Fluid Phase Equilibria最新文献

{"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}

{"title":"Ternary Liquid – Liquid and Binary Liquid – Liquid, Solid – Liquid, and Vapour – Liquid equilibria of systems containing ε-Caprolactam, Water, n-Hexadecane, and o-Xylene","authors":"Zubair Riaz,&nbsp;Petri Uusi-Kyyny,&nbsp;Roshi Dahal,&nbsp;Juha-Pekka Pokki,&nbsp;Ville Alopaeus","doi":"10.1016/j.fluid.2025.114503","DOIUrl":"10.1016/j.fluid.2025.114503","url":null,"abstract":"<div><div>This study reports equilibrium experimental data of binary and ternary systems containing ε-caprolactam. Solid – liquid equilibria (SLE), and isobaric bubble points were measured for the binary system ε-caprolactam + o-xylene. SLE and liquid – liquid equilibria (LLE) were measured for the binary system ε-caprolactam + n-hexadecane. Ternary LLE were measured for the systems ε-caprolactam + water + n-hexadecane or o-xylene at temperatures 298 – 323 K and atmospheric pressure. The isobaric bubble point and the ternary systems’ phase boundaries were predicted prior to the experiments with the universal quasi-chemical functional group activity coefficients – Dortmund modified (UNIFAC–Dortmund) model to ascertain the experimental conditions. Binary interaction parameters for the nonrandom, two-liquid (NRTL) model were regressed based on the measured systems of this work and additional data from the literature sources. Good agreement was found between the experimental data and the NTRL model. The results from this study provide insights into the phase behaviour of mixtures containing ε-caprolactam, facilitating process design in relevant industrial processes.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114503"},"PeriodicalIF":2.8,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144338867","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":"Effects of temperature and flue gas composition on miscibility behavior between flue gas and gas condensate","authors":"Changfeng Xi ,&nbsp;Fang Zhao ,&nbsp;Xiaokun Zhang ,&nbsp;Bojun Wang ,&nbsp;Changxu Wu ,&nbsp;Huazhou Li","doi":"10.1016/j.fluid.2025.114502","DOIUrl":"10.1016/j.fluid.2025.114502","url":null,"abstract":"<div><div>Thermal miscible flooding has shown promise in enhancing light oil recovery from gas condensate reservoirs. In this process, the generated flue gases could become miscible with gas condensate under elevated reservoir temperatures. To study the miscibility behavior between flue gas and gas condensate, we develop a thermodynamic model based on the Peng-Robinson equation of state (PR EOS) coupled with Peneloux volume translation, for a benchmark gas condensate sample. The pseudocomponents’ properties are tuned to match the constant composition expansion (CCE) and the constant volume depletion (CVD) test data. The tuned model can well reproduce measured data (e.g., relative volume and liquid dropout) in these tests. We then apply it to calculate the phase envelopes of N₂-gas condensate, CO₂-gas condensate, and CO₂_<img>N₂-gas condensate mixtures, revealing the shifts in original phase envelopes. Next, to investigate the influences of temperature and flue gas composition on miscibility behavior, we utilize the analytical tie line method and the cell-to-cell method to calculate the MMPs and drive types of different flue gas-gas condensate mixtures. It is found that the MMP of a given injection gas first increases with temperature, reaches a peak, and then decreases. The dimensionless fraction of vaporizing mechanism of a given injection gas decreases with temperature. The highest MMPs of CO₂ and N₂ are 506 bara at 350 °C and 620 bara at 250 °C, respectively. If the flue gas contains more N₂, the peak MMP and the dimensionless fraction of vaporizing mechanism increase, but the temperature corresponding to the peak MMP is reduced.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114502"},"PeriodicalIF":2.8,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144314094","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":"An equation-based batch distillation simulation to evaluate the effect of multiplicities in thermodynamic activity coefficients","authors":"Jennifer Werner ,&nbsp;Jochen Schmid ,&nbsp;Lorenz T. Biegler ,&nbsp;Michael Bortz","doi":"10.1016/j.fluid.2025.114465","DOIUrl":"10.1016/j.fluid.2025.114465","url":null,"abstract":"<div><div>In this paper, we investigate the influence of multiplicities in activity coefficients on batch distillation processes. In order to do so, we develop a rigorous simulation of batch distillation processes based on the MESH equations. In particular, we propose a novel index reduction method to transform the original index-2 system into a well-posed differential-algebraic system of index 1. With the help of this simulation, we then explore whether the alternative NRTL parameters, which yield indistinguishable activity coefficients and VLE diagrams when compared to the reference data, can produce distinguishable profiles in dynamic simulations. As it turns out, this can happen in general and we explain the reasons behind the dynamic distinguishability.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114465"},"PeriodicalIF":2.8,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144489338","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":"Prediction of pharmaceutical solubility in mixed-solvents with a local composition-quantum energy parameter model","authors":"Jia Lin Lee ,&nbsp;Gun Hean Chong ,&nbsp;Masaki Ota ,&nbsp;Haixin Guo ,&nbsp;Richard Lee Smith","doi":"10.1016/j.fluid.2025.114500","DOIUrl":"10.1016/j.fluid.2025.114500","url":null,"abstract":"<div><div>Theoretical approaches for estimating pharmaceutical solubility in solvents can reduce experimental effort for optimizing design of separation and purification steps. In this work, an approach is developed for solvent selection of pharmaceuticals that is based on geometric energy difference (GED), determined from interaction energies via density functional theory and time dependent density functional theory calculations. Interaction energies were optimized through surface charge density predictions at the aug-cc-pvdz/blyp level of theory, with computational efficiency enhanced via machine learning. Comparison between GED and Hansen solubility parameter (HSP) approaches for solvent selection revealed that the GED approach was more selective than the HSP relative energy difference solubility sphere approach. An activity coefficient model was developed to predict pharmaceutical solubility in mixed-solvents based on local composition theory and optimization of quantum energy parameters (LC-QEP model). For 41 pharmaceutical-mixed-solvent systems, the LC-QEP model predicted API solubility to within an average relative deviation logarithm (ARDln) of 0.669, compared with an ARDln of 1.755 for the RST model based on HSP. The LC-QEP model was compared with other molecular-based models for prediction of API solubility. For naproxen- and paracetamol- mixed-solvent systems, average ARDln values for the LC-QEP model (0.117) were lower than those of the PC-SAFT equation of state model (0.369). For the vanillin-water-ethanol system, average ARDln values were lower for the LC-QEP model (0.137) than the COSMO-RS model (ARDln=0.294). For the aspirin-methylcyclohexane-ethanol system, average ARDln values of the PC-SAFT equation of state based on COSMO (0.102) were lower than those of the LC-QEP model (0.153) which may be attributed to weak interactions being over-estimated by the LC-QEP model. The GED approach can be used to reliably select solvents for pharmaceuticals and the LC-QEP model is able to predict API solubilities in mixed-solvent systems with lower deviations than several predictive models.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114500"},"PeriodicalIF":2.8,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144314008","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 investigation of liquid density for n-pentane + n-decane mixtures at temperatures from 283 K to 363 K and pressures up to 100 MPa","authors":"Tao Jia ,&nbsp;Jinpeng Yang ,&nbsp;Jia Yu","doi":"10.1016/j.fluid.2025.114501","DOIUrl":"10.1016/j.fluid.2025.114501","url":null,"abstract":"<div><div>Knowledge of the accurate <em>pρTx</em> behavior of hydrocarbon mixtures at different temperatures and pressures is indispensable for simulating reservoir behavior, optimizing recovery processes, and predicting the thermodynamic properties. The compressed liquid densities of <em>n</em>-pentane(1) + <em>n</em>-decane(2) binary mixtures with mole fraction <em>x</em>₁ = 0.1024, 0.2978, 0.5145, 0.7036, and 0.9113 were measured using a vibrating tube densimeter at temperatures from 283 K to 363 K, and pressures up to 100 MPa. The relative uncertainty for density measurement of <em>n</em>-pentane + <em>n</em>-decane binary mixtures of 0.99 mol fraction purity is 0.1 %. The densities of binary mixtures were correlated with the modified Tait equation, and the absolute average deviations of the experimental and calculated values were 0.005 %, 0.005 %, 0.006 %, 0.008 %, and 0.009 %, respectively. In addition, the isothermal compressibility, the isobaric thermal expansivity, and excess molar volume were calculated from experimental densities.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"598 ","pages":"Article 114501"},"PeriodicalIF":2.8,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144314088","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}