Fluid Phase Equilibria最新文献

{"title":"Terpenoids as solvents for the separation of 2,3-butanediol from water: Phase equilibria and process evaluation","authors":"William Graf von Westarp,&nbsp;Janik Hense,&nbsp;Moritz Haas,&nbsp;Andreas Jupke","doi":"10.1016/j.fluid.2025.114572","DOIUrl":"10.1016/j.fluid.2025.114572","url":null,"abstract":"<div><div>2,3-butanediol (2,3-BDO) is a versatile platform chemical that can be produced via fermentation in aqueous solution. The energy intensive recovery of the high boiling 2,3-BDO from water via distillation hinders the economic viability of biotechnological produced 2,3-BDO. Hence, extraction-distillation processes using novel solvents from the class of terpenoids, namely menthol, thymol, and carvacrol, are proposed. To this end, binary and ternary liquid-liquid equilibrium (LLE) data for H₂O, 2,3-BDO, and each terpenoid, as well as boiling point data for 2,3-BDO and the respective terpenoid, are measured. The thermodynamic phase equilibria are correlated with the non-random two liquid (NRTL) model and consecutive process design of the extraction-distillation processes is conducted using Aspen Plus. Conventional solvents (isobutanol, 1-butanol, and oleylalcohol), thymol, and carvacrol are assessed in terms of specific exergy demand for the production of 2,3-BDO. The lowest specific exergy demands were found for oleyl alcohol (5.38 kJ g⁻¹) and thymol (5.14 kJ g⁻¹), carvacrol (5.49 kJ g⁻¹). Hence, terpenoids are a competitive class of solvents and should be included in solvent screening approaches.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"600 ","pages":"Article 114572"},"PeriodicalIF":2.7,"publicationDate":"2025-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144916915","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":"Experimental and theoretical study on ion association in [Hmim][halide] + methanol/dimethyl sulfoxide mixtures","authors":"Zhida Zuo ,&nbsp;Hui Wang ,&nbsp;Linghong Lu ,&nbsp;Xiaohua Lu ,&nbsp;Xiaoyan Ji","doi":"10.1016/j.fluid.2025.114571","DOIUrl":"10.1016/j.fluid.2025.114571","url":null,"abstract":"<div><div>The electrical conductivities of 1-hexyl-3-methylimidazolium halides ([Hmim][halide], halide = Cl^–, Br^–, I^–) were measured in methanol (MeOH) and dimethyl sulfoxide (DMSO) at dilute concentrations from 293.15 to 313.15 K, alongside liquid density measurements for parametrization. Molar conductivity (Λ) decreased with increasing IL concentration and decreasing temperature, with solvent effects predominating over those of anion size. Λ was higher in MeOH than in DMSO due to lower viscosity and greater ion dissociation of MeOH. Comparison with a previous study involving H₂O, MeOH, DMSO, and isopropanol confirmed that solvent viscosity is the dominant factor influencing Λ at infinite dilution. At higher IL concentrations, Λ in MeOH fell below that in H₂O, likely due to a reduced number of free ions and the formation of larger solvated ion complexes.</div><div>To analyze conductivity behavior, the Debye-Huckel-Onsager model was employed to determine the limiting molar conductivity (<em>Λ₀</em>), which was subsequently used in the Shedlovsky equation to calculate the association constant (<em>K_A</em>). For comparison, simultaneous regression of <em>Λ₀</em> and <em>K_A</em> was also performed. The results indicated that, within the same solvent, <em>Λ₀</em> increased with temperature, while <em>K_A</em> exhibited irregular trends. Across different solvents, <em>Λ₀</em> correlated with solvent viscosity, and <em>K_A</em> was influenced by dielectric constant and polarity. Solvent effects on both <em>Λ₀</em> and <em>K_A</em> were more pronounced than those of anion size, suggesting the dominant role of the solvent environment. Positive Eyring activation enthalpies showed the endothermic ion-pairing process. Additionally, the Walden product suggested stronger ion-solvent interactions and larger solvated ions in MeOH compared to DMSO. These findings provide deeper insight into IL conductivity in diverse solvent environments.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"600 ","pages":"Article 114571"},"PeriodicalIF":2.7,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144913458","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":"Bulk viscosity of hydrocarbon solutions at extreme state parameters. II. Solutions of cyclic and linear alkanes (C6H12 – C16H34)","authors":"A.N. Grigoriev,&nbsp;Yu.I. Kuzovkov,&nbsp;I.V. Markov,&nbsp;L.A. Bulavin","doi":"10.1016/j.fluid.2025.114552","DOIUrl":"10.1016/j.fluid.2025.114552","url":null,"abstract":"<div><div>Data on the bulk viscosity coefficient of a binary system composed of alkanes of different molecular structure, namely, cyclic (cyclohexane) and linear (n-hexadecane) are presented for the range of pressure 0.1–98.0 MPa and temperature 293–393 K for solutions with concentrations of 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0 mole fraction. The bulk viscosity coefficients were determined with an uncertainty of (8–10) % from experimental data on the absorption coefficient and sound velocity at the frequency of 28 MHz. The possibilities of the description of concentration dependences of the bulk viscosity coefficient <span><math><msub><mrow><mi>η</mi></mrow><mrow><mi>v</mi></mrow></msub></math></span>, with the help of Gruenberg–Nissan formula and the new approximation formula proposed here by authors are considered.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"600 ","pages":"Article 114552"},"PeriodicalIF":2.7,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144886858","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":"Microscopic description of the liquid–gas coexistence curve for Morse fluids in the immediate vicinity of the critical point","authors":"I.V. Pylyuk,&nbsp;M.P. Kozlovskii,&nbsp;R.V. Romanik","doi":"10.1016/j.fluid.2025.114551","DOIUrl":"10.1016/j.fluid.2025.114551","url":null,"abstract":"<div><div>The present work is aimed at investigating the behavior of Morse fluids in the immediate vicinity of the critical point within the framework of a cell model. This region is of both fundamental and practical importance, yet presents analytical challenges due to the significant influence of order parameter fluctuations. An analytical procedure is developed to construct the upper part of the liquid–gas coexistence curve and calculate its diameter, incorporating the non-Gaussian (quartic) distribution of fluctuations. An explicit expression is derived for the temperature-dependent analytical term appearing in the expression for the rectilinear diameter. The numerical evaluation of the relevant quantities is carried out using Morse potential parameters representative of sodium. The coexistence curve is constructed both with and without the inclusion of the analytical temperature-dependent term in the calculation. A specific condition is identified under which the agreement between the presented binodal branches and Monte Carlo simulation data from other study, extrapolated to the immediate vicinity of the critical point, is improved. It is shown that better agreement is achieved when the analytical term is included in the calculation of the liquid branch and omitted in the gas branch. The proposed analytical approach may provide useful insight for the theoretical study of critical phenomena in more complex fluid systems.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"600 ","pages":"Article 114551"},"PeriodicalIF":2.7,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144852457","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":"Optimized GC-PC-SAFT parameterization for high-accuracy thermodynamic prediction of diverse ionic liquids","authors":"Yiran Wang,&nbsp;Zhiyu Yan,&nbsp;Maogang He,&nbsp;Xiangyang Liu","doi":"10.1016/j.fluid.2025.114554","DOIUrl":"10.1016/j.fluid.2025.114554","url":null,"abstract":"<div><div>Ionic liquids (ILs) are emerging solvents, and the reliable prediction of thermodynamic properties is challenging for process design because of their diverse structures. The integration of the perturbed-chain statistical associating fluid theory equation of state (PC-SAFT EoS) with the group contribution (GC) method establishes a robust framework for thermodynamic property prediction. However, challenges remain in modeling properties of ILs through GC-PC-SAFT EoS, primarily due to limited group universality and insufficient systematic parameterization. In this study, complex anions and cations are divided into multiple smaller sub-groups, and the group contribution parameters of the GC-PC-SAFT EoS were determined based on extensive experimental data and the global search algorithm. The optimized parameterization achieved the accurate calculation, with average absolute relative deviations of 1.2% for the density and 2.5% for isobaric heat capacity across 129 ILs over a wide temperature and pressure range. Furthermore, model validation confirmed its strong predictive capability for the density, isobaric heat capacity, and speed of sound of both pure ILs and their binary mixtures.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"600 ","pages":"Article 114554"},"PeriodicalIF":2.7,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144829625","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":"Antisolvent selection method based on predictive thermodynamic models","authors":"Tae Hyun Kim ,&nbsp;Sung Shin Kang ,&nbsp;Seon Hwa Baek,&nbsp;Chae Hyun Bae,&nbsp;Jeong Won Kang","doi":"10.1016/j.fluid.2025.114553","DOIUrl":"10.1016/j.fluid.2025.114553","url":null,"abstract":"<div><div>Drowning-out crystallization is an effective technique for separating solutes from solutions by introducing a mass separation agent called an antisolvent. While previous studies using COSMO-SAC (SLE) were limited to binary solute–solvent equilibria, this research introduces the first integrated protocol for selecting an antisolvent. This protocol combines COSMO-SAC (SLE) with an infinite-dilution selectivity descriptor and a precipitation mass balance to analyze full ternary systems (solute, solvent, and antisolvent). New solid-liquid equilibrium (SLE) data were collected for succinic, glutaric, and adipic acids in 1-butanol or DMF with nine different antisolvents at a temperature of 298.15 K. Four predictive models—COSMO-SAC (SLE), COSMO-SAC (2017), NIST-modified UNIFAC, and original UNIFAC—were benchmarked against these data. The COSMO-SAC (SLE) model achieved a median relative deviation in precipitated mass of 58%, representing a threefold improvement over the next best model, marking the first quantitative validation of COSMO-SAC (SLE) for predicting precipitation yields. High selectivity values accurately forecast complete drowning-out or liquid-liquid phase separation, while low values indicate full solubility. Analysis of the σ-profile reveals a connection between the extent of polar and non-polar surface overlap and the observed phase behavior, providing a mechanistic understanding beyond simple empirical benchmarking. The resulting workflow—comprising model screening, selectivity ranking, σ-profile interpretation, and experimental validation—offers a reliable approach for selecting solvents and antisolvents in pharmaceutical and fine chemical crystallization.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"600 ","pages":"Article 114553"},"PeriodicalIF":2.7,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144913457","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":"Integrated experimental and theoretical investigation of hydrogen absorption and desorption in ZrMn2 compounds","authors":"Rached Ben Mehrez ,&nbsp;Chaker Briki ,&nbsp;Lilia El Amraoui ,&nbsp;Kais Ouni ,&nbsp;Abdelmajid Jemni","doi":"10.1016/j.fluid.2025.114543","DOIUrl":"10.1016/j.fluid.2025.114543","url":null,"abstract":"<div><div>This comprehensive study investigates the hydrogen absorption–desorption mechanisms in ZrMn₂ compounds through a combination of experimental and theoretical approaches. The research systematically explores the alloy's physical and thermodynamic properties, emphasizing its structural integrity and thermodynamic stability. Pressure–composition–temperature (PCT) isotherms are employed to evaluate the hydrogen storage capacity and reversibility. Concurrently, theoretical models based on statistical physics are used to elucidate macroscale interactions, internal energy variations, and lattice strain behavior during hydrogen cycling. The hydrogen uptake process begins with physisorption, followed by dissociative chemisorption of hydrogen molecules at the surface, which then diffuse into the alloy matrix. The findings advance the understanding of hydrogen-intermetallic interactions and offer valuable insights for the development of ZrMn₂-based materials in next-generation solid-state hydrogen storage systems, where optimizing storage capacity and kinetic performance is essential.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"599 ","pages":"Article 114543"},"PeriodicalIF":2.7,"publicationDate":"2025-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144750247","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":"Pressure and temperature dependent UNIQUAC model for methanol - water mixtures","authors":"Adina Werner ,&nbsp;Jongmin Kim ,&nbsp;Fabian Mauss","doi":"10.1016/j.fluid.2025.114533","DOIUrl":"10.1016/j.fluid.2025.114533","url":null,"abstract":"<div><div>A pressure dependency is included in a quadratic temperature dependent binary interaction parameter of the UNIQUAC model. The obtained activity coefficients for methanol-water mixtures are compared with only temperature dependent UNIQUAC and UNIFAC, and with calculated activity coefficients based on experimental data between 298.15 - 373.15 K and 0.1519 - 1.01325 bar produced with vapor-liquid equilibrium calculations and Wilson method. This model exhibits an overall good agreement. The predicted activity coefficients are more adaptable than those from models without pressure dependence, indicating potential for further improvement.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"599 ","pages":"Article 114533"},"PeriodicalIF":2.8,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144712888","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":"Mastering carbon nanotube dispersion: A simplified model for industrial and environmental innovation","authors":"Mohammad Hossein Keshavarz,&nbsp;Mojgan Fathi,&nbsp;Zeinab Shirazi","doi":"10.1016/j.fluid.2025.114534","DOIUrl":"10.1016/j.fluid.2025.114534","url":null,"abstract":"<div><div>Carbon nanotubes (CNTs) are celebrated for their extraordinary mechanical, electrical, and thermal properties, yet their industrial adoption remains hindered by aggregation issues. Achieving stable dispersion in organic solvents is critical for unlocking their potential in advanced composites, flexible electronics, energy storage, and environmental remediation. Current quantitative structure-property relationship (QSPR) models for predicting CNT dispersibility rely on computationally intensive descriptors, such as quantum-chemical or topological parameters, which limit their practical accessibility. This study introduces a streamlined predictive model that uses only three intuitive solvent descriptors—hydrogen-bonding capacity, hydrophobicity, and a novel π-π interaction parameter—to achieve exceptional accuracy (training r² = 0.917, external validation r² = 0.963) and precision (RMSE = 0.236 vs. 0.337 for prior models). Innovations include leveraging amine/amide functional groups for stabilization and eliminating dependence on complex computational tools. The model’s robustness is validated through rigorous statistical testing (leave-many-out cross-validation q² = 0.823) and applicability domain analysis. By prioritizing simplicity without compromising performance, this work bridges the gap between lab-scale nanotechnology research and scalable industrial applications, such as water purification and pollution remediation, offering a user-friendly alternative to traditional QSPR frameworks.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"599 ","pages":"Article 114534"},"PeriodicalIF":2.8,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144714441","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":"Solving the UVN-flash problem in TVN-space","authors":"Pardeep Kumar ,&nbsp;Patricio I. Rosen Esquivel","doi":"10.1016/j.fluid.2025.114528","DOIUrl":"10.1016/j.fluid.2025.114528","url":null,"abstract":"<div><div>In this paper, we investigate the phase equilibrium problem for multicomponent mixtures under specified internal energy (<span><math><mi>U</mi></math></span>), volume (<span><math><mi>V</mi></math></span>), and mole numbers (<span><math><mrow><msub><mrow><mi>N</mi></mrow><mrow><mn>1</mn></mrow></msub><mo>,</mo><msub><mrow><mi>N</mi></mrow><mrow><mn>2</mn></mrow></msub><mo>,</mo><mo>…</mo><mo>,</mo><msub><mrow><mi>N</mi></mrow><mrow><mi>n</mi></mrow></msub></mrow></math></span>), commonly known as the UVN-flash problem. While conventional phase equilibrium calculations typically use pressure–temperature-mole number (<span><math><mrow><mi>P</mi><mi>T</mi><mi>N</mi></mrow></math></span>) specifications, the UVN formulation is essential for dynamic simulations of closed systems and energy balance computations. Existing approaches, including those based on iterative pressure–temperature updates and direct entropy maximization, can suffer from computational inefficiencies due to inner Newton iterations needed to solve for temperature <span><math><mi>T</mi></math></span> at specified internal energy <span><math><mi>U</mi></math></span> and volume <span><math><mi>V</mi></math></span>.</div><div>In this work, we present a reformulation of the UVN-flash problem that eliminates the need for the inner Newton iterations, addressing a computational bottleneck. We begin with stability analysis and discuss a strategy to generate the initial guess for the UVN-flash from the stability analysis results. We then reformulate the UVN-flash problem in TVN-space as constrained entropy maximization. We provide a detailed derivation of Michelsen’s Q-function using the method of Lagrange multipliers, illustrating its direct application in solving the UVN-flash problem. Furthermore, we discuss the numerical methods used, including gradient and Hessian computations. The reformulation is validated against benchmark cases, demonstrating improved efficiency.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"599 ","pages":"Article 114528"},"PeriodicalIF":2.8,"publicationDate":"2025-07-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144672324","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}