Fluid Phase Equilibria最新文献

英文中文

A second-order Dry Glass Reference Perturbation Theory for modeling sorption in glassy polymers: applications to systems containing light gases, alcohols, and water vapor

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-03-11 DOI: 10.1016/j.fluid.2025.114410

Hasan Ismaeel , Bennett D. Marshall , Eleonora Ricci , Maria Grazia De Angelis

The solubility of gases and vapors plays a critical role in determining the overall performance of membrane-based separation processes. Through the use of advanced Equations of State (EoS), the Non-Equilibrium Thermodynamics for Glassy Polymers (NET-GP) theory rose into prominence as a powerful correlative and predictive tool for the sorption of guest species in glassy polymers. The recently proposed Dry Glass Reference Perturbation Theory (DGRPT) provided a method to account for the polymer swelling through the NET-GP framework. In this work, we introduce a second-order modification to the DGRPT that improves upon the model’s flexibility in representing different types of isotherms. We have also investigated different association and parameterization schemes for water and alcohol sorption using the PC-SAFT EoS in glassy polymers. For the non-self associating polymers investigated here, our results concluded that the sorption of alcohols can be represented adequately using the induced association assumptions formulated by Kleiner and Sadowski. On the contrary, the same assumptions often lead to poor water sorption results. We speculate that the Wolbach and Sandler combining rule may be incapable of representing the cross-association effects between water and the glassy polymer. As a result, we fitted the cross association volume of bonding (κ

_{A_{i} B_{j}}

) on the sorption data while fixing the cross association energetic parameter (ε

_{A_{i} B_{j}}

) to half of water’s parameter. The adjusted κ

_{A_{i} B_{j}}

can then be treated as a temperature-independent parameter, while the effects of temperature variation can be delegated to the binary interaction parameter (k

_{i j}

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引用次数: 0

Solid–liquid equilibria of selected ternary systems containing diphenyl carbonate, alcohol, dialkyl carbonate, and phenol

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-03-08 DOI: 10.1016/j.fluid.2025.114420

Hiroyuki Matsuda , Yuki Ohashi , Tomoya Tsuji , Ken Naito , Yusuke Kakuta , Kiyofumi Kurihara , Katsumi Tochigi

We studied the solid–liquid equilibria (SLE) of five ternary systems for application to the purification of diphenyl carbonate (DPC) during crystallization. These systems contained DPC, alcohol, dimethyl carbonate (DMC), diethyl carbonate (DEC), and phenol, i.e., ethanol + DEC + DPC, methanol + DMC + DPC, phenol + DMC + DPC, ethanol + phenol + DPC, and DEC + phenol + DPC. The SLE data of these ternary systems were experimentally determined at atmospheric pressure and temperatures of approximately 245 – 352 K. The SLE measurements of the ternary systems were made for pseudo-binary systems by varying the value of the mole fraction (on a DPC-free basis) of one component of the binary system. The melting points were experimentally determined using a synthetic, visual technique we designed in a previous study. The experimental SLE data of the ethanol + DEC + DPC and methanol + DMC + DPC systems were compared with the predictions of the nonrandom two-liquid model based on binary interaction parameters determined for the constituent binary systems. The predictions of the NIST modified UNIFAC group contribution method were also assessed.

{"title":"Solid–liquid equilibria of selected ternary systems containing diphenyl carbonate, alcohol, dialkyl carbonate, and phenol","authors":"Hiroyuki Matsuda , Yuki Ohashi , Tomoya Tsuji , Ken Naito , Yusuke Kakuta , Kiyofumi Kurihara , Katsumi Tochigi","doi":"10.1016/j.fluid.2025.114420","DOIUrl":"10.1016/j.fluid.2025.114420","url":null,"abstract":"<div><div>We studied the solid–liquid equilibria (SLE) of five ternary systems for application to the purification of diphenyl carbonate (DPC) during crystallization. These systems contained DPC, alcohol, dimethyl carbonate (DMC), diethyl carbonate (DEC), and phenol, i.e., ethanol + DEC + DPC, methanol + DMC + DPC, phenol + DMC + DPC, ethanol + phenol + DPC, and DEC + phenol + DPC. The SLE data of these ternary systems were experimentally determined at atmospheric pressure and temperatures of approximately 245 – 352 K. The SLE measurements of the ternary systems were made for pseudo-binary systems by varying the value of the mole fraction (on a DPC-free basis) of one component of the binary system. The melting points were experimentally determined using a synthetic, visual technique we designed in a previous study. The experimental SLE data of the ethanol + DEC + DPC and methanol + DMC + DPC systems were compared with the predictions of the nonrandom two-liquid model based on binary interaction parameters determined for the constituent binary systems. The predictions of the NIST modified UNIFAC group contribution method were also assessed.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114420"},"PeriodicalIF":2.8,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143644980","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

Modeling of ionic liquid solubility in supercritical carbon dioxide + co-solvent phase predicted by ε*-modified Sanchez-Lacombe equation of state

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-03-05 DOI: 10.1016/j.fluid.2025.114417

Yuya Hiraga , Ikuo Ushiki

Supercritical fluid deposition (SCFD) using supercritical carbon dioxide (CO₂) has environmental advantages and enables the uniform and precise impregnation of ionic liquids (ILs) into porous supports. In general, the solubility of ILs in CO₂ is extremely low, but it can be greatly increased by adding a co-solvent. However, due to the diversity of IL and co-solvent combinations, models for predicting IL solubility remain limited. This study employs the ε*-modified Sanchez-Lacombe equation of state (ε*-mod SL-EoS) to predict IL solubility in supercritical CO₂ + co-solvent systems. Compared to the Peng-Robinson equation of state (PR-EoS) previously used, ε*-mod SL-EoS, derived from lattice fluid theory, has superior predictive capabilities, particularly for systems involving heavy molecules like ILs. Pure component parameters for ILs, CO₂, and co-solvents were determined through high-pressure density and vapor pressure correlations. Binary interaction parameters for IL + CO₂, CO₂ + co-solvent, and IL + co-solvent systems were fitted using available phase equilibrium data. Ternary phase equilibrium predictions using ε*-mod SL-EoS showed improved accuracy, achieving an average logarithmic AARD of 11.0%, outperforming PR-EoS (13.8%). The results highlight the ε*-mod SL-EoS as a robust predictive tool for IL solubility in CO₂-rich phases, even under dilute conditions with co-solvents, offering valuable insights for optimizing the SCFD processes.

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引用次数: 0

Investigation of contribution of the intermolecular potential attraction term in surface tension of refrigerant fluids

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-03-04 DOI: 10.1016/j.fluid.2025.114408

Reza Khordad

Theoretical prediction of thermophysical properties of refrigerant fluids using different intermolecular potential models is an attractive challenge in condensed matter physics. For this purpose, in this work, both refrigerant fluids including pure and binary mixtures are considered and their surface tension (

γ

) has been theoretically calculated. To obtain the surface tension of refrigerant fluids, three potential models are proposed. The potentials have the same repulsive parts and different attractive terms. The Ornstein-Zernike (OZ) integral equation by the hypernetted chain (HNC) closure is employed to find the pair correlation functions. The OZ equation is numerically solved by expansion of the correlation functions and HC closure in terms of angular functions in Fourier space. After obtaining the radial distribution function for any potential, the surface tension has been computed. The surface tension of each refrigerant fluid is calculated by three potential models. Our obtained theoretical results are compared with the experimental available data. The findings show that for each refrigerant fluid, one of the potential models show better agreement in comparing with experimental results. It means that the attractive term is one of the influencing factors in predicting the surface tension of refrigerant fluids. For pure refrigerant fluids, the best results obtained for R32 with ADD

\sim ░ % 0.9

. The best result is obtained for the mixture of R32+R1234yf with ADD

\sim ░ % 1.2

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引用次数: 0

An improved crossover SRK EOS for more accurate assessment of thermodynamic properties of CO2+pentane binary system

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-03-01 DOI: 10.1016/j.fluid.2025.114409

Kexin Ren, Ao Dong, Yuhang Chen, Yiran Wang, Taotao Zhan, Maogang He, Ying Zhang

The CO₂ transcritical power cycles in medium-high temperature areas are gaining attention for industrial heat recovery. At present, increasing studies focus on CO₂-based mixtures, particularly the CO₂+pentane binary mixture, due to its high thermal efficiency and low operating pressure. Based on this, high-precision calculation of thermodynamic properties is essential. In this study, the crossover SRK (CSRK) equation of state (EoS) based on Kiselev's crossover method is established, then the phase equilibrium properties, second-order thermodynamic properties, and single-phase region density for pentane and CO₂+pentane binary system are investigated using CSRK. Our research reveals that CSRK can accurately describe the thermodynamic properties of working fluids in near-critical region, precisely explore the change law of critical region density, and improve calculation accuracy of thermodynamic properties in far-critical region, which is suitable for engineering application. The CSRK significantly improves the calculation accuracy on liquid density, reducing the average absolute relative deviation (AARD) by more than half to 1.89 % compared with multi-parameter EoS. Additionally, a new phase equilibrium iterative solution method of binary mixtures is proposed, which has higher calculation efficiency and faster evaluation of the response of system to different disturbances, providing important support for future dynamic analysis.

{"title":"An improved crossover SRK EOS for more accurate assessment of thermodynamic properties of CO2+pentane binary system","authors":"Kexin Ren, Ao Dong, Yuhang Chen, Yiran Wang, Taotao Zhan, Maogang He, Ying Zhang","doi":"10.1016/j.fluid.2025.114409","DOIUrl":"10.1016/j.fluid.2025.114409","url":null,"abstract":"<div><div>The CO<sub>2</sub> transcritical power cycles in medium-high temperature areas are gaining attention for industrial heat recovery. At present, increasing studies focus on CO<sub>2</sub>-based mixtures, particularly the CO<sub>2</sub>+pentane binary mixture, due to its high thermal efficiency and low operating pressure. Based on this, high-precision calculation of thermodynamic properties is essential. In this study, the crossover SRK (CSRK) equation of state (EoS) based on Kiselev's crossover method is established, then the phase equilibrium properties, second-order thermodynamic properties, and single-phase region density for pentane and CO<sub>2</sub>+pentane binary system are investigated using CSRK. Our research reveals that CSRK can accurately describe the thermodynamic properties of working fluids in near-critical region, precisely explore the change law of critical region density, and improve calculation accuracy of thermodynamic properties in far-critical region, which is suitable for engineering application. The CSRK significantly improves the calculation accuracy on liquid density, reducing the average absolute relative deviation (AARD) by more than half to 1.89 % compared with multi-parameter EoS. Additionally, a new phase equilibrium iterative solution method of binary mixtures is proposed, which has higher calculation efficiency and faster evaluation of the response of system to different disturbances, providing important support for future dynamic analysis.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114409"},"PeriodicalIF":2.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143577849","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

High pressure equilibrium data of CO2/cyclohexene oxide and CO2/limonene oxide systems in the context of polycarbonate synthesis using CO2 as a co-monomer

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-02-26 DOI: 10.1016/j.fluid.2025.114406

Edoardo Vittorio Pasini , Jérôme Durand , Séverine Camy

Polycarbonates are a class of high-performance polymers with a wide range of industrial applications. Traditionally, polycarbonate production involves the use of bisphenol A (BPA) and phosgene (COCl₂), which have raised concerns due to their high toxicity and the overall environmental impact of the process. To address these issues, more sustainable methods such as ring-opening copolymerization (ROCOP) of epoxides and carbon dioxide (CO₂) under supercritical CO₂ (sCO₂) are being developed. Recent research has focused on the synthesis of poly(cyclohexene carbonate) (PCHC) and poly(limonene carbonate) (PLC) from cyclohexene oxide (CHO) and limonene oxide (LO), respectively. Limonene oxide has attracted particular interest due to its non-toxic properties and its derivation from limonene, an available bio-based terpene. Reaction performance is strongly influenced by the initial physical state of the mixture, in particular the composition of the liquid and vapor phases. Therefore, access to this thermodynamic information, represented by phase diagrams, is essential for understanding and predicting reaction behavior. However, there is a lack of equilibrium data for these two systems. The aim of this study is to investigate the phase equilibria of the CO₂/CHO and CO₂/LO binary mixtures, thereby contributing to the advancement of greener polycarbonate production. The experiments were performed in a variable volume view-cell, covering a temperature range from 338.15 K to 363.15 K for the CO₂/CHO mixture and from 303.15 K to 343.15 K for the CO₂/LO system. The molar fraction of CO₂ was varied between 0.189 and 0.967 for the CO₂/CHO case, and between 0.227 and 0.997 for the CO₂/LO mixture. Vapor-liquid bubble point (VLE-BP) and dew point (VLE-DP) were determined for both mixtures, along with mixture critical points for the temperatures studied. The phase behavior was modeled using several equations of state (EoS). In particular, the Peng-Robinson (PR) equation of state with the volume translated Peng-Robinson (VTPR) complex mixing rule and the Wilson model for the activity coefficient provided a highly accurate description of the experimental results.

{"title":"High pressure equilibrium data of CO2/cyclohexene oxide and CO2/limonene oxide systems in the context of polycarbonate synthesis using CO2 as a co-monomer","authors":"Edoardo Vittorio Pasini , Jérôme Durand , Séverine Camy","doi":"10.1016/j.fluid.2025.114406","DOIUrl":"10.1016/j.fluid.2025.114406","url":null,"abstract":"<div><div>Polycarbonates are a class of high-performance polymers with a wide range of industrial applications. Traditionally, polycarbonate production involves the use of bisphenol A (BPA) and phosgene (COCl<sub>2</sub>), which have raised concerns due to their high toxicity and the overall environmental impact of the process. To address these issues, more sustainable methods such as ring-opening copolymerization (ROCOP) of epoxides and carbon dioxide (CO<sub>2</sub>) under supercritical CO<sub>2</sub> (sCO<sub>2</sub>) are being developed. Recent research has focused on the synthesis of poly(cyclohexene carbonate) (PCHC) and poly(limonene carbonate) (PLC) from cyclohexene oxide (CHO) and limonene oxide (LO), respectively. Limonene oxide has attracted particular interest due to its non-toxic properties and its derivation from limonene, an available bio-based terpene. Reaction performance is strongly influenced by the initial physical state of the mixture, in particular the composition of the liquid and vapor phases. Therefore, access to this thermodynamic information, represented by phase diagrams, is essential for understanding and predicting reaction behavior. However, there is a lack of equilibrium data for these two systems. The aim of this study is to investigate the phase equilibria of the CO<sub>2</sub>/CHO and CO<sub>2</sub>/LO binary mixtures, thereby contributing to the advancement of greener polycarbonate production. The experiments were performed in a variable volume view-cell, covering a temperature range from 338.15 K to 363.15 K for the CO<sub>2</sub>/CHO mixture and from 303.15 K to 343.15 K for the CO<sub>2</sub>/LO system. The molar fraction of CO<sub>2</sub> was varied between 0.189 and 0.967 for the CO<sub>2</sub>/CHO case, and between 0.227 and 0.997 for the CO<sub>2</sub>/LO mixture. Vapor-liquid bubble point (VLE-BP) and dew point (VLE-DP) were determined for both mixtures, along with mixture critical points for the temperatures studied. The phase behavior was modeled using several equations of state (EoS). In particular, the Peng-Robinson (PR) equation of state with the volume translated Peng-Robinson (VTPR) complex mixing rule and the Wilson model for the activity coefficient provided a highly accurate description of the experimental results.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114406"},"PeriodicalIF":2.8,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143527009","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

The deviation from ideal behavior in mixtures of propylene glycol and propylene carbonate at different temperatures: Experimental results and modeling

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-02-25 DOI: 10.1016/j.fluid.2025.114394

Alessandro Cazonatto Galvão , João Victor Thomas Feyh , Pedro Felipe Arce , Weber da Silva Robazza

The molecular interactions within a liquid mixture reflect the degree of nonideality present in the solution. This nonideality can be evaluated through various solution properties, including density, viscosity, and refractive index. A comprehensive analysis of these properties offers valuable insights into the interactions between molecules in the mixture. The advancement of models and the validation of theories depend on the precision of these interpretations. This study presents experimental data on the density, refractive index, kinematic viscosity, and dynamic viscosity of a binary liquid mixture comprising propylene glycol and propylene carbonate. The experiments cover a complete range of solution mole fractions at different temperatures. Density data were correlated using the Peng-Robinson and CPA equations of state, yielding binary interaction parameters. The Eyring equation, combined with the NRTL activity coefficient model, was used to correlate kinematic viscosity data, also resulting in binary interaction parameters. Furthermore, the predictive capability of the Lorentz-Lorenz N-mixing rule was assessed for the refractive index data. The deviations from ideal behavior, as indicated by excess molar volume, variations in viscosity, and changes in refractive index, can be attributed to the formation and breaking of hydrogen bonds between the molecules of propylene glycol. The models employed demonstrate a strong capacity to accurately represent the experimental data.

{"title":"The deviation from ideal behavior in mixtures of propylene glycol and propylene carbonate at different temperatures: Experimental results and modeling","authors":"Alessandro Cazonatto Galvão , João Victor Thomas Feyh , Pedro Felipe Arce , Weber da Silva Robazza","doi":"10.1016/j.fluid.2025.114394","DOIUrl":"10.1016/j.fluid.2025.114394","url":null,"abstract":"<div><div>The molecular interactions within a liquid mixture reflect the degree of nonideality present in the solution. This nonideality can be evaluated through various solution properties, including density, viscosity, and refractive index. A comprehensive analysis of these properties offers valuable insights into the interactions between molecules in the mixture. The advancement of models and the validation of theories depend on the precision of these interpretations. This study presents experimental data on the density, refractive index, kinematic viscosity, and dynamic viscosity of a binary liquid mixture comprising propylene glycol and propylene carbonate. The experiments cover a complete range of solution mole fractions at different temperatures. Density data were correlated using the Peng-Robinson and CPA equations of state, yielding binary interaction parameters. The Eyring equation, combined with the NRTL activity coefficient model, was used to correlate kinematic viscosity data, also resulting in binary interaction parameters. Furthermore, the predictive capability of the Lorentz-Lorenz N-mixing rule was assessed for the refractive index data. The deviations from ideal behavior, as indicated by excess molar volume, variations in viscosity, and changes in refractive index, can be attributed to the formation and breaking of hydrogen bonds between the molecules of propylene glycol. The models employed demonstrate a strong capacity to accurately represent the experimental data.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"595 ","pages":"Article 114394"},"PeriodicalIF":2.8,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143479215","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

CO2 solubility in aqueous 1-methylpiperazine and its blend with 2-amino-2-methyl-1-propanol: New experimental data and leveraging Random Forest model for accurate prediction

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-02-25 DOI: 10.1016/j.fluid.2025.114405

Vaibhav Vamja , Vinay Vakharia , Rajib Bandyopadhyay , Sukanta Kumar Dash

A new study of amines with enhanced properties is crucial for its use as an appropriate solvent for CO₂ absorption process. This is essential to overcome current financial and environmental obstacles to implementing large-scale CO₂ capture. In this work, the identified amines to formulate a good aqueous solvent mix are 1-methylpiperazine (1-MPZ) and 2-amino-2-methyl-1-propanol (AMP). 1-MPZ has a higher thermal resistance and lower CO₂ regeneration cost, which makes it a potential candidate for the process. This paper presents the results of experiments on the equilibrium solubility of CO₂ in aqueous 1-MPZ solutions and its blends with AMP along with new vapor pressure data for aqueous 1-MPZ and its blend with AMP. The study examined CO₂ solubility at 0.10, 0.20, 0.30, and 0.40 wt fraction (w) of 1-MPZ and temperatures of 303.15, 313.15, 323.15, and 393.15 K. The CO₂ solubility experiments for the new blended mixture of AMP + 1-MPZ were also performed in this study. Four different sets were prepared by varying the individual concentrations of 1-MPZ and AMP; keeping the total amine concentration 0.40 w for the same temperature range. The experimental results indicate that aqueous 1-MPZ exhibits good cyclic capacity for CO₂ intake which further enhances when combined with AMP. Results indicate that aqueous 1-MPZ exhibits high CO₂ solubility of 0.78 to 1.01 moles of CO₂/moles of amine at normal absorber conditions of temperature and composition. Again, the addition of 1-MPZ to AMP has increased the cyclic capacity. The blended aqueous amine (AMP+ 1-MPZ) shows a cyclic capacity of 118 g CO₂/kg-solution whereas aqueous 1-MPZ of the same amine strength shows only 81 g CO₂/kg-solution. Hence, an increase of about 45% cyclic capacity is achieved with the blended solvent. The combination of 1-MPZ+AMP allows for improved performance in terms of both solubility and regeneration efficiency. The study also incorporated Random Forest (RF) machine learning model to predict CO₂ solubility based on parameters like temperature, concentration, and CO₂ partial pressure. The RF model demonstrated excellent prediction accuracy with R² values of 0.98 and 0.99 for both solutions and least RMSE values of 0.03 and 0.02 for 1-MPZ and (1-MPZ +AMP) blend respectively.

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引用次数: 0

Improved ion-pairing equation of state and its use for various property calculations

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-02-23 DOI: 10.1016/j.fluid.2025.114396

Abtin Raeispour Shirazi , Fufang Yang , Tri Dat Ngo , Olivier Bernard , Jean-Pierre Simonin , Jean-Charles de Hemptinne

This work utilizes an advanced electrolyte polar perturbed chain SAFT theory (ePPC-SAFT) framework combined with the Binding MSA approach to simulate interactions between ions, solvents, and ion pairs in aqueous and mixed-solvent environments. The model allows a higher flexibility to quantify ion pairing and thus improve the accuracy in predicting key properties, such as mean ionic activity coefficients, solubility, and density. The findings underscore the importance of considering both ion pairing and solvation (here represented through association) in thermodynamic models for both aqueous and mixed solvent systems. The model makes it possible to evaluate the impact of the various molecular interactions for ionic activity coefficients and Gibbs energies of transfer.

引用次数: 0

Differential equations for fluid phase equilibria: Isothermal–isobaric case

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-02-21 DOI: 10.1016/j.fluid.2025.114387

Ulrich K. Deiters

Differential equations for two-phase equilibria under isothermal–isobaric conditions are derived. These equations can be used in connection with arbitrary equations of state (Helmholtz energy models) for fluid mixtures to compute phase envelopes. In contrast to conventional computation methods, which solve the (nonlinear) algebraic equations describing phase equilibrium by means of iterative methods and which often suffer from convergence problems, the differential equations merely have to be integrated, but not solved. Convergence problems are thus avoided. The computation of phase envelopes from differential equations is rapid, reliable, and advantageous in connection with complicated equations of state.

推导了等温等压条件下两相平衡的微分方程。这些方程可与流体混合物的任意状态方程（亥姆霍兹能量模型）结合使用，以计算相包络。传统计算方法通过迭代法求解描述相平衡的（非线性）代数方程，往往会出现收敛问题，而微分方程只需积分，无需求解。这样就避免了收敛问题。根据微分方程计算相位包络是一种快速、可靠的方法，在计算复杂的状态方程时非常有利。

引用次数: 0

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