Fluid Phase Equilibria最新文献

{"title":"Predictive QSPR modeling of pyridine extraction from fuels using deep eutectic solvents: Structural descriptors and neural network insights","authors":"Fatemeh Ghadimi,&nbsp;Mohammad Amin Sobati,&nbsp;Mahdieh Amereh","doi":"10.1016/j.fluid.2025.114522","DOIUrl":"10.1016/j.fluid.2025.114522","url":null,"abstract":"<div><div>This study employs the Quantitative-Structure-Property-Relationship (QSPR) method to investigate the extractive denitrogenation process of fuels employing deep eutectic solvents (DESs). In this regard, the distribution of pyridine (PY) as a typical nitrogen compound between the hydrocarbon and DES-rich phases was predicted. A comprehensive dataset, covering liquid-liquid equilibrium (LLE) data for 43 ternary systems was collected from various hydrocarbons and DESs containing different hydrogen bond donors (HBDs) and hydrogen bond acceptors (HBAs), enabled an extensive investigation of structural effects on PY distribution. Predictive linear model employing multiple linear regression (MLR) and non-linear models employing multi-layer perceptron (MLP), Radial Basis Function (RBF), Support Vector Machine (SVM), and Random Forest (RF) were developed. The linear model achieved statistical values of R² = 0.8025 and Average Absolute Relative Deviation (AARD) = 21.52 %, while among the non-linear models, the MLP model demonstrated the best performance with R² = 0.9581 and AARD = 9.30 %. The examination of molecular descriptors in the QSPR model demonstrated that PY distribution between the DES and hydrocarbon-rich phases is strongly affected by the average molecular weight of the HBA component and the hydrophilic characteristics of the HBD structure. These observations offer benefical insights for selecting and fine-tuning of molecular structure of DESs in the extractive denitrogenation applications.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"599 ","pages":"Article 114522"},"PeriodicalIF":2.8,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144655478","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}

{"title":"Vapor–liquid equilibrium measurements of the carbon dioxide ＋ water (CO2＋H2O) system and carbon dioxide ＋ water ＋ sodium chloride (CO2＋H2O+NaCl) system","authors":"Yannick Jooss,&nbsp;Anders Austegard,&nbsp;Jacob H. Stang,&nbsp;Ingeborg Treu Røe,&nbsp;Bjørn Strøm,&nbsp;Ailo Aasen","doi":"10.1016/j.fluid.2025.114516","DOIUrl":"10.1016/j.fluid.2025.114516","url":null,"abstract":"<div><div>Accurate phase equilibrium data for CO₂ mixtures are essential for safe and cost-effective design of carbon capture, transport and storage chains. We report measurements of the saturation water content of the carbon dioxide-rich phase for both the CO₂+H₂O and the CO₂+H₂O+NaCl system. The experiments span the temperatures 35–120 °C, pressures 1–70 MPa, and NaCl concentrations of 0, 78 and 150 g NaCl/kg water (NaCl molalities 0, 1.3 and 2.6). Total uncertainties in the reported water mole fractions are mostly between 100 and 300 ppm. The measurements are compared to previous literature data, and two equations of state: the Spycher model and EOS-CG. The EOS-CG model agrees well with our CO₂+H₂O data at high pressures, but generally overpredicts the water content at pressures below <span><math><mo>∼</mo></math></span> 15 MPa. The Spycher model agrees well with our data for CO₂+H₂O at pressures below <span><math><mo>∼</mo></math></span> 15 MPa, but exhibits some systematic deviations that can be traced to simplifying assumptions made in the model development. The Spycher model predicts the influence of NaCl on water content fairly well, but surprisingly we find that better results are obtained simply by applying Raoult’s law for the influence of ions on water activity. We derive theoretically-based bounds on the influence of salt on water content, and use them to investigate systematic errors in the measurements presented herein and in the literature. The present work indicates a clear potential to improve both models and that some previous water content measurements of the CO₂-rich phase may have substantial systematic errors.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"599 ","pages":"Article 114516"},"PeriodicalIF":2.8,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144548555","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}

{"title":"Viscosity prediction of asymmetric hydrocarbon mixtures by the soft-SAFT + entropy scaling model","authors":"Zhiyu Yan,&nbsp;Yiran Wang,&nbsp;Xiangyang Liu,&nbsp;Maogang He","doi":"10.1016/j.fluid.2025.114521","DOIUrl":"10.1016/j.fluid.2025.114521","url":null,"abstract":"<div><div>In this study, we combined the soft-SAFT equation of state (EoS) with entropy scaling to model the correlation between viscosity and residual entropy in pure hydrocarbons and their asymmetric binary mixtures with significant molecular weight disparities. For pure hydrocarbons, the dimensionless viscosity exhibits a distinct univariate dependence on residual entropy. When extended to mixtures, the viscosity is predicted by incorporating contributions from each component without introducing additional adjustable parameters. The model was validated against 1326 experimental viscosity data points for mixtures composed of hydrocarbons with carbon numbers ranging from 5 to 24, yielding an average absolute relative deviation (AARD) of 3.71 %. For the more challenging methane-containing mixtures (where methane viscosity differs by orders of magnitude from the other component), the predictive accuracy was significantly improved with an AARD of only 4.75 %.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"599 ","pages":"Article 114521"},"PeriodicalIF":2.8,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144579990","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}

{"title":"Measurements and modeling of vapor–liquid equilibrium for ternary mixtures of R290+R1234ze(E)+CO2","authors":"Yingxi Qi,&nbsp;Xiaolei Xu,&nbsp;Junqi Dong,&nbsp;Xi Chen,&nbsp;Hua Zhang","doi":"10.1016/j.fluid.2025.114519","DOIUrl":"10.1016/j.fluid.2025.114519","url":null,"abstract":"<div><div>Heat pumps are widely used for their high energy conversion efficiency and contribution to reducing greenhouse gas emissions. Developing low-GWP refrigerants has become a research focus, and mixed refrigerants are a potential solution. This study conducted the precise measurements of the vapor-liquid equilibrium properties of the ternary mixtures of R290(1)+R1234ze(E)(2)+CO₂(3) with the liquid mole fraction of R290 varying from 0.2 to 0.4 and R1234ze from 0.5 to 0.75 over the temperature range of 268.15 to 313.15 K. The experimental VLE data of the ternary mixtures were fitted by PRSV+vdW model. The Absolute Average Relative Deviations (<em>AARD</em>s) for the equilibrium pressures, and the Absolute Average Deviations (<em>AAD</em>s) for the vapor phase mole fractions of R290 and R1234ze(E) between the calculated results from the models and experimental ones were 0.82 %, 0.0038, and 0.0061 for the PRSV+vdW model. The model demonstrated a good correlation with the experimental data. The data reported is helpful for the application to new air-source heat pump system, and the VLE experiments and models are important for developing the thermophysical research of the environmental-friendly refrigerant mixtures.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114519"},"PeriodicalIF":2.8,"publicationDate":"2025-06-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144471568","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}

{"title":"Bubble point pressures for dimethyl ether – methanol, dimethyl ether – 2-methoxyethanol and dimethyl ether - 2-ethoxyethanol at (293.15–313.15) K, and their predictions considering pair interactions for three functional groups, -CH2OCH2-, -CH2OH and -CH2CH2CH2-","authors":"Aoi Enokido ,&nbsp;Tomoya Tsuji ,&nbsp;Andrea Jia Xin Lai ,&nbsp;Hiroaki Matsukawa ,&nbsp;Taka-aki Hoshina ,&nbsp;Hiroyuki Matsuda ,&nbsp;Katsumi Tochigi","doi":"10.1016/j.fluid.2025.114518","DOIUrl":"10.1016/j.fluid.2025.114518","url":null,"abstract":"<div><div>2-Alkoxyethanols enhance the miscibility for aqueous solvents with a propellant, dimethyl ether, in spray cans. Therefore, the bubble point pressures (BPs) were measured for dimethyl ether – methanol, dimethyl ether - 2-methoxyethanol and dimethyl ether – 2-ethoxyethanol by using static apparatuses at (293.15–313.15) K. The experimental BPs were compared with the previous data of dimethyl ether – 2-butoxyethanol. The BPs were larger than those of ideal solution. The order was dimethyl ether – methanol &gt; dimethyl ether - 2-methoxyethanol &gt; dimethyl ether – 2-ethoxyethanol &gt; dimethyl ether – 2-butoxyethanol. Analytical solution of groups (ASOG) model was modified for the predictions. The original model provides the activity coefficients by combining Flory-Huggins and Wilson equations, and the parameters have been determined for 43 functional groups. Only three groups, -CH₂OCH₂-, -CH₂OH and -CH₂CH₂CH₂-, were newly considered in this study. Then, 2-ethoxyethanol was assumed to be composed of -CH₂OCH₂-, -CH₂OH and one-third of -CH₂CH₂CH₂-. The group pair interaction parameters, for (-CH₂CH₂CH₂- and -CH₂OCH₂-) and (-CH₂CH₂CH₂- and -CH₂OH), were determined from the literature data of vapor-liquid equilibria for propane - dimethyl ether and propane - methanol. Two different methods were employed to determine the parameters for (-CH₂CH₂CH₂- and -CH₂OH). One was from the BPs of dimethyl ether – methanol. The other was from those of dimethyl ether - 2-methoxyethanol. The better reproducibilities were obtained by the latter method. The average values of relative deviation for BP were 4.14, 3.62 and 4.37 % for dimethyl ether - 2-methoxyethanol, dimethyl ether - 2-ethoxyethanol and dimethyl ether - 2-butoxyethanol, respectively.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114518"},"PeriodicalIF":2.8,"publicationDate":"2025-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144489339","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}

{"title":"Isobaric vapor-liquid equilibrium of fluorobenzene with alkyl carbonates and alcohols","authors":"Martin Wolke,&nbsp;Katharina Jasch,&nbsp;Stephan Scholl","doi":"10.1016/j.fluid.2025.114515","DOIUrl":"10.1016/j.fluid.2025.114515","url":null,"abstract":"<div><div>Isobaric vapor-liquid equilibrium (VLE) data was determined experimentally for binary mixtures of fluorobenzene (FB) with methanol (MeOH), ethanol (EtOH), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC). The measurements were conducted at total pressures of 500 mbar for alcohol mixtures and 100 mbar for alkyl carbonate mixtures. The data show azeotrope formation in the alcohol and DMC systems, while EMC and DEC mixtures exhibit nearly ideal behavior. Thermodynamic consistency was evaluated using Herington, Wisniak and Fredenslund tests, with varying outcomes. The VLE data were successfully correlated using the Non-Random Two-Liquid (NRTL) model, demonstrating good agreement with experimental results. The findings contribute to a comprehensive understanding of the separation behavior of mixtures composed of these components, which is relevant for the purification of recovered solvent mixtures during lithium-ion battery recycling.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114515"},"PeriodicalIF":2.8,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144501404","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}

{"title":"A deep investigation of neo-pentane freeze-out in methane","authors":"Marco Campestrini,&nbsp;Salem Hoceini,&nbsp;Paolo Stringari","doi":"10.1016/j.fluid.2025.114517","DOIUrl":"10.1016/j.fluid.2025.114517","url":null,"abstract":"<div><div>The investigation of the phase equilibrium behaviour of the methane + neopentane system has attracted a lot of interest in recent years seeing that neopentane is one of the heaviest natural gas components, a characteristic that poses a risk of freeze-out for the natural gas liquefaction process. Despite its high triple-point temperature (256.6 K), the solubility of solid neopentane in liquid methane is expected to be relatively high (a few percent at LNG temperatures) according to recent works dealing with the measurement and prediction of the solid-liquid(-vapor) equilibrium behaviour of this mixture. However, experimental phase equilibrium data are only available at temperatures down to 200 K or below 125 K, meaning that information is still missing in the 125 <em>K</em> &lt; <em>T</em> &lt; 200 K range. The aim of this work is to enhance the understanding of the thermodynamic behaviour of the methane + neopentane system by further experimental results concerning the solid-liquid, solid-vapor, solid-liquid-vapor, and vapor-liquid equilibria between 100 K and 240 K. If the results presented in this work confirm that neopentane is quite soluble in the liquid phase, they also indicate that the liquefaction pressure should be carefully chosen since neopentane is poorly soluble in vapor methane.-</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114517"},"PeriodicalIF":2.8,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144471567","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}

{"title":"Modeling polycyclic aromatic hydrocarbons (PAH) and liquid organic hydrogen carriers (LOHC) with the SAFT-γ Mie group-contribution equation of state","authors":"Edgar Velásquez Sarmiento,&nbsp;Patrice Paricaud","doi":"10.1016/j.fluid.2025.114514","DOIUrl":"10.1016/j.fluid.2025.114514","url":null,"abstract":"<div><div>Liquid organic hydrogen carriers (LOHC) are being studied as a promising and feasible alternative for hydrogen storage and transportation due to their high hydrogen uptake capacity, low flammability, and stability at ambient conditions. This work focuses on expanding the applications of the SAFT-γ Mie group-contribution equation of state by estimating the parameters of two new groups: an aromatic bridgehead carbon (aC), and a methylene “elbow” group connecting two aromatic rings (aCCH₂aC), starting from readily available experimental data on polyaromatic hydrocarbons (PAH) and LOHC candidates such as alkylcarbazoles, diphenylmethane, and isomers of benzyltoluene and dibenzyltoluene. The model describes with good accuracy the vapor pressure and saturated liquid density of these substances, with a <span><math><mrow><mo>%</mo><mi>A</mi><mi>A</mi><msubsup><mi>D</mi><mrow><msup><mrow><mi>P</mi></mrow><mrow><mi>v</mi><mi>a</mi><mi>p</mi></mrow></msup></mrow><mrow><mi>o</mi><mi>v</mi><mi>e</mi><mi>r</mi><mi>a</mi><mi>l</mi><mi>l</mi></mrow></msubsup></mrow></math></span> of 9.67 %, and a <span><math><mrow><mo>%</mo><mi>A</mi><mi>A</mi><msubsup><mi>D</mi><mrow><msub><mi>ρ</mi><mrow><mi>l</mi><mi>i</mi><mi>q</mi></mrow></msub></mrow><mrow><mi>o</mi><mi>v</mi><mi>e</mi><mi>r</mi><mi>a</mi><mi>l</mi><mi>l</mi></mrow></msubsup></mrow></math></span> of 0.82 %, as well as the vapor-liquid equilibria of PAH + long-chain alkane mixtures, but has some limitations when describing the structural nuances of molecules that present the same functional groups. As a result, second-order interaction parameters are proposed to improve the correlation of the calculated and experimental data.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114514"},"PeriodicalIF":2.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144365106","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}

{"title":"Modeling of interfacial phenomena in disperse liquid-liquid systems","authors":"Matthias Singer ,&nbsp;Patrick Zimmermann ,&nbsp;Tim Zeiner","doi":"10.1016/j.fluid.2025.114504","DOIUrl":"10.1016/j.fluid.2025.114504","url":null,"abstract":"<div><div>Interfaces are critical in chemical engineering, as they govern mass transfer between phases and play a key role in the formation and behavior of droplets and bubbles. This is particularly true in liquid-liquid extraction columns, where droplet interactions such as coalescence and breakage are pivotal. In decades of research, droplet coalescence remains a complex phenomenon that is not yet fully understood, partly due to the challenges in experimentally analyzing the small-scale and fluid nature of interfaces. To address this gap, we propose a thermodynamically consistent simulation approach to accurately resolve interfaces and study droplet interactions. The developed model builds on the incompressible Density Gradient Theory (DGT) by Cahn and Hilliard, coupling it with the Navier-Stokes equations to form a novel Navier-Stokes/DGT framework. Within this framework, the Non-Random Two-Liquid model is employed as the thermodynamic foundation, enabling the accurate modeling of interfacial properties and prediction of coalescence behavior in liquid-liquid systems. The Navier-Stokes/DGT model, comprising a system of highly nonlinear partial differential equations is solved using the finite volume method in OpenFOAM. This approach enables the simulation of the single stages of droplet coalescence. Furthermore, complex interfacial effects like Marangoni convection and de-mixing behavior are investigated in more detail.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114504"},"PeriodicalIF":2.8,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144510678","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}

{"title":"Monte Carlo optimization method based QSPR modeling of micelle–water partition coefficient","authors":"Jelena V. Živković,&nbsp;Goran M. Nikolić,&nbsp;Žarko Mitić,&nbsp;Aleksandar M. Veselinović","doi":"10.1016/j.fluid.2025.114499","DOIUrl":"10.1016/j.fluid.2025.114499","url":null,"abstract":"<div><div>This study investigates the development of quantitative structure-property relationship (QSPR) models for predicting micelle-water partition coefficients based on 2D molecular representations that does not require conformational sampling or 3D geometry optimization. The Monte Carlo (MC) optimization method was employed to construct these models, utilizing a combination of SMILES notation descriptors and local molecular graph invariants. The MC method served as the model developer for both training and test sets, analyzing three independent splits of 291 organic compounds with experimentally determined micelle-water partition coefficients obtained from sodium dodecyl sulfate (SDS) solutions. The developed QSPR models were rigorously validated using a battery of statistical parameters, demonstrating excellent predictive ability and robustness. Additionally, the study identified key molecular fragments derived from the SMILES notation descriptors that influence the micelle-water partition coefficient (increase or decrease). Overall, this work underscores the efficacy of the MC optimization method in constructing QSPR models with strong predictive power for micelle-water partition coefficients. These models have the potential to streamline drug discovery by facilitating the identification of drug candidates with targeted micelle-water partitioning behavior.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114499"},"PeriodicalIF":2.8,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144298049","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}