Pub Date : 2025-11-19DOI: 10.1016/j.fluid.2025.114632
Cleiton S. Beraldo , Xiaodong Liang , Georgios M. Kontogeorgis , Luis A. Follegatti-Romero
We evaluate the performance of two electrolyte variants of the Statistical Associating Fluid Theory for Variable Range interactions (SAFT-VR) in the generic Mie form, the SAFT-VRE Mie and eSAFT-VR Mie equations of state, in predicting liquid-phase densities and the speed of sound for imidazolium-based ionic liquids (ILs) and their mixtures with water, methanol, and ethanol. A strictly predictive modeling strategy was employed: only pure-component IL densities were used to derive ion-specific molecular parameters (segment length, size, and energy) for imidazolium-based cations and anions, while solvent parameters were taken from the literature. Ion-solvent and ion-ion pair interactions were calculated via a simplified Hudson-McCoubrey combining rule, assuming equal ionization potentials and avoiding any binary parameter fitting. Six formulations of the relative static permittivity (constant, temperature‐dependent, linear in composition, and a volumetric‐composition model) were evaluated within both the SAFT-VRE Mie and eSAFT-VR Mie frameworks. We introduce a novel Born size interpretation that explicitly accounts for hydrogen‐bonding in IL ions, yielding improved agreement with experimental data. Furthermore, we identify quantitative correlations between these Born size and the underlying SAFT parameters, enabling predictive parametrization of related IL systems. The electrolyte models enhance performance over the SAFT-VR Mie, particularly in mixed‐solvent regions, though further refinement is needed near the pure‐IL limit. All calculations were conducted using the open‐source Clapeyron.jl toolkit, ensuring full reproducibility and extensibility.
{"title":"Modeling the thermodynamic properties of imidazolium ionic liquids in water, methanol, and ethanol using SAFT-VRE Mie and eSAFT-VR Mie equations of state","authors":"Cleiton S. Beraldo , Xiaodong Liang , Georgios M. Kontogeorgis , Luis A. Follegatti-Romero","doi":"10.1016/j.fluid.2025.114632","DOIUrl":"10.1016/j.fluid.2025.114632","url":null,"abstract":"<div><div>We evaluate the performance of two electrolyte variants of the Statistical Associating Fluid Theory for Variable Range interactions (SAFT-VR) in the generic Mie form, the SAFT-VRE Mie and eSAFT-VR Mie equations of state, in predicting liquid-phase densities and the speed of sound for imidazolium-based ionic liquids (ILs) and their mixtures with water, methanol, and ethanol. A strictly predictive modeling strategy was employed: only pure-component IL densities were used to derive ion-specific molecular parameters (segment length, size, and energy) for imidazolium-based cations and anions, while solvent parameters were taken from the literature. Ion-solvent and ion-ion pair interactions were calculated via a simplified Hudson-McCoubrey combining rule, assuming equal ionization potentials and avoiding any binary parameter fitting. Six formulations of the relative static permittivity (constant, temperature‐dependent, linear in composition, and a volumetric‐composition model) were evaluated within both the SAFT-VRE Mie and eSAFT-VR Mie frameworks. We introduce a novel Born size interpretation that explicitly accounts for hydrogen‐bonding in IL ions, yielding improved agreement with experimental data. Furthermore, we identify quantitative correlations between these Born size and the underlying SAFT parameters, enabling predictive parametrization of related IL systems. The electrolyte models enhance performance over the SAFT-VR Mie, particularly in mixed‐solvent regions, though further refinement is needed near the pure‐IL limit. All calculations were conducted using the open‐source <em>Clapeyron.jl</em> toolkit, ensuring full reproducibility and extensibility.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"603 ","pages":"Article 114632"},"PeriodicalIF":2.7,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616575","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 : 2025-11-17DOI: 10.1016/j.fluid.2025.114630
M. G. De Angelis , E. Ricci , M. Minelli , E.A. Macedo
{"title":"Preface to the proceedings of the 33rd European symposium on applied thermodynamics (50th anniversary of ESAT) special issue","authors":"M. G. De Angelis , E. Ricci , M. Minelli , E.A. Macedo","doi":"10.1016/j.fluid.2025.114630","DOIUrl":"10.1016/j.fluid.2025.114630","url":null,"abstract":"","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"603 ","pages":"Article 114630"},"PeriodicalIF":2.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146022886","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 : 2025-11-13DOI: 10.1016/j.fluid.2025.114629
Mars Z. Faizullin, Eugene D. Nikitin
The two-phase (liquid + vapor) heat capacities of glymes CH3(OCH2CH2)nOCH3 with n from 1 to 4 (monoglyme, diglyme, triglyme and tetraglyme), as well as ethylene glycol, 2-propanol, n-octane, and benzoic acid have been measured by a differential scanning calorimeter DSC 204 F1 Phoenix (Netzsch, Germany) at atmospheric pressure in the temperature range from 298.2 K to approximately the normal boiling points of the compounds under study. The last four compounds have served as testing ones. The saturation heat capacity and isobaric heat capacity have been calculated. The experiments with testing compounds have shown that the uncertainty of the measurements is less than 0.03. The deviations of the literature data on the isobaric heat capacity of the glymes from the values measured in this work do not in general exceed the uncertainty of the experiments. The temperature dependences of the heat capacity of glymes have been approximated by third-order polynomials. The dependence of the molar heat capacity of glymes on the number of repeating units in a molecule n is linear.
用差示扫描量热计DSC 204 F1 Phoenix （Netzsch, Germany）测量了n为1 ~ 4（单lyme，二lyme，三lyme和四lyme）的glymes CH3(OCH2CH2)nOCH3以及乙二醇，2-丙醇，正辛烷和苯甲酸的两相（液+气）热容，温度范围从298.2 K到所研究化合物的正常沸点。后四种化合物被用作测试物。计算了饱和热容和等压热容。实验结果表明，测量结果的不确定度小于0.03。文献中关于糖份等压热容的数据与本工作测量值的偏差一般不超过实验的不确定度。glymes热容量的温度依赖性已用三阶多项式近似。分子的摩尔热容与分子中重复单位的数目呈线性关系。
{"title":"Heat capacity of glymes from monoglyme to tetraglyme","authors":"Mars Z. Faizullin, Eugene D. Nikitin","doi":"10.1016/j.fluid.2025.114629","DOIUrl":"10.1016/j.fluid.2025.114629","url":null,"abstract":"<div><div>The two-phase (liquid + vapor) heat capacities of glymes CH<sub>3</sub>(OCH<sub>2</sub>CH<sub>2</sub>)<sub>n</sub>OCH<sub>3</sub> with <em>n</em> from 1 to 4 (monoglyme, diglyme, triglyme and tetraglyme), as well as ethylene glycol, 2-propanol, n-octane, and benzoic acid have been measured by a differential scanning calorimeter DSC 204 F1 Phoenix (Netzsch, Germany) at atmospheric pressure in the temperature range from 298.2 K to approximately the normal boiling points of the compounds under study. The last four compounds have served as testing ones. The saturation heat capacity and isobaric heat capacity have been calculated. The experiments with testing compounds have shown that the uncertainty of the measurements is less than 0.03. The deviations of the literature data on the isobaric heat capacity of the glymes from the values measured in this work do not in general exceed the uncertainty of the experiments. The temperature dependences of the heat capacity of glymes have been approximated by third-order polynomials. The dependence of the molar heat capacity of glymes on the number of repeating units in a molecule <em>n</em> is linear.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"602 ","pages":"Article 114629"},"PeriodicalIF":2.7,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569060","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}
<div><div>The presence of impurities in CO<sub>2</sub> streams has implications in the design and operation of CCS systems. Due to the wide range of potential emitters and the chemical nature of the impurities, the phase behaviour of CO<sub>2</sub>-rich mixtures may be affected leading to integrity risks. Polar impurities, even at trace or low ppm-mol levels, can influence water solubility and induce a free aqueous phase at temperatures higher than the pure water dew point. This risk can manifest at conditions at which transport pipelines operate, highlighting the need for accurate determination of the dew point of the aqueous phase in the presence of polar molecules.</div><div>This paper evaluates the performance of various Equation of State (EoS) against experimental solubility data for polar components in CO<sub>2</sub>, aiming to highlight potential uncertainties inherent in standard industry tools used for Carbon Capture and Storage (CCS) pipeline transport systems. Specifically, the Cubic-Plus-Association (CPA) EoS, as implemented in the commercial property package <em>Multiflash</em>, was assessed for its ability to predict the solubility of polar impurities—such as methanol (MeOH), triethylene glycol (TEG), and ethylene glycol (MEG)—in binary CO<sub>2</sub>-rich systems. The results reveal the capabilities and limitations of the CPA EoS in accurately estimating polar component solubilities of polar component. Significant discrepancies were observed in the solubility predictions of MeOH, TEG, and MEG, with Average Absolute Deviations (AAD) of 34.4 %, 65.8 %, and 27.8 %, respectively. These deviations underscore the model’s limitations under varying conditions, primarily due to the complexity of intermolecular interactions and the inherent challenges in capturing them within a cubic EoS framework.</div><div>To enhance the prediction accuracy of the solubility of the polar component solubility in CO<sub>2</sub>, the CPA EoS was tuned using available literature experimental data. The EoS was optimized through a calibration process that involved fitting temperature-dependent binary interaction parameters (BIPs), and cross-association parameters. We focused on improving the accuracy of solubility predictions for MeOH, TEG, and MEG in CO<sub>2</sub>, as evidenced by a reduction in the Absolute Average Deviation (AAD) down to 21.6 %,19.3 %, and 13.4 %, respectively.</div><div>While the estimations of the CPA EoS are improved, there are still some limitations. Furthermore, experimental data deviations under similar pressure and temperature conditions, along with the limited availability of reliable measurements in CO<sub>2</sub> gas and supercritical conditions relevant to CCS pipeline operations, pose additional challenges for model validation and improving predictive capability across the wide range of conditions encountered in the CCS industry. To address these limitations, this study emphasizes the need for further experimental research to gen
{"title":"Solubility of TEG, MEG, and MeOH in CO2: Improving CPA EoS modelling for CCS transport applications","authors":"Dhanaraj Turunawarasu, Paula S.C. Farias, Ayuni Saidi, Arfa Amir, Eduardo Luna-Ortiz","doi":"10.1016/j.fluid.2025.114628","DOIUrl":"10.1016/j.fluid.2025.114628","url":null,"abstract":"<div><div>The presence of impurities in CO<sub>2</sub> streams has implications in the design and operation of CCS systems. Due to the wide range of potential emitters and the chemical nature of the impurities, the phase behaviour of CO<sub>2</sub>-rich mixtures may be affected leading to integrity risks. Polar impurities, even at trace or low ppm-mol levels, can influence water solubility and induce a free aqueous phase at temperatures higher than the pure water dew point. This risk can manifest at conditions at which transport pipelines operate, highlighting the need for accurate determination of the dew point of the aqueous phase in the presence of polar molecules.</div><div>This paper evaluates the performance of various Equation of State (EoS) against experimental solubility data for polar components in CO<sub>2</sub>, aiming to highlight potential uncertainties inherent in standard industry tools used for Carbon Capture and Storage (CCS) pipeline transport systems. Specifically, the Cubic-Plus-Association (CPA) EoS, as implemented in the commercial property package <em>Multiflash</em>, was assessed for its ability to predict the solubility of polar impurities—such as methanol (MeOH), triethylene glycol (TEG), and ethylene glycol (MEG)—in binary CO<sub>2</sub>-rich systems. The results reveal the capabilities and limitations of the CPA EoS in accurately estimating polar component solubilities of polar component. Significant discrepancies were observed in the solubility predictions of MeOH, TEG, and MEG, with Average Absolute Deviations (AAD) of 34.4 %, 65.8 %, and 27.8 %, respectively. These deviations underscore the model’s limitations under varying conditions, primarily due to the complexity of intermolecular interactions and the inherent challenges in capturing them within a cubic EoS framework.</div><div>To enhance the prediction accuracy of the solubility of the polar component solubility in CO<sub>2</sub>, the CPA EoS was tuned using available literature experimental data. The EoS was optimized through a calibration process that involved fitting temperature-dependent binary interaction parameters (BIPs), and cross-association parameters. We focused on improving the accuracy of solubility predictions for MeOH, TEG, and MEG in CO<sub>2</sub>, as evidenced by a reduction in the Absolute Average Deviation (AAD) down to 21.6 %,19.3 %, and 13.4 %, respectively.</div><div>While the estimations of the CPA EoS are improved, there are still some limitations. Furthermore, experimental data deviations under similar pressure and temperature conditions, along with the limited availability of reliable measurements in CO<sub>2</sub> gas and supercritical conditions relevant to CCS pipeline operations, pose additional challenges for model validation and improving predictive capability across the wide range of conditions encountered in the CCS industry. To address these limitations, this study emphasizes the need for further experimental research to gen","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"602 ","pages":"Article 114628"},"PeriodicalIF":2.7,"publicationDate":"2025-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517717","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 : 2025-11-06DOI: 10.1016/j.fluid.2025.114618
Peiming Wang , Mohiedin Bagheri Hariri , Jerzy J. Kosinski , Basil Perdicakis , Andre Anderko
The dissolution behavior of iron oxides in high-temperature water containing various dissolved species is a critical factor for understanding and predicting the conditions that control flow-accelerated corrosion (FAC). Predicting the stability of passivating films under steam-generating conditions, which may give rise to FAC, requires an accurate thermodynamic model that is capable of predicting the solubility of film materials, particularly magnetite (Fe3O4), hematite (Fe2O3) and iron oxyhydroxides (FeOOH). This is essential for accurate corrosion prediction, particularly in applications such as steam generation for hydrocarbon recovery from oil sands, water/steam cycle boilers, power plants, boiler feedwater systems, etc. In this study, available experimental solubility data have been evaluated for iron oxides/hydroxides, and a comprehensive thermodynamic model has been developed using the Mixed Solvent Electrolyte (MSE) framework for temperatures up to 600 K and pressures exceeding 50 MPa. The MSE model reproduces solubility in the presence of various inorganic ions and additives used in all-volatile treatments (AVT) wherein volatile alkalizing agents are employed under either reducing conditions (i.e., AVT(R)) or oxidizing conditions (i.e., AVT(O)). The accuracy of model predictions is, in general, consistent with the inherent uncertainty of experimental solubility data while the distribution of errors is a function of pH and temperature, with elevated uncertainty observed for neutral and alkaline solutions. Further, the MSE model has been applied to predict magnetite stability across various AVT(R) scenarios with different dosages of alkaline and non-alkaline reducing agents (i.e., hydrazine, hydrogen) to provide a thermodynamic foundation for controlling environmental variables in mitigating AVT(R) flow-accelerated corrosion risks. This work is especially relevant to the Canadian oil sands industry, in particular to industrial steam generation applications such as oilfield once-through steam generation systems, where high temperatures and high pH conditions affect corrosion behavior.
{"title":"Modeling the solubility of iron oxides in wide temperature ranges: thermodynamic foundation for understanding flow-accelerated corrosion","authors":"Peiming Wang , Mohiedin Bagheri Hariri , Jerzy J. Kosinski , Basil Perdicakis , Andre Anderko","doi":"10.1016/j.fluid.2025.114618","DOIUrl":"10.1016/j.fluid.2025.114618","url":null,"abstract":"<div><div>The dissolution behavior of iron oxides in high-temperature water containing various dissolved species is a critical factor for understanding and predicting the conditions that control flow-accelerated corrosion (FAC). Predicting the stability of passivating films under steam-generating conditions, which may give rise to FAC, requires an accurate thermodynamic model that is capable of predicting the solubility of film materials, particularly magnetite (Fe<sub>3</sub>O<sub>4</sub>), hematite (Fe<sub>2</sub>O<sub>3</sub>) and iron oxyhydroxides (FeOOH). This is essential for accurate corrosion prediction, particularly in applications such as steam generation for hydrocarbon recovery from oil sands, water/steam cycle boilers, power plants, boiler feedwater systems, etc. In this study, available experimental solubility data have been evaluated for iron oxides/hydroxides, and a comprehensive thermodynamic model has been developed using the Mixed Solvent Electrolyte (MSE) framework for temperatures up to 600 K and pressures exceeding 50 MPa. The MSE model reproduces solubility in the presence of various inorganic ions and additives used in all-volatile treatments (AVT) wherein volatile alkalizing agents are employed under either reducing conditions (i.e., AVT(R)) or oxidizing conditions (i.e., AVT(O)). The accuracy of model predictions is, in general, consistent with the inherent uncertainty of experimental solubility data while the distribution of errors is a function of pH and temperature, with elevated uncertainty observed for neutral and alkaline solutions. Further, the MSE model has been applied to predict magnetite stability across various AVT(R) scenarios with different dosages of alkaline and non-alkaline reducing agents (i.e., hydrazine, hydrogen) to provide a thermodynamic foundation for controlling environmental variables in mitigating AVT(R) flow-accelerated corrosion risks. This work is especially relevant to the Canadian oil sands industry, in particular to industrial steam generation applications such as oilfield once-through steam generation systems, where high temperatures and high pH conditions affect corrosion behavior.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"602 ","pages":"Article 114618"},"PeriodicalIF":2.7,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517720","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 : 2025-11-06DOI: 10.1016/j.fluid.2025.114615
Qing Yang, Shuai Peng, Yueting Zhu, Ke Chen, Jianfang Liu
The dissolution behavior of drugs is critical for understanding dissolution mechanisms and optimizing pharmaceutical formulations. This study investigated the solubility of the anti-rheumatic drug Iguratimod (IGU) in 12 organic solvents between 283.15 and 323.15 K at 101.3 kPa. Notably, solvent-induced polymorphic transformation yielded two distinct crystal forms: α and β. The Apelblat, λh, Yaws, NRTL, and Wilson models were employed to correlate the solubility data, with the Apelblat equation providing the most accurate prediction. Thermodynamic analysis shows that the dissolution of both polymorphs is endothermic and enthalpy-driven. Correlation analysis and Hirshfeld surface analysis indicate that the stability and solubility of crystal form α are mainly influenced by solvent polarity and hydrogen bond acidity. The crystal structure may be stabilized through an intrinsic hydrogen bonding network, and solubility is achieved in solvents that exhibit high polarity and low hydrogen bonding self-association tendency. The formation and solubility of crystal form β are determined by its unique crystal stacking mode, the formation of crystal structure is determined by the steric hindrance and weak hydrogen bonding donor ability of the solvent through dynamic pathway selection, and its solubility is mainly guided by the thermodynamic equilibrium between the lower lattice energy (HH and HO interactions) of the crystal itself and the high polarity solvation ability of the solvent. This work provides fundamental insights into solvent-induced polymorphic transformation, offering a theoretical basis for rational polymorph control and solvent selection in pharmaceutical processing.
{"title":"Solvent-driven polymorphic transformation and dissolution thermodynamics study of Iguratimod","authors":"Qing Yang, Shuai Peng, Yueting Zhu, Ke Chen, Jianfang Liu","doi":"10.1016/j.fluid.2025.114615","DOIUrl":"10.1016/j.fluid.2025.114615","url":null,"abstract":"<div><div>The dissolution behavior of drugs is critical for understanding dissolution mechanisms and optimizing pharmaceutical formulations. This study investigated the solubility of the anti-rheumatic drug Iguratimod (IGU) in 12 organic solvents between 283.15 and 323.15 K at 101.3 kPa. Notably, solvent-induced polymorphic transformation yielded two distinct crystal forms: α and β. The Apelblat, λh, Yaws, NRTL, and Wilson models were employed to correlate the solubility data, with the Apelblat equation providing the most accurate prediction. Thermodynamic analysis shows that the dissolution of both polymorphs is endothermic and enthalpy-driven. Correlation analysis and Hirshfeld surface analysis indicate that the stability and solubility of crystal form α are mainly influenced by solvent polarity and hydrogen bond acidity. The crystal structure may be stabilized through an intrinsic hydrogen bonding network, and solubility is achieved in solvents that exhibit high polarity and low hydrogen bonding self-association tendency. The formation and solubility of crystal form β are determined by its unique crystal stacking mode, the formation of crystal structure is determined by the steric hindrance and weak hydrogen bonding donor ability of the solvent through dynamic pathway selection, and its solubility is mainly guided by the thermodynamic equilibrium between the lower lattice energy (H<img>H and H<img>O interactions) of the crystal itself and the high polarity solvation ability of the solvent. This work provides fundamental insights into solvent-induced polymorphic transformation, offering a theoretical basis for rational polymorph control and solvent selection in pharmaceutical processing.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"602 ","pages":"Article 114615"},"PeriodicalIF":2.7,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569059","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 : 2025-11-05DOI: 10.1016/j.fluid.2025.114617
Ibtissem Guennoun , Ilham Mokbel , Latifa Negadi , Jacques Jose , Joseph Saab
This study investigates the vapor pressures of the platform chemicals furfural and 5-methylfurfural, as well as their binary mixtures with bio-derived solvents γ-valerolactone and γ-butyrolactone, using a static isothermal apparatus. Measurements were conducted over a range of 5 Pa to 10 kPa and 273.15 K to 363.15 K. The experimental data for the pure compounds were compared with literature values, while no reference data were available for the binary systems. The results were subsequently correlated using the NRTL and UNIQUAC models.
{"title":"Experimental vapor-liquid equilibria of pure compounds and binary systems (furfural + γ-valerolactone or γ-butyrolactone) and (5-methylfurfural + γ-valerolactone or γ-butyrolactone) encountered in biorefineries","authors":"Ibtissem Guennoun , Ilham Mokbel , Latifa Negadi , Jacques Jose , Joseph Saab","doi":"10.1016/j.fluid.2025.114617","DOIUrl":"10.1016/j.fluid.2025.114617","url":null,"abstract":"<div><div>This study investigates the vapor pressures of the platform chemicals furfural and 5-methylfurfural, as well as their binary mixtures with bio-derived solvents γ-valerolactone and γ-butyrolactone, using a static isothermal apparatus. Measurements were conducted over a range of 5 Pa to 10 kPa and 273.15 K to 363.15 K. The experimental data for the pure compounds were compared with literature values, while no reference data were available for the binary systems. The results were subsequently correlated using the NRTL and UNIQUAC models.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"602 ","pages":"Article 114617"},"PeriodicalIF":2.7,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517719","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 : 2025-11-05DOI: 10.1016/j.fluid.2025.114616
Ricardo Macías-Salinas , María Antonieta Zúñiga-Hinojosa , Obed Andrés Solis-González
The well-known Gradient Theory of Fluid Interfaces (GTFI) was coupled with a simple cubic equation of state (CEoS) to accurately calculate the surface tension of non-polar, polar, and associating fluids over a wide temperature range, from the triple point to the critical region. For most of the pure fluids studied, a remarkably accurate representation of reference surface tensions was obtained near their critical points, even though the homogeneous fluid portion of the GTFI was modeled using a simple CEoS, which typically fails to accurately describe fluid phase behavior near the critical point. To mitigate this limitation of the CEoS within the GTFI framework, a new scaling function for the influence parameter of the inhomogeneous fluid was introduced. The proposed expression for the influence parameter proved highly satisfactory, particularly near the critical point, when combined with the Soave-Redlich-Kwong (SRK) or Peng-Robinson (PR) CEoS in representing the reference surface tensions of various pure fluids, including normal paraffins, aromatics, CO2, SF6, alcohols, water, acetone, and others, thus yielding overall values of average absolute relative deviations of 1.67 % using the GTFI-SRK approach, and 1.78 % using the GTFI-PR approach.
{"title":"Surface-tension modeling of pure fluids using the gradient theory coupled with a cubic EoS","authors":"Ricardo Macías-Salinas , María Antonieta Zúñiga-Hinojosa , Obed Andrés Solis-González","doi":"10.1016/j.fluid.2025.114616","DOIUrl":"10.1016/j.fluid.2025.114616","url":null,"abstract":"<div><div>The well-known Gradient Theory of Fluid Interfaces (GTFI) was coupled with a simple cubic equation of state (CEoS) to accurately calculate the surface tension of non-polar, polar, and associating fluids over a wide temperature range, from the triple point to the critical region. For most of the pure fluids studied, a remarkably accurate representation of reference surface tensions was obtained near their critical points, even though the homogeneous fluid portion of the GTFI was modeled using a simple CEoS, which typically fails to accurately describe fluid phase behavior near the critical point. To mitigate this limitation of the CEoS within the GTFI framework, a new scaling function for the influence parameter of the inhomogeneous fluid was introduced. The proposed expression for the influence parameter proved highly satisfactory, particularly near the critical point, when combined with the Soave-Redlich-Kwong (SRK) or Peng-Robinson (PR) CEoS in representing the reference surface tensions of various pure fluids, including normal paraffins, aromatics, CO<sub>2</sub>, SF<sub>6</sub>, alcohols, water, acetone, and others, thus yielding overall values of average absolute relative deviations of 1.67 % using the GTFI-SRK approach, and 1.78 % using the GTFI-PR approach.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"602 ","pages":"Article 114616"},"PeriodicalIF":2.7,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517716","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 : 2025-11-04DOI: 10.1016/j.fluid.2025.114614
Masoume Najafi, Fatemeh Zarei, Hosseinali Zarei
This contribution reports the PρT properties of pure Poly ethylene glycol 200 and Poly ethylene glycol 300 at 12 isotherms ranging from (293.15–473.15 K) and 19 isobars starting at 0.1 MPa up to 40 MPa. Additionally, the values of density and speed of sound for these same solvents at different temperatures T = (293.15 - 343.15 K), and ambient pressure (81.5 kPa) were measured experimentally. The PρT data were initially examined using the new modified Tammann–Tait equation to derive the thermal expansion coefficient, ( ), and isothermal compressibility, (). Finally, for the studied solvents, the parameters of the PC-SAFT equation of the state were obtained based on the PρT data. The AADs of liquid density correlated with the PC-SAFT EOS were 0.08 % and 0.06 % for PEG 200 and PEG 300, respectively.Then, the performance PC-SAFT equation was evaluated for predicting key thermodynamic properties such as thermal expansion coefficient ,(), isothermal compressibility, (), isobaric heat capacity, (), and speed of sound, ().These results were compared with values obtained from the modified Tammann– Tait equation and literature data and showed satisfactory agreement with AAD% <13 %.
{"title":"Measurements of the PρT data of liquids Poly ethylene glycol 200 and Poly ethylene glycol 300 from (293.15 to 473.15) K and up to 40 MPa: Correlating and modelling using the modified Tammann-Tait and PC-SAFT equations","authors":"Masoume Najafi, Fatemeh Zarei, Hosseinali Zarei","doi":"10.1016/j.fluid.2025.114614","DOIUrl":"10.1016/j.fluid.2025.114614","url":null,"abstract":"<div><div>This contribution reports the <em>PρT</em> properties of pure Poly ethylene glycol 200 and Poly ethylene glycol 300 at 12 isotherms ranging from (293.15–473.15 K) and 19 isobars starting at 0.1 MPa up to 40 MPa. Additionally, the values of density and speed of sound for these same solvents at different temperatures <em>T</em> = (293.15 - 343.15 K), and ambient pressure (81.5 kPa) were measured experimentally. The <em>PρT</em> data were initially examined using the new modified Tammann–Tait equation to derive the 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>). Finally, for the studied solvents, the parameters of the PC-SAFT equation of the state were obtained based on the <em>PρT</em> data. The AADs of liquid density correlated with the PC-SAFT EOS were 0.08 % and 0.06 % for PEG 200 and PEG 300, respectively.Then, the performance PC-SAFT equation was evaluated for predicting key thermodynamic properties such as 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>).These results were compared with values obtained from the modified Tammann– Tait equation and literature data and showed satisfactory agreement with AAD% <13 %.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"602 ","pages":"Article 114614"},"PeriodicalIF":2.7,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145517718","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 : 2025-11-01DOI: 10.1016/j.fluid.2025.114613
Alexandre M.S. Jorge , Ramesh L. Gardas , Jorge F.B. Pereira
The textile industry is a major global consumer and polluter of water, with dye-contaminated wastewater posing serious environmental risks. Aqueous Two-Phase Systems (ATPS), particularly those based on alcohol/salt combinations, present a simple and efficient approach for dye removal owing to rapid phase separation and high solute concentration capacity. However, limited understanding of the phase separation and partition mechanisms has limited their rational design and broader industrial application. This study investigates the formation of nineteen alcohol/salt ATPS composed of short-chain alcohols [ethanol (EtOH), isopropyl alcohol (IPA), 1-propyl alcohol (PA), tert-butyl alcohol (TBA), isobutyl alcohol (IBA)] and sodium salts [acetate (NaCH3COO), citrate (Na3C6H5O7), sulphate (Na2SO4), and carbonate (Na2CO3)], as well as the partitioning behaviour of methyl red (MR) as the target compound. The results were analysed based on physicochemical properties of the alcohols and salts, and supported by thermodynamic data obtained from the COnductor-like Screening MOdel for Real Solvents (COSMO-RS). Systems formed with more hydrophobic alcohols and stronger salting-out salts exhibited larger biphasic regions, consistent with COSMO-RS predictions of higher excess Gibbs free energy of mixing (GE) for alcohol-water binary systems and lower entropic contributions (-TSE) for salt-water binary mixtures. These results allowed the differentiation between systems behaving as classic organic/aqueous systems, dominated by alcohol–water immiscibility, and aqueous two-phase systems, where phase separation is governed by a careful balance of intermolecular interactions between alcohol hydrophobicity and salt salting-out strength. Partitioning studies revealed log K values ranging from 0.4 to 3.4 and extraction efficiencies (EE) between 75 % and 100 % for MR. Larger tie-line lengths (TLL) enhanced the partitioning of MR into the more hydrophobic alcohol-rich phase. Higher log K values also correlated with increasing salting-out strength of the salts (NaCH₃COO < Na₃C₆H₅O₇ < Na₂SO₄ < Na₂CO₃). This study provides valuable thermodynamic insights into the design of alcohol/salt ATPS for dye extraction, while also distinguishing between classical organic/aqueous and all-aqueous biphasic systems based on their phase behaviour.
{"title":"Phase separation and partitioning in alcohol/salt aqueous two-phase systems: Experimental and COSMO-RS insights","authors":"Alexandre M.S. Jorge , Ramesh L. Gardas , Jorge F.B. Pereira","doi":"10.1016/j.fluid.2025.114613","DOIUrl":"10.1016/j.fluid.2025.114613","url":null,"abstract":"<div><div>The textile industry is a major global consumer and polluter of water, with dye-contaminated wastewater posing serious environmental risks. Aqueous Two-Phase Systems (ATPS), particularly those based on alcohol/salt combinations, present a simple and efficient approach for dye removal owing to rapid phase separation and high solute concentration capacity. However, limited understanding of the phase separation and partition mechanisms has limited their rational design and broader industrial application. This study investigates the formation of nineteen alcohol/salt ATPS composed of short-chain alcohols [ethanol (EtOH), isopropyl alcohol (IPA), 1-propyl alcohol (PA), <em>tert</em>-butyl alcohol (TBA), isobutyl alcohol (IBA)] and sodium salts [acetate (NaCH<sub>3</sub>COO), citrate (Na<sub>3</sub>C<sub>6</sub>H<sub>5</sub>O<sub>7</sub>), sulphate (Na<sub>2</sub>SO<sub>4</sub>), and carbonate (Na<sub>2</sub>CO<sub>3</sub>)], as well as the partitioning behaviour of methyl red (MR) as the target compound. The results were analysed based on physicochemical properties of the alcohols and salts, and supported by thermodynamic data obtained from the COnductor-like Screening MOdel for Real Solvents (COSMO-RS). Systems formed with more hydrophobic alcohols and stronger salting-out salts exhibited larger biphasic regions, consistent with COSMO-RS predictions of higher excess Gibbs free energy of mixing (<em>G</em><sup>E</sup>) for alcohol-water binary systems and lower entropic contributions (-T<em>S</em><sup>E</sup>) for salt-water binary mixtures. These results allowed the differentiation between systems behaving as classic organic/aqueous systems, dominated by alcohol–water immiscibility, and aqueous two-phase systems, where phase separation is governed by a careful balance of intermolecular interactions between alcohol hydrophobicity and salt salting-out strength. Partitioning studies revealed log <em>K</em> values ranging from 0.4 to 3.4 and extraction efficiencies (EE) between 75 % and 100 % for MR. Larger tie-line lengths (TLL) enhanced the partitioning of MR into the more hydrophobic alcohol-rich phase. Higher log <em>K</em> values also correlated with increasing salting-out strength of the salts (NaCH₃COO < Na₃C₆H₅O₇ < Na₂SO₄ < Na₂CO₃). This study provides valuable thermodynamic insights into the design of alcohol/salt ATPS for dye extraction, while also distinguishing between classical organic/aqueous and all-aqueous biphasic systems based on their phase behaviour.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"602 ","pages":"Article 114613"},"PeriodicalIF":2.7,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464119","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号