Pub Date : 2024-10-16DOI: 10.1016/j.fluid.2024.114250
Simon Müller , Thomas Nevolianis , Miquel Garcia-Ratés , Christoph Riplinger , Kai Leonhard , Irina Smirnova
In this study, we introduce openCOSMO-RS 24a, an improved version of the open-source COSMO-RS model parameterized using quantum chemical calculations from ORCA 6.0, leveraging a comprehensive dataset that includes solvation free energies, partition coefficients, and infinite dilution activity coefficients for various solutes and solvents mainly at 25 °C. This is the first version of the model also capable of predicting solvation free energies based on ORCA calculations. Additionally, we develop a Quantitative Structure-Property Relationships model to predict molar volumes of the solvents, an essential requirement for predicting solvation free energies and partition coefficients from structure alone. Our results show that openCOSMO-RS 24a achieves an average absolute deviation of 0.45 kcal mol1 for solvation free energies, 0.76 for the logarithm of the partition coefficients, and 0.51 for the logarithm of infinite dilution activity coefficients, demonstrating improvements over the previous openCOSMO-RS 22 parameterization and comparable results to COSMOtherm 24 BP-TZVP. The user interface was extended to be able to use it as solvation model directly from within ORCA 6.0 or from the command line to provide researchers with a robust tool for applications in chemical and materials science.
{"title":"Predicting solvation free energies for neutral molecules in any solvent with openCOSMO-RS","authors":"Simon Müller , Thomas Nevolianis , Miquel Garcia-Ratés , Christoph Riplinger , Kai Leonhard , Irina Smirnova","doi":"10.1016/j.fluid.2024.114250","DOIUrl":"10.1016/j.fluid.2024.114250","url":null,"abstract":"<div><div>In this study, we introduce openCOSMO-RS 24a, an improved version of the open-source COSMO-RS model parameterized using quantum chemical calculations from ORCA 6.0, leveraging a comprehensive dataset that includes solvation free energies, partition coefficients, and infinite dilution activity coefficients for various solutes and solvents mainly at 25 °C. This is the first version of the model also capable of predicting solvation free energies based on ORCA calculations. Additionally, we develop a Quantitative Structure-Property Relationships model to predict molar volumes of the solvents, an essential requirement for predicting solvation free energies and partition coefficients from structure alone. Our results show that openCOSMO-RS 24a achieves an average absolute deviation of 0.45 kcal mol<sup>1</sup> for solvation free energies, 0.76 for the logarithm of the partition coefficients, and 0.51 for the logarithm of infinite dilution activity coefficients, demonstrating improvements over the previous openCOSMO-RS 22 parameterization and comparable results to COSMOtherm 24 BP-TZVP. The user interface was extended to be able to use it as solvation model directly from within ORCA 6.0 or from the command line to provide researchers with a robust tool for applications in chemical and materials science.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114250"},"PeriodicalIF":2.8,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142552759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-15DOI: 10.1016/j.fluid.2024.114244
Oleg V. Kashurin , Vladimir I. Deshchenya , Nikolay D. Kondratyuk
The shear viscosity of organic liquids is very important for industrial applications. This paper focuses on the blind prediction of concentration-viscosity dependencies for organic mixtures at 298.15 K and 1 bar using molecular dynamics methods. Two mixtures are considered: tributyrin+1-decanol and 1,2-butanediol+1-decanol. The interatomic interactions are described using the COMPASS force field, which is modified for the reproduction of pure compound viscosities. The Green–Kubo method is used to calculate the shear viscosities. Our approach provides accurate predictions for the viscosities of mixtures with a relative mean absolute error below 10%. This work is devoted to the participation in the 12th Industrial Fluid Properties Simulation Challenge.
有机液体的剪切粘度对工业应用非常重要。本文的重点是利用分子动力学方法，对 298.15 K 和 1 bar 下有机混合物的浓度-粘度依赖关系进行盲预测。本文考虑了两种混合物：三丁炔+1-癸醇和 1,2-丁二醇+1-癸醇。原子间的相互作用使用 COMPASS 力场进行描述，为再现纯化合物的粘度对其进行了修改。格林-久保法用于计算剪切粘度。我们的方法可以准确预测混合物的粘度，相对平均绝对误差低于 10%。这项工作是为了参加第 12 届工业流体特性模拟挑战赛。
{"title":"Predicting viscosity-concentration dependencies of binary organic mixtures using molecular dynamics methods","authors":"Oleg V. Kashurin , Vladimir I. Deshchenya , Nikolay D. Kondratyuk","doi":"10.1016/j.fluid.2024.114244","DOIUrl":"10.1016/j.fluid.2024.114244","url":null,"abstract":"<div><div>The shear viscosity of organic liquids is very important for industrial applications. This paper focuses on the blind prediction of concentration-viscosity dependencies for organic mixtures at 298.15 K and 1 bar using molecular dynamics methods. Two mixtures are considered: tributyrin+1-decanol and 1,2-butanediol+1-decanol. The interatomic interactions are described using the COMPASS force field, which is modified for the reproduction of pure compound viscosities. The Green–Kubo method is used to calculate the shear viscosities. Our approach provides accurate predictions for the viscosities of mixtures with a relative mean absolute error below 10%. This work is devoted to the participation in the 12th Industrial Fluid Properties Simulation Challenge.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114244"},"PeriodicalIF":2.8,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142528150","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}
Pub Date : 2024-10-15DOI: 10.1016/j.fluid.2024.114256
Ying Zhou , Zhuo Chen , Nobuo Maeda , Huazhou Li
The effects of iodide salts and ion specificity on the thermodynamic inhibition of CH4 and CO2 hydrates have not been thoroughly investigated. In this study, we employ the isochoric pressure-search method to measure the dissociation temperature (272.48 – 286.54 K) and pressure (1.38 – 11.24 MPa) of CH4 and CO2 hydrates in iodide solutions with concentrations of 6.24 wt% and 12.48 wt%. The measured data are subsequently used to validate a thermodynamic model integrating the Pitzer model into the van der Waals-Platteeuw (vdW-P) model for predicting the dissociation pressure of gas hydrates. The model can accurately predict the dissociation conditions of CH4 and CO2 hydrates in iodide solutions. The experimental results reveal that the inhibition effect of iodide salts on CH4 and CO2 hydrates is enhanced with an increasing salt concentration. Additionally, the dissociation temperature suppression of CH4 and CO2 hydrates is correlated with water activities of different salt solutions to investigate the effect of ion specificity on the thermodynamic inhibition of these hydrates. Our analysis demonstrates that ion specificity exists in the thermodynamic inhibition of CO2 hydrate but does not apply to CH4 hydrate. In addition, anions play a major role in the thermodynamic inhibition of CO2 hydrate.
碘盐和离子特异性对 CH4 和 CO2 水合物热力学抑制作用的影响尚未得到深入研究。在本研究中，我们采用等时压力搜索法测量了浓度为 6.24 wt% 和 12.48 wt% 的碘化物溶液中 CH4 和 CO2 水合物的解离温度（272.48 - 286.54 K）和压力（1.38 - 11.24 MPa）。测量数据随后被用于验证一个热力学模型，该模型将皮策模型集成到范德瓦耳斯-普拉蒂奥乌（vdW-P）模型中，用于预测气体水合物的解离压力。该模型可以准确预测 CH4 和 CO2 水合物在碘化物溶液中的解离条件。实验结果表明，碘盐对 CH4 和 CO2 水合物的抑制作用随盐浓度的增加而增强。此外，CH4 和 CO2 水合物的解离温度抑制与不同盐溶液的水活度相关，以研究离子特异性对这些水合物热力学抑制作用的影响。我们的分析表明，离子特异性存在于 CO2 水合物的热力学抑制中，但不适用于 CH4 水合物。此外，阴离子在二氧化碳水合物的热力学抑制作用中起主要作用。
{"title":"Effect of Ion Specificity on Thermodynamic Inhibition of CH4 and CO2 Hydrates: An Experimental and Modeling Study","authors":"Ying Zhou , Zhuo Chen , Nobuo Maeda , Huazhou Li","doi":"10.1016/j.fluid.2024.114256","DOIUrl":"10.1016/j.fluid.2024.114256","url":null,"abstract":"<div><div>The effects of iodide salts and ion specificity on the thermodynamic inhibition of CH<sub>4</sub> and CO<sub>2</sub> hydrates have not been thoroughly investigated. In this study, we employ the isochoric pressure-search method to measure the dissociation temperature (272.48 – 286.54 K) and pressure (1.38 – 11.24 MPa) of CH<sub>4</sub> and CO<sub>2</sub> hydrates in iodide solutions with concentrations of 6.24 wt% and 12.48 wt%. The measured data are subsequently used to validate a thermodynamic model integrating the Pitzer model into the van der Waals-Platteeuw (vdW-P) model for predicting the dissociation pressure of gas hydrates. The model can accurately predict the dissociation conditions of CH<sub>4</sub> and CO<sub>2</sub> hydrates in iodide solutions. The experimental results reveal that the inhibition effect of iodide salts on CH<sub>4</sub> and CO<sub>2</sub> hydrates is enhanced with an increasing salt concentration. Additionally, the dissociation temperature suppression of CH<sub>4</sub> and CO<sub>2</sub> hydrates is correlated with water activities of different salt solutions to investigate the effect of ion specificity on the thermodynamic inhibition of these hydrates. Our analysis demonstrates that ion specificity exists in the thermodynamic inhibition of CO<sub>2</sub> hydrate but does not apply to CH<sub>4</sub> hydrate. In addition, anions play a major role in the thermodynamic inhibition of CO<sub>2</sub> hydrate.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114256"},"PeriodicalIF":2.8,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142528148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-12DOI: 10.1016/j.fluid.2024.114249
Romain Privat , Jean-Noël Jaubert , Georgios M. Kontogeorgis
In modern versions of cubic equations of state (EoS), the mixing rules for EoS parameters are derived from an activity coefficient model using either the Huron-Vidal or the Zero Reference Pressure (ZRP) approach. As it is a fact that Wilson's activity coefficient model cannot predict liquid-liquid equilibria (LLE), this article attempts to answer the question: if Wilson's model is coupled with a cubic EoS, is the resulting model capable of predicting LLE?
This question is actually becoming increasingly important as recent EoS rely on such a coupling (e.g., the tc-PR EoS). We show that although Wilson's model is mathematically unable to predict instable liquid phases, this is not true for Wilson-EoS models (i.e., EoS incorporating Wilson's model). However, it is also shown that the capacity of Wilson-EoS to predict LLE depends not only on the approach chosen (Huron-Vidal or ZRP) but also on mixture characteristics (such as the ratio of covolumes, the ratio of critical attractive parameters, the binary interaction parameters etc.).
在现代版本的立方状态方程（EoS）中，EoS 参数的混合规则是通过使用休伦-维达尔法（Huron-Vidal）或零参考压力法（ZRP）的活度系数模型推导出来的。事实上，威尔逊的活度系数模型无法预测液液平衡（LLE），因此本文试图回答这样一个问题：如果将威尔逊模型与立方 EoS 相耦合，得到的模型是否能够预测 LLE？我们的研究表明，虽然威尔逊模型在数学上无法预测不稳定液相，但威尔逊-EoS 模型（即包含威尔逊模型的 EoS）却并非如此。然而，研究还表明，Wilson-EoS 预测 LLE 的能力不仅取决于所选择的方法（Huron-Vidal 或 ZRP），还取决于混合物的特征（如共容比、临界吸引力参数比、二元相互作用参数等）。
{"title":"Can liquid-liquid equilibria be predicted by the combination of a cubic equation of state and a gE model not suitable for liquid-liquid equilibria?","authors":"Romain Privat , Jean-Noël Jaubert , Georgios M. Kontogeorgis","doi":"10.1016/j.fluid.2024.114249","DOIUrl":"10.1016/j.fluid.2024.114249","url":null,"abstract":"<div><div>In modern versions of cubic equations of state (EoS), the mixing rules for EoS parameters are derived from an activity coefficient model using either the Huron-Vidal or the Zero Reference Pressure (ZRP) approach. As it is a fact that Wilson's activity coefficient model cannot predict liquid-liquid equilibria (LLE), this article attempts to answer the question: if Wilson's model is coupled with a cubic EoS, is the resulting model capable of predicting LLE?</div><div>This question is actually becoming increasingly important as recent EoS rely on such a coupling (e.g., the tc-PR EoS). We show that although Wilson's model is mathematically unable to predict instable liquid phases, this is not true for Wilson-EoS models (i.e., EoS incorporating Wilson's model). However, it is also shown that the capacity of Wilson-EoS to predict LLE depends not only on the approach chosen (Huron-Vidal or ZRP) but also on mixture characteristics (such as the ratio of covolumes, the ratio of critical attractive parameters, the binary interaction parameters etc.).</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114249"},"PeriodicalIF":2.8,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142528735","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ionic liquids (ILs) have garnered considerable attention for their diverse applications, notably in controlling wettability on specific solid substrates, which holds ramifications for various processes reliant on interfacial behaviour encompassing adhesion and wetting. This review encompasses key advancements in IL wetting behavior and its implications. Factors such as drop size, temperature, alkyl chain structure, anion type, water concentration, and external electric fields influence the contact angle of ILs and their aqueous solutions. Despite challenges arising from IL property susceptibility to water content and wettability measurement sensitivity to solid surface, this review navigates the extent of IL wetting research, addressing line tension, surface tension measurement, and hydrogen bonding. The study aspires to furnish profound insights into IL wetting dynamics, informing IL-based fluidic technology design and elucidating intricate static and dynamic wetting attributes in analogous complex fluids.
离子液体（IL）因其多样化的应用而备受关注，尤其是在控制特定固体基底的润湿性方面，这对依赖于包括粘附和润湿在内的界面行为的各种工艺都有影响。本综述涵盖了 IL 润湿行为及其影响方面的主要进展。液滴大小、温度、烷基链结构、阴离子类型、水浓度和外部电场等因素都会影响 IL 及其水溶液的接触角。尽管 IL 特性易受含水量的影响以及润湿性测量对固体表面的敏感性带来了挑战，但本综述仍对 IL 润湿研究的范围进行了导航，探讨了线张力、表面张力测量和氢键等问题。本研究旨在提供有关 IL 润湿动力学的深刻见解，为基于 IL 的流体技术设计提供信息，并阐明类似复杂流体中错综复杂的静态和动态润湿属性。
{"title":"Wetting and interfacial behavior of imidazolium-based ionic liquids and water: A comprehensive review","authors":"Sanchari Bhattacharjee, Devargya Chakraborty, Sandip Khan","doi":"10.1016/j.fluid.2024.114252","DOIUrl":"10.1016/j.fluid.2024.114252","url":null,"abstract":"<div><div>Ionic liquids (ILs) have garnered considerable attention for their diverse applications, notably in controlling wettability on specific solid substrates, which holds ramifications for various processes reliant on interfacial behaviour encompassing adhesion and wetting. This review encompasses key advancements in IL wetting behavior and its implications. Factors such as drop size, temperature, alkyl chain structure, anion type, water concentration, and external electric fields influence the contact angle of ILs and their aqueous solutions. Despite challenges arising from IL property susceptibility to water content and wettability measurement sensitivity to solid surface, this review navigates the extent of IL wetting research, addressing line tension, surface tension measurement, and hydrogen bonding. The study aspires to furnish profound insights into IL wetting dynamics, informing IL-based fluidic technology design and elucidating intricate static and dynamic wetting attributes in analogous complex fluids.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114252"},"PeriodicalIF":2.8,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142528734","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}
Pub Date : 2024-10-11DOI: 10.1016/j.fluid.2024.114253
Qing-Yi Xiao , Xi-Yue Li , Dong-Liang Zhong , Jin Yan
This work presents a calorimetric and Raman spectroscopy investigation on the phase behavior of DIOX (1,3-Dioxolane) + CO2 hydrate. A high-pressure micro-differential scanning calorimeter (HP μ-DSC) was used to determine the phase equilibrium data of DIOX + CO2 hydrate formed at 1 mol% and 5.56 mol% DIOX. A high-pressure in situ Raman spectroscopy apparatus was used to record the transient CO2 Raman spectra. The spectra were employed to study CO2 incorporation into the hydrate cages during the DIOX hydrate formation process. The results indicate that the DIOX + CO2 hydrate formed at 5.56 mol% DIOX is more stable than that formed at 1 mol% DIOX. The amount of DIOX + CO2 hydrate is increased when increasing the pressure from 3.0 MPa to 4.8 MPa, and more CO2 molecules are captured in the hydrate. Through the in situ Raman spectroscopy experiments, it is found that DIOX hydrate formed quickly at the beginning of the experiment and CO2 molecules were trapped in the small cages more slowly than the incorporation of DIOX into the hydrate. The results reported in this work have confirmed the feasibility of using DIOX as a thermodynamic additive to promote the hydrate-based CO2 capture.
本研究采用热量计和拉曼光谱对 DIOX（1,3-二氧戊环）+ CO2 水合物的相行为进行了研究。使用高压微差扫描量热仪（HP μ-DSC）测定了 DIOX + CO2 水合物在 1 mol% 和 5.56 mol% DIOX 浓度下形成的相平衡数据。使用高压原位拉曼光谱仪器记录了瞬态 CO2 拉曼光谱。这些光谱被用来研究 DIOX 水合物形成过程中二氧化碳掺入水合物笼子的情况。结果表明，在 5.56 摩尔 DIOX 浓度下形成的 DIOX + CO2 水合物比在 1 摩尔 DIOX 浓度下形成的 DIOX + CO2 水合物更稳定。当压力从 3.0 兆帕增加到 4.8 兆帕时，DIOX + CO2 水合物的数量增加，水合物中捕获了更多的 CO2 分子。通过原位拉曼光谱实验发现，DIOX 水合物在实验开始时形成较快，CO2 分子被捕获到小笼中的速度比 DIOX 融入水合物的速度慢。这项工作报告的结果证实了使用 DIOX 作为热力学添加剂来促进基于水合物的二氧化碳捕获的可行性。
{"title":"A calorimetric and Raman spectroscopy study on the phase behavior of DIOX + CO2 hydrate","authors":"Qing-Yi Xiao , Xi-Yue Li , Dong-Liang Zhong , Jin Yan","doi":"10.1016/j.fluid.2024.114253","DOIUrl":"10.1016/j.fluid.2024.114253","url":null,"abstract":"<div><div>This work presents a calorimetric and Raman spectroscopy investigation on the phase behavior of DIOX (1,3-Dioxolane) + CO<sub>2</sub> hydrate. A high-pressure micro-differential scanning calorimeter (HP μ-DSC) was used to determine the phase equilibrium data of DIOX + CO<sub>2</sub> hydrate formed at 1 mol% and 5.56 mol% DIOX. A high-pressure in situ Raman spectroscopy apparatus was used to record the transient CO<sub>2</sub> Raman spectra. The spectra were employed to study CO<sub>2</sub> incorporation into the hydrate cages during the DIOX hydrate formation process. The results indicate that the DIOX + CO<sub>2</sub> hydrate formed at 5.56 mol% DIOX is more stable than that formed at 1 mol% DIOX. The amount of DIOX + CO<sub>2</sub> hydrate is increased when increasing the pressure from 3.0 MPa to 4.8 MPa, and more CO<sub>2</sub> molecules are captured in the hydrate. Through the in situ Raman spectroscopy experiments, it is found that DIOX hydrate formed quickly at the beginning of the experiment and CO<sub>2</sub> molecules were trapped in the small cages more slowly than the incorporation of DIOX into the hydrate. The results reported in this work have confirmed the feasibility of using DIOX as a thermodynamic additive to promote the hydrate-based CO<sub>2</sub> capture.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114253"},"PeriodicalIF":2.8,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142528499","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}
To study the effects of temperature as well as molecular interaction of a fluid system on the thermophysical properties of 2-propanol and n-Decane binary mixture, the density (ρ), dynamic viscosity (η), speed of sound (), and refractive index () of pure 2-propanol and n-Decane, along with their binary mixtures, were experimentally measured across the entire compositional range at temperatures from 283.15 to 343.15 K and atmospheric pressure. These experimental measurements helped in the evaluation of various thermophysical properties, such as excess molar volume , coefficient of thermal expansion (), and isentropic compressibility . The experimental dynamic viscosity (η) and density (ρ) data were used to evaluate kinematic viscosity (v) and Gibbs free energy (ΔG) of flow with an equation based on Eyring's absolute state theory, and their corresponding excess properties. The excess properties of the binary mixtures were correlated using a Redlich-Kister type polynomial equation via the least-squares regression method, with fitting parameters determined for the binary system. Moreover, the Prigogine–Flory–Patterson theory (PFP) was utilized to identify the primary molecular interactions contributing to the excess molar volume at 293.15, 308.15, and 323.15 K for the binary mixtures. Additionally, the capability of the Eyring-NRTL model was tested to predict the viscosity as well as vapor-liquid equilibrium (VLE) of the binary system, and the correlated model results agreed with literature data.
{"title":"Thermophysical properties: Viscosity, density, and excess properties of 2-propanol and n-Decane mixtures from 283.15 K to 343.15 K under atmospheric conditions","authors":"Abdulalim Ibrahim , Christophe Coquelet , Alain Valtz , Fabienne Espitalier","doi":"10.1016/j.fluid.2024.114254","DOIUrl":"10.1016/j.fluid.2024.114254","url":null,"abstract":"<div><div>To study the effects of temperature as well as molecular interaction of a fluid system on the thermophysical properties of 2-propanol and n-Decane binary mixture, the density (ρ), dynamic viscosity (η), speed of sound (<span><math><mi>u</mi></math></span>), and refractive index (<span><math><msub><mi>n</mi><mi>D</mi></msub></math></span>) of pure 2-propanol and n-Decane, along with their binary mixtures, were experimentally measured across the entire compositional range at temperatures from 283.15 to 343.15 K and atmospheric pressure. These experimental measurements helped in the evaluation of various thermophysical properties, such as excess molar volume <span><math><mrow><mo>(</mo><msup><mrow><mi>v</mi></mrow><mi>E</mi></msup><mo>)</mo></mrow></math></span>, coefficient of thermal expansion (<span><math><msup><mrow><mi>α</mi></mrow><mi>E</mi></msup></math></span>), and isentropic compressibility <span><math><mrow><mo>(</mo><msup><mrow><msub><mi>κ</mi><mi>s</mi></msub></mrow><mi>E</mi></msup><mo>)</mo></mrow></math></span>. The experimental dynamic viscosity (η) and density (ρ) data were used to evaluate kinematic viscosity (<strong><em>v</em></strong>) and Gibbs free energy (Δ<em>G</em>) of flow with an equation based on Eyring's absolute state theory, and their corresponding excess properties. The excess properties of the binary mixtures were correlated using a Redlich-Kister type polynomial equation via the least-squares regression method, with fitting parameters determined for the binary system. Moreover, the Prigogine–Flory–Patterson theory (PFP) was utilized to identify the primary molecular interactions contributing to the excess molar volume at 293.15, 308.15, and 323.15 K for the binary mixtures. Additionally, the capability of the Eyring-NRTL model was tested to predict the viscosity as well as vapor-liquid equilibrium (VLE) of the binary system, and the correlated model results agreed with literature data.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114254"},"PeriodicalIF":2.8,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142445075","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}
Pub Date : 2024-10-09DOI: 10.1016/j.fluid.2024.114251
Qinxi Fan , Mingdong Zhang , Yewei Ding , Alexey I. Victorov , Yuanhui Ji
In this work, the solubility of oxcarbazepine in polymers (PEG 6000, PEG 20,000, PVP K25, and PVP K30) and their aqueous solutions was investigated by experimental measurement and thermodynamic modeling. Firstly, the solubility of oxcarbazepine in water and polymers was modeled and the corresponding binary interaction parameters (oxcarbazepine + water and oxcarbazepine + polymer) were determined based on the experimental phase equilibrium data. Furthermore, the solubility of oxcarbazepine in the polymer aqueous solution (the mass ratios of polymers in water were 2 %, 4 %, and 6 %) was predicted by the solid-liquid equilibrium (SLE) coupled with the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT). It was observed that the predicted results agreed well with the experimental data, and the average relative deviation (ARD) was <7 %. In this study, the solubility of oxcarbazepine in polymer aqueous solution was successfully predicted through the SLE coupled with the PC-SAFT, which was expected to provide theoretical guidance for the selection of pharmaceutical excipients and the rational design of preparations.
{"title":"Influence of excipients on solubility of oxcarbazepine: Modeling and prediction based on thermodynamic models","authors":"Qinxi Fan , Mingdong Zhang , Yewei Ding , Alexey I. Victorov , Yuanhui Ji","doi":"10.1016/j.fluid.2024.114251","DOIUrl":"10.1016/j.fluid.2024.114251","url":null,"abstract":"<div><div>In this work, the solubility of oxcarbazepine in polymers (PEG 6000, PEG 20,000, PVP K25, and PVP K30) and their aqueous solutions was investigated by experimental measurement and thermodynamic modeling. Firstly, the solubility of oxcarbazepine in water and polymers was modeled and the corresponding binary interaction parameters (oxcarbazepine + water and oxcarbazepine + polymer) were determined based on the experimental phase equilibrium data. Furthermore, the solubility of oxcarbazepine in the polymer aqueous solution (the mass ratios of polymers in water were 2 %, 4 %, and 6 %) was predicted by the solid-liquid equilibrium (SLE) coupled with the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT). It was observed that the predicted results agreed well with the experimental data, and the average relative deviation (ARD) was <7 %. In this study, the solubility of oxcarbazepine in polymer aqueous solution was successfully predicted through the SLE coupled with the PC-SAFT, which was expected to provide theoretical guidance for the selection of pharmaceutical excipients and the rational design of preparations.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114251"},"PeriodicalIF":2.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142528733","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}
Pub Date : 2024-10-09DOI: 10.1016/j.fluid.2024.114246
Divya Baskaran , Jongho Kim , Uma Sankar Behera, Hun-Soo Byun
New binary isotherms are crucial for designing chemical separation processes within supercritical carbon dioxide (CO2) + trialkoxysilane systems. Vapor-liquid equilibria (VLE) were investigated for two-component systems, trimethoxymethylsilane + CO2 and triethoxymethylsilane + CO2, at five temperatures (313.2, 333.2, 353.2, 373.2, and 393.2 K) and pressures up to 14.07 MPa using a synthetic high-pressure phase equilibria apparatus. The pressure-temperature (P-T) plot indicates that the critical mixture curve lies between the critical points of CO2 and the trialkoxysilane compounds. The solubility of trimethoxymethylsilane and triethoxymethylsilane in CO2 increased with increasing temperature at constant pressure, following a type-I phase behavior characteristic. The experimentally observed VLE values of the CO2 + trialkoxysilane systems were correlated using the Peng-Robinson equation of state with binary parameters (kij and ηij) in the conventional mixing rule. The model accuracy was validated by calculating the average relative deviation percentage for the pressure of the binary systems, resulting in values of 4.98% for the trimethoxymethylsilane + CO2 system and 3.64% for the triethoxymethylsilane + CO2 system. The estimated variables fell within reasonable limits and showed no significant differences between the predicted and observed VLE data for both systems.
新的二元等温线对于设计超临界二氧化碳（CO2）+三烷氧基硅烷体系中的化学分离过程至关重要。使用合成的高压相平衡仪器，在五种温度（313.2、333.2、353.2、373.2 和 393.2 K）和最高 14.07 MPa 的压力下，研究了双组分系统（三甲氧基甲基硅烷 + CO2 和三甲氧基甲基硅烷 + CO2）的汽液平衡 (VLE)。压力-温度（P-T）图表明，临界混合物曲线位于二氧化碳和三烷氧基硅烷化合物的临界点之间。在恒压条件下，三甲氧基甲基硅烷和三甲氧基甲基硅烷在 CO2 中的溶解度随着温度的升高而增加，这符合 I 型相行为特征。利用彭-罗宾逊状态方程和传统混合规则中的二元参数（kij 和 ηij），将实验观察到的 CO2 + 三烷氧基硅烷体系的 VLE 值联系起来。通过计算二元体系压力的平均相对偏差百分比验证了模型的准确性，结果是三甲氧基甲基硅烷 + CO2 体系的相对偏差百分比为 4.98%，三甲氧基甲基硅烷 + CO2 体系的相对偏差百分比为 3.64%。估算的变量均在合理范围内，且两种体系的预测 VLE 数据与观测 VLE 数据之间无明显差异。
{"title":"Vapor-liquid equilibria for the CO2 + trimethoxymethylsilane and CO2 + triethoxymethylsilane systems under high-pressure conditions","authors":"Divya Baskaran , Jongho Kim , Uma Sankar Behera, Hun-Soo Byun","doi":"10.1016/j.fluid.2024.114246","DOIUrl":"10.1016/j.fluid.2024.114246","url":null,"abstract":"<div><div>New binary isotherms are crucial for designing chemical separation processes within supercritical carbon dioxide (CO<sub>2</sub>) + trialkoxysilane systems. Vapor-liquid equilibria (VLE) were investigated for two-component systems, trimethoxymethylsilane + CO<sub>2</sub> and triethoxymethylsilane + CO<sub>2</sub>, at five temperatures (313.2, 333.2, 353.2, 373.2, and 393.2 K) and pressures up to 14.07 MPa using a synthetic high-pressure phase equilibria apparatus. The pressure-temperature (<em>P-T</em>) plot indicates that the critical mixture curve lies between the critical points of CO<sub>2</sub> and the trialkoxysilane compounds. The solubility of trimethoxymethylsilane and triethoxymethylsilane in CO<sub>2</sub> increased with increasing temperature at constant pressure, following a type-I phase behavior characteristic. The experimentally observed VLE values of the CO<sub>2</sub> + trialkoxysilane systems were correlated using the Peng-Robinson equation of state with binary parameters (<em>k<sub>ij</sub></em> and <em>η<sub>ij</sub></em>) in the conventional mixing rule. The model accuracy was validated by calculating the average relative deviation percentage for the pressure of the binary systems, resulting in values of 4.98% for the trimethoxymethylsilane + CO<sub>2</sub> system and 3.64% for the triethoxymethylsilane + CO<sub>2</sub> system. The estimated variables fell within reasonable limits and showed no significant differences between the predicted and observed VLE data for both systems.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114246"},"PeriodicalIF":2.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431978","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}
Pub Date : 2024-10-09DOI: 10.1016/j.fluid.2024.114248
Eugene G. Pashuk , Jiangtao Wu , Ilmutdin M. Abdulagatov
Bio-jet fuel is a key element in the aviation industry to reduce operating costs and environmental impacts. Bio-jet fuel is a complex mixture of four hydrocarbons (n-alkanes, isoalkanes, cycloalkanes and aromatics). In the present work, the speed of sound in pure n-octane, ethylcyclohexane, and their mixtures with six selected compositions of (0.3004, 0.4191, 0.4999, 0.5538, 0.6991, and 0.7852 mole fraction of ethylcyclohexane) has been measured along the l-G saturation curve in the temperature ranges from (286 to 443) K using the pulse method with a constant (acoustic) sounding base. The combined expanded absolute and relative uncertainties (0.95 level of confidence, k = 2) of the temperature, concentration, and speed of sound measurements are estimated to be 20 mK, 0.0006 mole fraction, and 0.2 %, respectively. The measured speed of sound data together with our previous reported density data for the pure component (ethylcyclohexane) and the mixture were used to calculate derived thermodynamic properties, such as isentropic compressibility and heat capacity ratios as a function of temperature along the l-G saturation curve for the pure components and the mixture for selected concentration of x = 0.8 mole fraction of ethylcyclohexane. The deviation of the measured speed of sound data for the mixture from the linear additive rule has been determined using the pure component data.
{"title":"Speed of sound measurements of binary n-octane+ ethylcyclohexane mixture at liquid-gas phase transition curve","authors":"Eugene G. Pashuk , Jiangtao Wu , Ilmutdin M. Abdulagatov","doi":"10.1016/j.fluid.2024.114248","DOIUrl":"10.1016/j.fluid.2024.114248","url":null,"abstract":"<div><div>Bio-jet fuel is a key element in the aviation industry to reduce operating costs and environmental impacts. Bio-jet fuel is a complex mixture of four hydrocarbons (<em>n</em>-alkanes, isoalkanes, cycloalkanes and aromatics). In the present work, the speed of sound in pure <em>n</em>-octane, <em>ethylcyclohexane</em>, and their mixtures with six selected compositions of (0.3004, 0.4191, 0.4999, 0.5538, 0.6991, and 0.7852 mole fraction of ethylcyclohexane) has been measured along the l-G saturation curve in the temperature ranges from (286 to 443) K using the pulse method with a constant (acoustic) sounding base. The combined expanded absolute and relative uncertainties (0.95 level of confidence, <em>k</em> = 2) of the temperature, concentration, and speed of sound measurements are estimated to be 20 mK, 0.0006 mole fraction, and 0.2 %, respectively. The measured speed of sound data together with our previous reported density data for the pure component (<em>ethylcyclohexane</em>) and the mixture were used to calculate derived thermodynamic properties, such as isentropic compressibility <span><math><msub><mi>k</mi><mi>S</mi></msub></math></span> and heat capacity ratios <span><math><mfrac><msub><mi>C</mi><mi>P</mi></msub><msub><mi>C</mi><mi>V</mi></msub></mfrac></math></span> as a function of temperature along the l-G saturation curve for the pure components and the mixture for selected concentration of <em>x</em> = 0.8 mole fraction of <em>ethylcyclohexane</em>. The deviation of the measured speed of sound data for the mixture from the linear additive rule has been determined using the pure component data.</div></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"589 ","pages":"Article 114248"},"PeriodicalIF":2.8,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142432696","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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