Fluid Phase Equilibria最新文献

Freezing transitions in colloidal nanoparticles: Interplay of dispersive and electrostatic interactions in confined two-dimensional systems 胶体纳米颗粒中的冻结转变：在受限的二维系统中色散和静电相互作用的相互作用

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-25 DOI: 10.1016/j.fluid.2025.114448

Moushila Bayen, Anupam Kumar, Pankaj Mishra

引用次数: 0

Thermodynamic modeling of poorly specified mixtures using NMR fingerprinting and group-contribution equations of state 使用核磁共振指纹和群体贡献状态方程的不良指定混合物的热力学建模

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-24 DOI: 10.1016/j.fluid.2025.114446

Jens Wagner, Zeno Romero, Kerstin Münnemann, Thomas Specht, Fabian Jirasek, Hans Hasse

{"title":"Thermodynamic modeling of poorly specified mixtures using NMR fingerprinting and group-contribution equations of state","authors":"Jens Wagner, Zeno Romero, Kerstin Münnemann, Thomas Specht, Fabian Jirasek, Hans Hasse","doi":"10.1016/j.fluid.2025.114446","DOIUrl":"10.1016/j.fluid.2025.114446","url":null,"abstract":"<div><div>Mixtures of which the composition is only partially known are ubiquitous in chemical and biotechnological processes and pose a significant challenge for process design and optimization since classical thermodynamic models require complete speciation, which cannot be obtained with reasonable effort in many situations. In prior work, we have introduced a framework combining standard nuclear magnetic resonance (NMR) experiments and machine-learning (ML) algorithms for the automated elucidation of the group composition of unknown mixtures and the rational definition of pseudo-components and have applied the results together with group-contribution (GC) models of the Gibbs excess energy. In the present work, we extend this approach to the application of group-contribution equations of state (GC-EOS), enabling the predictive modeling of basically all thermodynamic properties of such mixtures. As an example, we discuss the application of the SAFT-<span><math><mi>γ</mi></math></span> Mie GC-EOS for predicting the CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> solubility in several test mixtures of known composition. However, the information on their composition was not used in applying our method; it was only used to generate reference results with the SAFT-<span><math><mi>γ</mi></math></span> Mie EOS that were compared to the predictions from our method. In addition, the CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> solubility in the test mixtures was also determined experimentally by NMR spectroscopy. The results demonstrate that the new approach for modeling poorly specified mixtures also works with GC-EOS, which further extends its applicability in process design and optimization.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114446"},"PeriodicalIF":2.8,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143873745","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Vapor–liquid and liquid–liquid equilibrium in mixtures of water + isobutanol/n-butanol + isobutylal/n-butylal 水+异丁醇/正丁醇+异丁醛/正丁醛混合物的汽液平衡和液液平衡

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-22 DOI: 10.1016/j.fluid.2025.114440

Lukas Winklbauer, Jieyu Qian, Jakob Burger

引用次数: 0

Effect of MgCl2 and pressure on vapor-liquid equilibrium in separation of water in water + ethylene glycol system MgCl2和压力对水+乙二醇体系中水分离汽液平衡的影响

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-22 DOI: 10.1016/j.fluid.2025.114451

Weichao Tang , Mengjie Luo , Hang Chen , Xingfu Song

{"title":"Effect of MgCl2 and pressure on vapor-liquid equilibrium in separation of water in water + ethylene glycol system","authors":"Weichao Tang , Mengjie Luo , Hang Chen , Xingfu Song","doi":"10.1016/j.fluid.2025.114451","DOIUrl":"10.1016/j.fluid.2025.114451","url":null,"abstract":"<div><div>In the process of preparing anhydrous magnesium chloride by the alcohol-ammonia method using ethylene glycol (EG) as the solvent, the dehydration process of the water + EG + magnesium chloride (MgCl<sub>2</sub>) system is crucial. Therefore, this work analyzed the effect of MgCl<sub>2</sub> and pressure on vapor-liquid equilibrium in separation of water in water + ethylene glycol system. The isobaric vapor-liquid equilibrium (VLE) data for the water + EG + MgCl<sub>2</sub> system were measured at 101.3 kPa with MgCl<sub>2</sub> mass fractions of 0, 0.05, 0.07, and 0.10. It was found that the addition of MgCl<sub>2</sub> raised the phase equilibrium temperature of the water + EG system and decreased the relative volatility of water relative to EG. Additionally, the VLE data for the water + EG + MgCl<sub>2</sub> system at 71.3, 41.3 and 11.3 kPa were measured with the MgCl<sub>2</sub> mass fraction of 0.10. The equilibrium temperature was effectively lowered, and the relative volatility was significantly increased by reducing the system pressure. The experimental data obtained in this work was consistent in thermodynamics test through Van Ness method. Moreover, the NRTL model was used to correlate experimental data. The root - mean - square deviations between the measured and calculated values of temperature (T) and vapor phase mole fraction (y<sub>1</sub>) were less than 0.53 K and 0.006 respectively. The NRTL model prediction with the regressed parameters was found in agreement with the experimental data.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114451"},"PeriodicalIF":2.8,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143882862","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Thermodynamic properties of some aqueous ionic liquid solutions using ion-SAFT-VR EOS 离子液体水溶液热力学性质的离子- saft - vr EOS研究

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-18 DOI: 10.1016/j.fluid.2025.114447

Ayeh Emrani, Ali Maghari

{"title":"Thermodynamic properties of some aqueous ionic liquid solutions using ion-SAFT-VR EOS","authors":"Ayeh Emrani, Ali Maghari","doi":"10.1016/j.fluid.2025.114447","DOIUrl":"10.1016/j.fluid.2025.114447","url":null,"abstract":"<div><div>The statistical association fluid theory (SAFT) approach for attractive potentials of variable range combined with interionic interactions, to describe some aqueous solutions of imidazolium ionic liquids (ILs) with different anion structures. The anions analyzed encompass [SCN]<sup>-</sup>, [DCA]<sup>–</sup>, [BF4]<sup>-</sup>, [NTF<sub>2</sub>]<sup>-</sup> and [PF<sub>6</sub>]<sup>-</sup> which show the effect of systematically change of the substituents on the anion. The proposed equation of state is a combination of a square-well variable range and a mean spherical approximation (MSA) corresponding to the restrictive primitive model to describe the long-range interactions of ILs. Water is characterized as a bipolar associating liquid combining the four-site model and a square-well potential with a constant dielectric continuum. The accurate predictions of volumetric properties for pure ILs and <span><math><mrow><mi>p</mi><mi>ρ</mi><mi>T</mi></mrow></math></span> of water as well as the thermodynamic properties of binary aqueous IL solutions are significant evidence of the capability and excellent performance of the ion-SAFT-VR model. Parameters of the new version of the model have been reported and the model tested for an impressively large number of data sets. For binary mixtures of ILs and water, binary interaction coefficients were obtained by fitting experimental data at constant pressure and phase concentrations. The results show the satisfactory predictability of the ion-SAFT-VR EOS in modeling the thermodynamic properties of bulk systems, which indicates the reliability of the employed EOS. Due to the excellent results obtained for pure IL densities and the satisfactory results observed for aqueous solution of ILs, we can confidently conclude that the approach provides an overall commendable description of most IL systems.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114447"},"PeriodicalIF":2.8,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143863664","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Solubility of water in bitumen 水在沥青中的溶解度

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-15 DOI: 10.1016/j.fluid.2025.114442

B. Zuluaga, F.F. Schoeggl, H.W. Yarranton

{"title":"Solubility of water in bitumen","authors":"B. Zuluaga, F.F. Schoeggl, H.W. Yarranton","doi":"10.1016/j.fluid.2025.114442","DOIUrl":"10.1016/j.fluid.2025.114442","url":null,"abstract":"<div><div>Liquid/liquid-vapor (L/LV) and aqueous-liquid/aqueous-liquid-vapor (AL/ALV) boundaries of pseudo-binary mixtures of bitumen and water were measured using the isothermal stepwise volume expansion method at conditions relevant to <em>in situ</em> heavy oil operations (temperatures from 180 to 280 °C and pressures from 1.5 to 5 MPa). The L/AL boundary was determined from the intersection of the L/LV and AL/ALV boundaries. An activity coefficient model of the pseudo-binary system was used to check the self-consistency of the L/LV measurements. The Advanced Peng Robinson equation of state, which has a distinct alpha function for water, was used to model the VLE and VLLE data. For this model, the oil was characterized into pseudo-components based on a SimDist assay and the specific gravity and asphaltene content of the oil. Temperature dependent binary interaction parameters between bitumen pseudo-components and water were tuned such that the model fit the measurements to within the experimental error. Isothermal pressure-composition phase diagrams were generated for the pseudo-binary mixtures at each temperature. Finally, a straightforward correlation for the solubility limit of water in bitumen as a function of temperature was developed using the data in this study and from the literature. The average deviation of the correlation was 0.5 wt % below 340 °C.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114442"},"PeriodicalIF":2.8,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834442","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Thermodiffusion of CO2 mixtures in the extended critical region CO2混合物在扩展临界区域的热扩散

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-14 DOI: 10.1016/j.fluid.2025.114438

Gabriela Guevara-Carrion, Denis Saric, Jadran Vrabec

{"title":"Thermodiffusion of CO2 mixtures in the extended critical region","authors":"Gabriela Guevara-Carrion, Denis Saric, Jadran Vrabec","doi":"10.1016/j.fluid.2025.114438","DOIUrl":"10.1016/j.fluid.2025.114438","url":null,"abstract":"<div><div>Thermodiffusion, also known as Soret effect, stands for the mass flux driven by a temperature gradient, leading to partial component separation in fluid mixtures. While typically small in magnitude and often neglected, thermodiffusion can become significant under specific conditions, such as in the extended critical region. In this work, the thermodiffusion behavior of diluted supercritical mixtures of carbon dioxide with methane, ethane, or isobutane is investigated with molecular simulation techniques. Thermodiffusion is studied along the <span><math><mrow><mn>9</mn><mspace></mspace><mi>MPa</mi></mrow></math></span> isobar over a temperature range from <span><math><mrow><mi>T</mi><mo>=</mo><mn>290</mn></mrow></math></span> to 345 K, where singular thermodynamic and transport properties are observed. Attention is given to the crossover region near the critical point, where asymptotic power laws no longer apply, but long-range fluctuations still influence fluid behavior. Within this region, characterized by the Widom line, extreme values for the thermodiffusion and Soret coefficients are predicted. The underlying mechanisms responsible for this behavior are explored, and it is shown to be primarily driven by the extrema of the partial molar enthalpy of the solvent in the extended critical region.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114438"},"PeriodicalIF":2.8,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842525","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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ANN-based estimation of pure-component parameters of PC-SAFT equation of state using quantum chemical data 基于神经网络的量子化学PC-SAFT状态方程纯组分参数估计

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-14 DOI: 10.1016/j.fluid.2025.114444

Hiroaki Matsukawa, Yusuke Miyagi, Katsuto Otake

{"title":"ANN-based estimation of pure-component parameters of PC-SAFT equation of state using quantum chemical data","authors":"Hiroaki Matsukawa, Yusuke Miyagi, Katsuto Otake","doi":"10.1016/j.fluid.2025.114444","DOIUrl":"10.1016/j.fluid.2025.114444","url":null,"abstract":"<div><div>The perturbed chain-statistical associating fluid theory equation of state (PC-SAFT EoS) is a physical property estimation tool that can be used to calculate a wide range of substance types, temperatures, and pressures. To perform calculations using the PC-SAFT EoS, substance-specific pure-component parameters are required, which are generally determined from liquid density and saturated vapor pressure. Few studies have reported on these parameters, and methods that can obtain pure-component parameters without relying on measured physical properties remain elusive. In this study, an artificial neural network (ANN) is introduced to predict the pure-component parameters of the PC-SAFT EoS. The molecular information estimated from a Gaussian software was used as the input. In addition, we optimized the structure of the ANN by varying the transfer function, number of neurons, and number of hidden layers. The optimized ANN comprises a hard sigmoid transfer function composed of two hidden layers, with 20 and 10 neurons in the first and second layer, respectively. This model can determine the pure-component parameters of the PC-SAFT EoS for a wide range of substance types. Furthermore, SHapley Additive exPlanations analysis on the optimized ANN demonstrates that the contributions of the polarizability and dipole moment are large. However, the feature values related to the shape of the substance are lacking. These results contribute to expanding the range of applications for property estimation using EoS.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114444"},"PeriodicalIF":2.8,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143842524","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Using Physical Property Models and Artificial Intelligence to Design Chemical Products 利用物理性质模型和人工智能设计化工产品

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-11 DOI: 10.1016/j.fluid.2025.114441

Kevin G. Joback

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Artificial neural network-based estimation of interaction parameters between carbon dioxide and organic solvents using the Peng–Robinson equation of state with the van der Waals one-fluid mixing rule and quantum chemical data 基于van der Waals单流体混合规则的Peng-Robinson状态方程和量子化学数据的二氧化碳与有机溶剂相互作用参数的人工神经网络估计

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-11 DOI: 10.1016/j.fluid.2025.114443

Hiroaki Matsukawa, Emiri Kobayashi, Katsuto Otake

{"title":"Artificial neural network-based estimation of interaction parameters between carbon dioxide and organic solvents using the Peng–Robinson equation of state with the van der Waals one-fluid mixing rule and quantum chemical data","authors":"Hiroaki Matsukawa, Emiri Kobayashi, Katsuto Otake","doi":"10.1016/j.fluid.2025.114443","DOIUrl":"10.1016/j.fluid.2025.114443","url":null,"abstract":"<div><div>The Peng–Robinson (PR)-van der Waals (vdW) model, which combines the PR equation of state with the vdW one-fluid mixing rule, is often used to estimate the physical properties of CO<sub>2</sub>/organic solvent mixtures. Calculating these properties using the PR-vdW model requires interaction parameters <em>k<sub>ij</sub></em>; however, reports on these parameters are limited. This article introduces an artificial neural network (ANN) to predict <em>k<sub>ij</sub></em> between CO<sub>2</sub> and organic solvents, using pure-component parameters and molecular information as inputs. The molecular information is obtained through the general-purpose quantum chemical calculation software Gaussian. In addition, the ANN is optimized by varying the transfer function, number of neurons, and number of hidden layers. The optimized ANN employs a tanh function as the transfer function for the hidden layers, with two hidden layers containing 40 and 10 neurons. This model effectively predicts <em>k<sub>ij</sub></em> for a wide range of substances and temperature conditions. Furthermore, SHapley Additive exPlanations analysis of the optimized ANN reveals a significant contribution from the quadrupole moment, likely due to quadrupole interactions between CO<sub>2</sub> and the organic solvents. These results support the estimation of the physical properties of CO<sub>2</sub>/organic solvent mixtures.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"596 ","pages":"Article 114443"},"PeriodicalIF":2.8,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143834443","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}

引用次数: 0