Fluid Phase Equilibria最新文献_第2页

Thermodynamic perturbation theory for associating fluids with coupling to isotropic attractions 将流体与各向同性引力耦合联系起来的热力学摄动理论

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-05-03 DOI: 10.1016/j.fluid.2025.114461

Bennett D. Marshall

{"title":"Thermodynamic perturbation theory for associating fluids with coupling to isotropic attractions","authors":"Bennett D. Marshall","doi":"10.1016/j.fluid.2025.114461","DOIUrl":"10.1016/j.fluid.2025.114461","url":null,"abstract":"<div><div>The coupling between dispersion and hydrogen bonding attractions is mostly ignored in the development of equations of state for hydrogen bonding fluids. While a reasonable approximation in the development of semi-empirical equations of state, the independence of hydrogen bonding and dispersion attractions is not rigorously justifiable. Both hydrogen bonding and dispersion attractions result from the interaction of electrons between two molecules, hence they emerge from the same underlying phenomena. In the pursuit of more accurate equations of state, including the coupling between hydrogen bonding and dispersion attractions in a self-consistent manner should be explored. In this work the coupling of dispersion and hydrogen bonding attractions is incorporated in the development of Wertheim’s thermodynamic perturbation theory for hydrogen bonding molecules. The developed theory is general for pure hydrogen bonding fluids with any number of association sites. The theory is applied to the case of hard spheres with isotropic square well attractions and a single association site. The theory gives counter intuitive predictions.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"597 ","pages":"Article 114461"},"PeriodicalIF":2.8,"publicationDate":"2025-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143916310","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

A theoretical model of gas-liquid phase transition near the critical point 临界点附近气液相变的理论模型

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-05-02 DOI: 10.1016/j.fluid.2025.114456

Wenbin Liu , Jing Liu

{"title":"A theoretical model of gas-liquid phase transition near the critical point","authors":"Wenbin Liu , Jing Liu","doi":"10.1016/j.fluid.2025.114456","DOIUrl":"10.1016/j.fluid.2025.114456","url":null,"abstract":"<div><div>In this study, the internal pressure strength term in the Van der Waals multiphase interface equation has been adjusted to better fit the interface region. By applying the principle of normal isopressure, we can ascertain the thickness of the gas-liquid interface and the material's density distribution along the normal direction. At the gas-liquid interface, molecules experience both an attractive force pulling them into the liquid and a repulsive force from collisions with the gas. By considering the combined effect of these two forces, we can derive an expression for the latent heat of evaporation that includes the molecular volume parameter b, using the normal path integral. This expression is capable of predicting the latent heat of evaporation for substances like water, ranging from the boiling point to the critical point. The maximum deviation for conventional substances is under 30 %, while the prediction error using the Boltzmann distribution ranges from 40 % to 60 %. After introducing the dimensionless parameter τ<sub>c</sub>, the maximum prediction deviation for H<sub>2</sub>O drops to below 8 %, significantly enhancing the prediction accuracy for other substances as well. For subcritical temperatures (T<sub>c</sub>-3 <em>K</em> < <em>T</em>< T<sub>c</sub>), the new expression successfully predicts the latent heat of evaporation for over 30 substances, with an error margin of no >1 %. Additionally, it predicts the critical volume of a substance with a deviation of no >2.4 %. Thus, the latent heat of evaporation expression that incorporates molecular volume parameters demonstrates excellent predictive capability in the gas-liquid phase transition process near critical temperatures, providing a foundation for advancing the average field theory of gas-liquid phase transitions for various substances at near-critical temperatures.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"597 ","pages":"Article 114456"},"PeriodicalIF":2.8,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143922165","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

Thermodynamic description of aqueous solutions of silver nitrate: Experimental and modeling 硝酸银水溶液的热力学描述：实验和模型

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-30 DOI: 10.1016/j.fluid.2025.114459

Mouad Arrad , Mehriban Aliyeva , Mónia A.R. Martins , Kaj Thomsen , Simão P. Pinho

{"title":"Thermodynamic description of aqueous solutions of silver nitrate: Experimental and modeling","authors":"Mouad Arrad , Mehriban Aliyeva , Mónia A.R. Martins , Kaj Thomsen , Simão P. Pinho","doi":"10.1016/j.fluid.2025.114459","DOIUrl":"10.1016/j.fluid.2025.114459","url":null,"abstract":"<div><div>The water activity of silver nitrate solutions was measured at 298.2 K and 313.2 K using a humidity sensor instrument. Concentrations of silver nitrate up to almost saturation were included. The thermodynamic properties of the system were described by the Pitzer model, the specific interaction theory (SIT), and the Extended UNIQUAC model. The interaction parameters for the models were estimated using experimental freezing points, osmotic coefficients, and solubility for silver nitrate aqueous solutions collected from the open literature, as well as the water activity data measured in this work. Pitzer and SIT parameters were applied by introducing a temperature dependency, enabling these models to cover a more comprehensive temperature range and extrapolate the calculation to higher molalities. Both approaches represent the data satisfactorily up to moderate molalities. The Extended UNIQUAC model, with its built-in temperature dependence, provides the best thermodynamic description of this binary system. It has a very satisfactory solubility diagram and a good description of the osmotic and activity coefficients.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"597 ","pages":"Article 114459"},"PeriodicalIF":2.8,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143906003","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

Corrigendum to “Study of surface tension of CO2+water and CO2+ethanol solutions from combined CPA and PC-SAFT EoSs with gradient theory and artificial neural network” [Fluid Phase Equilibria, volume 593C, FLUID 114338] “用梯度理论和人工神经网络研究CPA和PC-SAFT组合eos中CO2+水和CO2+乙醇溶液的表面张力”[流体相平衡，卷593C，流体114338]的勘误。

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-30 DOI: 10.1016/j.fluid.2025.114452

Parisa Tabarzadi , Mohammad Niksirat , Fatemeh Aeenjan , Ariel Hernandez , Shahin Khosharay

引用次数: 0

Impact of nanostructuration on the transport properties of ionic liquids 纳米结构对离子液体输运性质的影响

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-26 DOI: 10.1016/j.fluid.2025.114458

Carlos F.P. Miranda, Luís M.N.B.F. Santos

{"title":"Impact of nanostructuration on the transport properties of ionic liquids","authors":"Carlos F.P. Miranda, Luís M.N.B.F. Santos","doi":"10.1016/j.fluid.2025.114458","DOIUrl":"10.1016/j.fluid.2025.114458","url":null,"abstract":"<div><div>The impact of nanostructuration on the transport properties of ionic liquids (ILs) was explored by a systematic and high-resolution study of the temperature dependence of the viscosity and electrical conductivity of seven ILs homolog series: [C<em><sub>n</sub></em>C<sub>1</sub>im]BF<sub>4</sub>, [C<em><sub>n</sub></em>C<sub>1</sub>im]PF<sub>6</sub>, [C<em><sub>n</sub></em>C<sub>1</sub>im][OTf], [C<em><sub>n</sub></em>C<sub>1</sub>im][FAP], [C<em><sub>n</sub></em>C<sub>1</sub>im][NTf<sub>2</sub>], [C<em><sub>n</sub></em>C<sub>1</sub>pyr][NTf<sub>2</sub>], [C<em><sub>n</sub></em>py][NTf<sub>2</sub>]. The increase of the alkyl chain length was found to increase the viscosity and decrease the molar conductivity due to a reduction of the overall mobility of the liquid and enhancement of the van der Waals interactions. The temperature dependency of transport properties was fitted to the Vogel-Fulcher-Tammann equation (VFT), and the energy barrier and pre-exponential coefficients were derived. The obtained results highlight the trendshift (<em>n</em> = 6–7) in the profile of the transport properties, which is a reflection of the intensification of nanostructuration and describes the transition from a liquid with a strong ionic character to a nanostructured liquid dominated by the hydrophobic domain. The derived energy barriers were found to correspond to around 0.2–0.35 of the cohesive interactions of the ionic liquids, with the spherical anions BF<sub>4</sub><sup>−</sup> and PF<sub>6</sub><sup>−</sup> showing a higher fraction than the more stretched and larger anions, such as NTf<sub>2</sub>. This fraction was found to not be affected by the alkyl chain length. The increase of the nonpolar region was also reflected in a more pronounced deviation from the ideal Walden relation. This highlights the increased complexity of the electric conductivity when compared with viscosity due to the heterogeneity of charge distribution, revealing the impact of ionic surface-volume ratio and anion-cation size ratio.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"597 ","pages":"Article 114458"},"PeriodicalIF":2.8,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143916309","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

Investigation of the molecular architecture influence on the solid-liquid transition of ethylene/1-octene copolymers in butylal 丁醛中乙烯/1-辛烯共聚物固液转变的分子结构影响研究

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-26 DOI: 10.1016/j.fluid.2025.114457

Jana Zimmermann, Zengxuan Fan, Matti Jänicke, Michael Fischlschweiger

{"title":"Investigation of the molecular architecture influence on the solid-liquid transition of ethylene/1-octene copolymers in butylal","authors":"Jana Zimmermann, Zengxuan Fan, Matti Jänicke, Michael Fischlschweiger","doi":"10.1016/j.fluid.2025.114457","DOIUrl":"10.1016/j.fluid.2025.114457","url":null,"abstract":"<div><div>The molecular architecture, in terms of molecular weight and branching, linked with the semi-crystallinity of the polymer, plays a key role in solid-liquid equilibria in polyethylene-solvent systems. Lattice Cluster Theory, in combination with continuous thermodynamics, captures these molecular features and has been successfully applied in the past to predict solid-liquid equilibria of polymer solvent systems. While the solubility of linear low-density polyethylenes in chlorinated solvents has been studied in depth in the past, few investigations have addressed their solubility in less toxic and environmentally more friendly solvents, particularly in relation to the influence of molecular architecture. This study aims to fill this gap by investigating the relationship between molecular architecture of ethylene/1-octene copolymers, covering a wide range of branching levels from 3.5 to 54.6 CH/1000 C, and their solid-liquid phase transitions in butylal. By combining cross-fractionation chromatography, preparative crystallisation fractionation and Lattice Cluster Theory, the solid-liquid transitions of these material systems are elucidated and an architecture-solubility relationship is established. This approach provides detailed insights into how molecular architecture influences crystallisation behaviour, provides a basis for the design of ethylene/1-octene copolymer fractions with tailored microstructural features, and demonstrates the predictive power of Lattice Cluster Theory.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"597 ","pages":"Article 114457"},"PeriodicalIF":2.8,"publicationDate":"2025-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143895131","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

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}

引用次数: 0

High-pressure phase equilibria of liquid CO2 with ethanol - water mixtures 液态CO2与乙醇-水混合物的高压相平衡

IF 2.8 3区工程技术

Fluid Phase Equilibria Pub Date : 2025-04-24 DOI: 10.1016/j.fluid.2025.114450

Masato Urabe , Masaki Ota , Richard Lee Smith Jr. , Masaru Watanabe

{"title":"High-pressure phase equilibria of liquid CO2 with ethanol - water mixtures","authors":"Masato Urabe , Masaki Ota , Richard Lee Smith Jr. , Masaru Watanabe","doi":"10.1016/j.fluid.2025.114450","DOIUrl":"10.1016/j.fluid.2025.114450","url":null,"abstract":"<div><div>Although many data have been reported for the CO<sub>2</sub> (1) - ethanol (2) - water (3) system, gaps in the literature exist for liquid CO<sub>2</sub> at conditions where stripping of ethanol for flavor fractionation has been suggested. In this work, a flow-type device was used to measure the phase equilibria of CO<sub>2</sub> - ethanol - water mixtures at (278 to 298) K and (8 to 20) MPa. Ethanol/water feed ratios were varied from 0.22 to 1.7 which gave corresponding equilibrium ratios (=<em>y</em><sub>i</sub>/<em>x</em><sub>i</sub>) of <em>K</em><sub>1</sub> (39 to 4), <em>K</em><sub>2</sub> (0.12 to 0.21) and <em>K</em><sub>3</sub> (0.006 to 0.04) giving ethanol/water selectivities, <em>β</em> (=<em>K</em><sub>2</sub>/<em>K</em><sub>3</sub>), that ranged from 27.9 to 5. While the <em>K</em><sub>2</sub> values tended to be invariant with ethanol/water feed ratio, the <em>K</em><sub>1</sub> and <em>K</em><sub>3</sub> values varied greatly. Among the equations of state evaluated in this work, the Peng-Robinson equation of state with the Wong-Sandler mixing rule model based on the NRTL activity coefficient expression gave the lowest deviations and could correlate <em>K</em> values for CO<sub>2</sub>, ethanol and water with an average relative deviation of 6.9 %, 22.3 % and 28.1 %, respectively.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"597 ","pages":"Article 114450"},"PeriodicalIF":2.8,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143895130","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

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