provided reasonably accurate descriptions of the measured data in the dew- and bubble point composition ranges at moderate temperatures. However, future work should focus on improving the model's performance at temperatures near the solvent's critical temperature and compositions near the mixture critical region. Additionally, an in-house thermodynamic model can be developed to better describe complex phase behaviour.
{"title":"High-pressure phase behaviour and modelling of the 1‑nonanol + n‑hexadecane + supercritical CO2 system","authors":"Corine Mouton, Cara E. Schwarz","doi":"10.1016/j.fluid.2025.114587","DOIUrl":"10.1016/j.fluid.2025.114587","url":null,"abstract":"<div><div>This work presents measured high-pressure phase transition data for mixtures containing 1‑nonanol + <em>n</em>‑hexadecane (solute + solute) with supercritical CO<sub>2</sub> (solvent) and thermodynamic modelling of the measured data. The data was measured using the static synthetic visual phase method for four (1‑nonanol + <em>n</em>‑hexadecane) mixtures with CO<sub>2</sub> as well as 1‑nonanol + CO<sub>2</sub> at temperatures between 308.2 K and 358.2 K and solute mass fractions ranging from 0.008 to 0.65 g·g<sup>-1</sup>. Solute-solute interactions strongly influence the observed phase behaviour, resulting in complex phenomena such as cosolvency effects and temperature inversions. The measured data revealed distinct cosolvency effects and exhibited temperature inversions at 308.2 K and 318.2 K for solvent-free alcohol compositions of 0 g·g<sup>-1</sup>, 0.8 g·g<sup>-1</sup> and 1 g·g<sup>-1</sup>.</div><div>A modified version of the Soave-Redlich-Kwong (SRK) equation of state implemented in Aspen Plus®, RK‑Aspen, was used to correlate experimental pure component and binary data, and to predict the high-pressure phase transition data for the ternary system. Incorporating polar parameters, solute-solvent binary interaction parameters (BIPs), and solute-solute BIPs in the RK-Aspen model provided reasonably accurate descriptions of the measured data in the dew- and bubble point composition ranges at moderate temperatures. However, future work should focus on improving the model's performance at temperatures near the solvent's critical temperature and compositions near the mixture critical region. Additionally, an in-house thermodynamic model can be developed to better describe complex phase behaviour.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"601 ","pages":"Article 114587"},"PeriodicalIF":2.7,"publicationDate":"2025-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145061124","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-04DOI: 10.1016/j.fluid.2025.114574
Mami Inagaki , Kazuki Tsubaki , Sota Kawakami , Chang Yi Kong , Toshitaka Funazukuri
Piperine is one of key components of peppers, and supercritical fluid extraction has been applied to isolate such heat-sensitive natural substances. The diffusion coefficient (D12) of piperine in supercritical (sc) carbon dioxide is essential for the process design, but no data are available in the literature. In the present study the infinite dilution binary diffusion coefficient (D12) of piperine in scCO2 was measured at temperatures from 308.2 K to 343.2 K and at pressures from 12 MPa to 30 MPa by the chromatographic impulse response method, and those in methanol, ethanol, 1-propanol and 1-butanol were measured at atmospheric pressure and at temperatures from 303.2 K to 343.2 K by the Taylor dispersion method. The hydrodynamic equation, D12/T =αηβ, T is the temperature and η is the CO2 and alcohol viscosity, was found to well represent all of the D12 values measured in both scCO2 and atmospheric liquid alcohols, with a single set of two constants α = 3.655 × 10–15 kg-βmβ+2sβ-1K-1 and β = -0.9145 with the average absolute relative deviation of 4.41 % and maximum deviation of 14.0 % with 72 measurement conditions. Partial molar volumes(PMV) of piperine determined from the retention factors were negative and decreased substantially closer to the CO2 critical point, as observed for various solutes in scCO2 reported in the literature. To evaluate the accuracy of the determined PMV values new reliable models and reliable solubility data are needed to describe the PMV values, especially near the critical region.
{"title":"Measurements of infinite dilution binary diffusion coefficient and partial molar volume of piperine in supercritical carbon dioxide","authors":"Mami Inagaki , Kazuki Tsubaki , Sota Kawakami , Chang Yi Kong , Toshitaka Funazukuri","doi":"10.1016/j.fluid.2025.114574","DOIUrl":"10.1016/j.fluid.2025.114574","url":null,"abstract":"<div><div>Piperine is one of key components of peppers, and supercritical fluid extraction has been applied to isolate such heat-sensitive natural substances. The diffusion coefficient (<em>D</em><sub>12</sub>) of piperine in supercritical (sc) carbon dioxide is essential for the process design, but no data are available in the literature. In the present study the infinite dilution binary diffusion coefficient (<em>D</em><sub>12</sub>) of piperine in scCO<sub>2</sub> was measured at temperatures from 308.2 K to 343.2 K and at pressures from 12 MPa to 30 MPa by the chromatographic impulse response method, and those in methanol, ethanol, 1-propanol and 1-butanol were measured at atmospheric pressure and at temperatures from 303.2 K to 343.2 K by the Taylor dispersion method. The hydrodynamic equation, <em>D</em><sub>12</sub>/<em>T</em> =α<em>η</em><sup>β</sup>, <em>T</em> is the temperature and <em>η</em> is the CO<sub>2</sub> and alcohol viscosity, was found to well represent all of the <em>D</em><sub>12</sub> values measured in both scCO<sub>2</sub> and atmospheric liquid alcohols, with a single set of two constants <em>α</em> = 3.655 × 10<sup>–15</sup> kg<sup>-β</sup>m<sup>β+2</sup>s<sup>β-1</sup>K<sup>-1</sup> and <em>β</em> = -0.9145 with the average absolute relative deviation of 4.41 % and maximum deviation of 14.0 % with 72 measurement conditions. Partial molar volumes(PMV) of piperine determined from the retention factors were negative and decreased substantially closer to the CO<sub>2</sub> critical point, as observed for various solutes in scCO<sub>2</sub> reported in the literature. To evaluate the accuracy of the determined PMV values new reliable models and reliable solubility data are needed to describe the PMV values, especially near the critical region.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"601 ","pages":"Article 114574"},"PeriodicalIF":2.7,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145266716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-04DOI: 10.1016/j.fluid.2025.114577
Masoume Najafi, Zohre Mokhtari, Hosseinali Zarei
pρT experimental data of pure 1-methoxypropan-2-ol and 2-(2-hexoxyethoxy) ethanol were measured at twelve different temperatures ranging from (293.15 - 473.15) K and at pressures up to 40 MPa. The experimental measurements were conducted using a high-pressure vibrating tube densimeter, with a combined expanded density uncertainty of 1. Furthermore, the densities and speed of sounds of these solvents were measured at seven isotherms, T = (293.15 - 343.15) K, under ambient pressure (81.5 kPa), using an Anton Paar DSA 5000. The obtained pρT data obtained were effectively correlated using a modified Tait equation. This correlation allowed for derivation of thermal expansion coefficient () and isothermal compressibility () across the same temperature and pressure ranges. In addition, the PC-SAFT equation of state (EOS) was employed to further correlate the liquid pρT experimental data. Using the parameters of the PC-SAFT EOS, several thermodynamic properties were estimated, including the thermal expansion coefficient (), isothermal compressibility (), isobaric heat capacity (), and speed of sound ().
{"title":"pρT experimental data of 1-methoxypropan-2-ol and 2-(2-hexoxyethoxy) ethanol at temperatures from (293.15 to 473.15) K and pressures up to 40 MPa: modified Tait and PC-SAFT modeling","authors":"Masoume Najafi, Zohre Mokhtari, Hosseinali Zarei","doi":"10.1016/j.fluid.2025.114577","DOIUrl":"10.1016/j.fluid.2025.114577","url":null,"abstract":"<div><div><em>pρT</em> experimental data of pure 1-methoxypropan-2-ol and 2-(2-hexoxyethoxy) ethanol were measured at twelve different temperatures ranging from (293.15 - 473.15) K and at pressures up to 40 MPa. The experimental measurements were conducted using a high-pressure vibrating tube densimeter, with a combined expanded density uncertainty of 1<span><math><mrow><mtext>kg</mtext><mo>·</mo><msup><mrow><mi>m</mi></mrow><mrow><mo>−</mo><mn>3</mn></mrow></msup></mrow></math></span>. Furthermore, the densities and speed of sounds of these solvents were measured at seven isotherms, <em>T</em> = (293.15 - 343.15) K, under ambient pressure (81.5 kPa), using an Anton Paar DSA 5000. The obtained <em>pρT</em> data obtained were effectively correlated using a modified Tait equation. This correlation allowed for derivation of thermal expansion coefficient (<span><math><msub><mi>α</mi><mi>p</mi></msub></math></span>) and isothermal compressibility (<span><math><msub><mi>κ</mi><mi>T</mi></msub></math></span>) across the same temperature and pressure ranges. In addition, the PC-SAFT equation of state (EOS) was employed to further correlate the liquid <em>pρT</em> experimental data. Using the parameters of the PC-SAFT EOS, several thermodynamic properties were estimated, including the thermal expansion coefficient (<span><math><msub><mi>α</mi><mi>p</mi></msub></math></span>), isothermal compressibility (<span><math><msub><mi>κ</mi><mi>T</mi></msub></math></span>), isobaric heat capacity (<span><math><msub><mi>C</mi><mi>p</mi></msub></math></span>), and speed of sound (<span><math><mi>u</mi></math></span>).</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"601 ","pages":"Article 114577"},"PeriodicalIF":2.7,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-29DOI: 10.1016/j.fluid.2025.114576
Kang Qing , Erqi Wang , Qiang Song , Zhen Yang , Yuanyuan Duan
The vapor pressure equation is an effective tool for describing the pressure-temperature relationship along the liquid-vapor coexistence curve. However, most existing equations are merely used to correlate experimental data, but lack reliability when extrapolating beyond the experimental temperature range. Based on the thermodynamic characteristics of vapor pressure, this study summarizes the mathematical constraints of vapor pressure equation, and proposes a new, accurate and reliable vapor pressure equation with four fitting parameters for the correlation and extrapolation of experimental data. The new equation is compared with the Park equation and Wagner equation in terms of correlation and extrapolation performance using experimental data of 62 fluids from the triple point to the critical point. Results show that the new equation matches or slightly outperforms the Park equation and Wagner equation in correlation accuracy, while it has more regular fitting parameters. In terms of extrapolation, the new equation significantly outperforms the Park equation and Wagner equation without parameter constraints, especially towards low-temperature and low-pressure region. And the new equation presents stable extrapolation across different data ranges, achieving a balance between correlation accuracy and extrapolation ability through rigorously validated function forms and reasonably set fitting parameters.
{"title":"A new vapor pressure equation with accurate extrapolation capabilities","authors":"Kang Qing , Erqi Wang , Qiang Song , Zhen Yang , Yuanyuan Duan","doi":"10.1016/j.fluid.2025.114576","DOIUrl":"10.1016/j.fluid.2025.114576","url":null,"abstract":"<div><div>The vapor pressure equation is an effective tool for describing the pressure-temperature relationship along the liquid-vapor coexistence curve. However, most existing equations are merely used to correlate experimental data, but lack reliability when extrapolating beyond the experimental temperature range. Based on the thermodynamic characteristics of vapor pressure, this study summarizes the mathematical constraints of vapor pressure equation, and proposes a new, accurate and reliable vapor pressure equation with four fitting parameters for the correlation and extrapolation of experimental data. The new equation is compared with the Park equation and Wagner equation in terms of correlation and extrapolation performance using experimental data of 62 fluids from the triple point to the critical point. Results show that the new equation matches or slightly outperforms the Park equation and Wagner equation in correlation accuracy, while it has more regular fitting parameters. In terms of extrapolation, the new equation significantly outperforms the Park equation and Wagner equation without parameter constraints, especially towards low-temperature and low-pressure region. And the new equation presents stable extrapolation across different data ranges, achieving a balance between correlation accuracy and extrapolation ability through rigorously validated function forms and reasonably set fitting parameters.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"601 ","pages":"Article 114576"},"PeriodicalIF":2.7,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997814","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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