Fluid Phase Equilibria最新文献

英文中文

Determining state points through the radial distribution function of Yukawa fluids at equilibrium 通过平衡状态下汤川流体的径向分布函数确定状态点

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-24 DOI: 10.1016/j.fluid.2024.114270

Xurui Li , Jianxiang Tian

Based on our previous work [Fluid Phase Equilibria, 2023, 567, 113709], we here use the radial distribution function (RDF) to determine the state points (density and temperature) of a fluid under the Yukawa potential at equilibrium. The reduced density and reduced temperature are defined as

ρ^{*} = ρ σ^{3}

and

β^{*} = 1 / T^{*} = ϵ / k_{B} T

, respectively. Through the Molecular Dynamics (MD) simulations, we obtain equilibrium configurations and use these data for building models via two methods. The first method establishes two empirical correlations for each potential considered, one between the heights of the first peaks of the RDFs and state points, as well as the other between the displacements of the first peaks of the RDFs and state points. Through these empirical correlations, we can determine the state points of new Yukawa fluid systems with 100% accuracy. The second method utilizes artificial neural network models to predict state points from the heights and displacements of the first peaks of the RDFs, achieving 100% accuracy when the predicted results are rounded to one decimal place. The success of these methods again demonstrates the feasibility of determining state points solely based on equilibrium configurations, is an extension from the Lennard-Jones fluids to the Yukawa potential related fluids.

基于我们之前的工作[Fluid Phase Equilibria, 2023, 567, 113709]，我们在此使用径向分布函数（RDF）来确定流体在尤卡娃势平衡下的状态点（密度和温度）。还原密度和还原温度分别定义为 ρ*=ρσ3 和 β*=1/T*=ϵ/kBT 。通过分子动力学（MD）模拟，我们获得了平衡构型，并利用这些数据通过两种方法建立模型。第一种方法是为所考虑的每种电位建立两种经验相关性，一种是 RDFs 的第一个峰的高度与状态点之间的相关性，另一种是 RDFs 的第一个峰的位移与状态点之间的相关性。通过这些经验相关性，我们可以 100% 准确地确定新汤川流体系统的状态点。第二种方法是利用人工神经网络模型，根据 RDF 第一个峰的高度和位移预测状态点，当预测结果四舍五入到小数点后一位时，准确率达到 100%。这些方法的成功再次证明了仅根据平衡构型确定状态点的可行性，这是从伦纳德-琼斯流体扩展到尤卡瓦势相关流体的一种方法。

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引用次数: 0

A critical review of experimental methods, data, and predictions of water content 对含水量的实验方法、数据和预测的批判性评述

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-23 DOI: 10.1016/j.fluid.2024.114259

Larissa F. Torres , Thales Barbalho , Iuri Segtovich , Cláudio Dariva , Frederico W. Tavares , Papa M. Ndiaye

The capability to accurately determine and predict the water content is essential to assess and plan potential flow assurance issues associated with water condensing from gas in pipelines and leading to hydrate formation. Various experimental techniques and devices have been evaluated/tested to determine water content and different equations of state are used to describe these data. Here, a critical review of experimental techniques and thermodynamic methods to determine water content is presented. Particular attention is paid to the experimental techniques using Chilled Mirror, Quartz Crystal Microbalance (QCM), and Tunable Diode Laser Spectroscopy (TDLAS). A literature review and an experimental data bank of water content in binary and ternary gas mixtures with methane and/or CO₂ are also presented.

准确测定和预测含水量的能力对于评估和规划与管道中气体凝结水并导致水合物形成有关的潜在流量保证问题至关重要。为确定含水量，已经评估/测试了各种实验技术和设备，并使用不同的状态方程来描述这些数据。在此，将对确定含水量的实验技术和热力学方法进行严格审查。其中特别关注使用冷镜、石英晶体微天平（QCM）和可调谐二极管激光光谱（TDLAS）的实验技术。此外，还介绍了甲烷和/或二氧化碳二元和三元气体混合物中水含量的文献综述和实验数据库。

引用次数: 0

Phase equilibria and guest gas occupancy characteristics of H2-DIOX sII hydrates based on calorimetric and Raman analysis 基于量热和拉曼分析的 H2-DIOX sII 水合物的相平衡和客气占位特征

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-22 DOI: 10.1016/j.fluid.2024.114262

Jibao Zhang , Yan Li , Yang Li , Mengqi Xiao , Yizhi Rao , Praveen Linga , Lijie Chen , Zhenyuan Yin

Hydrogen (H₂) as the most abundant element offers a clean energy solution for a sustainable future. Thermodynamic hydrate promoters can enhance hydrate-based H₂ storage under mild pressure conditions. 1,3-dioxolane (DIOX) as a low-toxicity promoter has attracted attention for its potential to improve H₂ hydrate kinetics. However, the phase equilibria of H₂-DIOX in the presence of DIOX and its thermodynamic promotion mechanism are not fully elaborated and warrant thorough investigation. In this study, the phase equilibria of H₂-DIOX hydrates were measured for DIOX concentrations (C_DIOX) ranging from 2.0 mol% to 5.56 mol%. The equilibrium temperature of H₂-DIOX hydrates shifted rightward by 2.3 K at 15.0 MPa for 5.56 mol% DIOX compared to 2.0 mol% DIOX. The measured thermodynamic data were validated by fitting the H₂-DIOX hydrate phase equilibira using the Clausius–Clapeyron equation. The cage occupancy of H₂ and DIOX in H₂-DIOX sII hydrates was revealed through Raman spectroscopy and DSC thermal analysis. Two types of hydrates (DIOX and H₂-DIOX) were observed for all C_DIOX. Single H₂ molecules were enclathrated in the 5¹² cages of H₂-DIOX hydrates and increasing C_DIOX effectively enhanced DIOX molecules enclathration in the 5¹²6⁴ cages but had limited effect on the H₂ molecules in the 5¹² cages. The findings of this study provide fundametnal thermodynamic data and cage occupancy charateristics for H₂-DIOX sII hydrates below 15.0 MPa. The results provide guidance on the optimal thermodynamic promoter concentrations for future large-scale hydrate-based H₂ storage application.

氢（H2）作为最丰富的元素，为可持续发展的未来提供了清洁能源解决方案。热力学水合物促进剂可以在温和的压力条件下提高基于水合物的 H2 储存。1,3-二氧戊环（DIOX）作为一种低毒性促进剂，因其改善 H2 水合物动力学的潜力而备受关注。然而，H2-DIOX 在 DIOX 存在下的相平衡及其热力学促进机制尚未得到充分阐述，需要进行深入研究。本研究测量了 DIOX 浓度（CDIOX）从 2.0 摩尔% 到 5.56 摩尔% 时 H2-DIOX 水合物的相平衡。与 2.0 摩尔% 的 DIOX 相比，5.56 摩尔% 的 DIOX 在 15.0 兆帕时的 H2-DIOX 水合物平衡温度向右移动了 2.3 K。通过使用克劳修斯-克拉皮隆方程拟合 H2-DIOX 水合物相平衡，验证了测得的热力学数据。拉曼光谱和 DSC 热分析揭示了 H2-DIOX sII 水合物中 H2 和 DIOX 的笼占位。在所有 CDIOX 中都观察到了两种水合物（DIOX 和 H2-DIOX）。单个 H2 分子在 H2-DIOX 水合物的 512 个笼子中包层，增加 CDIOX 能有效增强 DIOX 分子在 51264 个笼子中的包层，但对 512 个笼子中的 H2 分子影响有限。本研究结果提供了 15.0 兆帕以下 H2-DIOX sII 水合物的基本热力学数据和笼占位特征。研究结果为未来基于水合物的大规模 H2 储存应用提供了最佳热力学促进剂浓度的指导。

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引用次数: 0

Coupling cubic equations of state with the concept of entropy scaling to model the viscosity of ionic liquids 将立方状态方程与熵缩放概念耦合以模拟离子液体的粘度

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-21 DOI: 10.1016/j.fluid.2024.114261

Aghilas Dehlouz , Romain Privat , Jean-Noël Jaubert

This short paper investigates the applicability of our previously developed entropy scaling model to pure ionic liquids and concludes that it can be used without any modification and leads to very satisfactory results when coupled with the Peng-Robinson or Soave-Redlich-Kwong cubic equations of state. For the considered ionic liquids, the average deviations between calculated and experimental viscosities were found to be around 4.6 and 5.8% for the two cubic equations of state, respectively.

这篇短文研究了我们之前开发的熵缩放模型在纯离子液体中的适用性，并得出结论：该模型无需任何修改即可使用，与 Peng-Robinson 或 Soave-Redlich-Kwong 立方状态方程结合使用可获得非常令人满意的结果。对于所考虑的离子液体，两种立方状态方程的计算粘度与实验粘度之间的平均偏差分别约为 4.6% 和 5.8%。

引用次数: 0

How reliable is the Real Adsorbed Solution Theory (RAST) for estimating ternary mixture equilibrium in microporous host materials? 真实吸附溶液理论（RAST）在估算微孔主材料中的三元混合物平衡时有多可靠？

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-20 DOI: 10.1016/j.fluid.2024.114260

Rajamani Krishna, Jasper M. van Baten

Microporous crystalline adsorbents such as zeolites, and metal-organic frameworks (MOFs) have potential use in a wide variety of separations applications. In applications such as CO₂ capture, the Ideal Adsorbed Solution Theory (IAST) often fails to provide a quantitative description of mixture adsorption equilibrium especially in cation-exchanged zeolites. The failure of the IAST is ascribable to non-compliance with one or more tenets mandated by the IAST such as (a) homogeneous distribution of adsorbates within the pore landscape, (b) no preferential location of guest species, and (c) absence of molecular clustering due to say hydrogen bonding. The focus of this article is on the reliability of the Real Adsorbed Solution Theory (RAST) models for quantitative estimation of adsorption equilibrium. Configurational-Bias Monte Carlo (CBMC) simulations are undertaken to determine the adsorption equilibrium for ternary CO₂/CH₄/N₂, CO₂/CH₄/C₃H₈, CO₂/CH₄/H₂, and water/methanol/ethanol mixtures in NaX, LTA-4A, CHA, DDR, and MFI zeolites. Additionally, CBMC simulations of the constituent binary pairs are used to determine the Wilson or NRTL parameters, taking due account of the dependence of the activity coefficients on the spreading pressure. Use of the binary pair Wilson or NRTL parameters allows the estimation of ternary mixture adsorption equilibrium, that is tested against the CBMC data on component loadings. In all investigated guest/host combinations, the RAST provides a good estimation of ternary mixture adsorption equilibrium.

沸石和金属有机框架（MOFs）等微孔结晶吸附剂具有广泛的分离应用潜力。在二氧化碳捕获等应用中，理想吸附溶液理论（IAST）往往无法定量描述混合物的吸附平衡，特别是在阳离子交换沸石中。IAST 的失效可归因于没有遵守 IAST 规定的一个或多个原则，例如：（a）吸附剂在孔隙中的均匀分布；（b）客体物种没有优先位置；以及（c）没有因氢键而导致的分子团聚。本文的重点是真实吸附溶液理论（RAST）模型在定量估计吸附平衡方面的可靠性。通过配置偏置蒙特卡罗（CBMC）模拟，确定了三元 CO2/CH4/N2、CO2/CH4/C3H8、CO2/CH4/H2 和水/甲醇/乙醇混合物在 NaX、LTA-4A、CHA、DDR 和 MFI 沸石中的吸附平衡。此外，对组成二元对的 CBMC 模拟用于确定 Wilson 或 NRTL 参数，同时适当考虑活性系数对扩散压力的依赖性。使用二元对 Wilson 或 NRTL 参数可以估算三元混合物的吸附平衡，并根据 CBMC 对组分负载的数据进行测试。在所有研究过的客体/主体组合中，RAST 都能很好地估计三元混合物的吸附平衡。

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引用次数: 0

Phase equilibria and volumetric properties of mixtures of highly fluorinated alcohols and water 高氟化醇和水混合物的相平衡和体积特性

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-18 DOI: 10.1016/j.fluid.2024.114258

Gonçalo M.C. Silva, José Santos Pereira, Milton Ponte, Tiago M. Eusébio, Diogo Machacaz, Pedro Morgado, Eduardo J.M. Filipe

New thermodynamic data are reported for aqueous solutions of highly fluorinated alcohols of different chain lengths. The liquid-liquid equilibrium (LLE) T-x diagram of the binary mixture (1H,1H-perfluoropropanol + water) was determined, as well as the LLE phase diagram of the ternary mixture (1H,1H-perfluoropropanol + 1-propanol + water) at 298.15 K and atmospheric pressure. The mutual solubilities of water with several linear perfluorinated alcohols (CF₃(CF₂)_nCH₂OH, n = 1–5) and the tertiary alcohol perfluoro-t-butanol ((CF₃)₃COH) were also measured at 298.15 K. Finally, volumetric properties such as the excess molar volumes and partial molal volumes at infinite dilution of the different fluorinated alcohols in water were also determined and discussed comparing with equivalent data from the literature for the corresponding hydrogenated alcohols.

报告了不同链长的高氟化醇水溶液的新热力学数据。确定了二元混合物（1H,1H-全氟丙醇 + 水）的液液平衡（LLE）T-x 图，以及三元混合物（1H,1H-全氟丙醇 + 1-丙醇 + 水）在 298.15 K 和大气压力下的液液平衡相图。最后，还测定了水与几种线性全氟醇（CF3(CF2)nCH2OH，n = 1-5）和全氟叔丁醇（(CF3)3COH）在 298.15 K 下的互溶性。

引用次数: 0

Molecular dynamics simulation of the interaction between ionic liquid [OPy][BF4] and SO2 离子液体 [OPy][BF4] 与二氧化硫相互作用的分子动力学模拟

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-16 DOI: 10.1016/j.fluid.2024.114257

Guanglai Zhu , Siwen Zhou , Zhaopeng Ma , Jianqiang Xu

Ionic liquids possess novel properties and can efficiently absorb harmful gases, potentially serving as a new type of absorbent. In this study, the binary system of ionic liquid N-octylpyridinium tetrafluoroborate [OPy][BF₄] and sulfur dioxide (SO₂) has been selected as the research object, and the structure and properties of the system have been studied by molecular dynamics simulation. The interaction between SO₂ and ionic liquids is explored by using the radial distribution functions (RDFs), coordination numbers (CNs) and spatial distribution functions (SDFs). The results of microstructures show that due to the strong interaction with anions, SO₂ is mostly orderly distributed around the anions of ionic liquids. However, the coordination ability of the polar region of the ionic liquid and SO₂ is nearly equivalent to that of the non-polar region. At the same time, it is found that the addition of SO₂ enhanced the order degree of the polar and the non-polar regions of ionic liquids, especially on non-polar regions. Through the discussion of the interaction between [OPy][BF₄] and SO₂, it can be concluded that the mechanism of SO₂ absorption by [OPy][BF₄] is the combined effect of anions and cations. This study aims to provide new insights for the potential applications of ionic liquids in industrial fields such as petroleum and flue gas desulfurization.

离子液体具有新颖的特性，能有效吸收有害气体，有可能成为一种新型吸收剂。本研究以离子液体 N-辛基吡啶鎓四氟硼酸盐[OPy][BF4]和二氧化硫（SO2）的二元体系为研究对象，通过分子动力学模拟研究了该体系的结构和性质。利用径向分布函数（RDF）、配位数（CN）和空间分布函数（SDF）探讨了 SO2 与离子液体之间的相互作用。微观结构结果表明，由于与阴离子的强相互作用，二氧化硫大多有序地分布在离子液体的阴离子周围。然而，离子液体极性区域与 SO2 的配位能力几乎等同于非极性区域。同时，研究发现 SO2 的加入增强了离子液体极性区和非极性区的有序度，尤其是在非极性区。通过讨论[OPy][BF4]与 SO2 的相互作用，可以得出[OPy][BF4]吸收 SO2 的机理是阴阳离子的共同作用。本研究旨在为离子液体在石油和烟气脱硫等工业领域的潜在应用提供新的见解。

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引用次数: 0

Predicting solvation free energies for neutral molecules in any solvent with openCOSMO-RS 利用 openCOSMO-RS 预测中性分子在任何溶剂中的溶解自由能

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-16 DOI: 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.

在本研究中，我们介绍了 openCOSMO-RS 24a，它是开源 COSMO-RS 模型的改进版本，利用 ORCA 6.0 中的量子化学计算进行参数化，充分利用了一个综合数据集，其中包括溶解自由能、分配系数和无限稀释活性系数，主要适用于 25 °C 下的各种溶质和溶剂。这是该模型的第一个版本，它还能根据 ORCA 计算结果预测溶解自由能。此外，我们还开发了一个定量结构-性质关系模型来预测溶剂的摩尔体积，这是仅从结构预测溶解自由能和分配系数的基本要求。我们的结果表明，openCOSMO-RS 24a 的溶解自由能平均绝对偏差为 0.45 kcal mol1，分配系数对数为 0.76，无限稀释活性系数对数为 0.51，与之前的 openCOSMO-RS 22 参数化相比有所改进，与 COSMOtherm 24 BP-TZVP 的结果相当。用户界面经过扩展，可以直接在 ORCA 6.0 中或通过命令行将其用作溶解模型，从而为研究人员在化学和材料科学领域的应用提供了一个强大的工具。

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引用次数: 0

Predicting viscosity-concentration dependencies of binary organic mixtures using molecular dynamics methods 利用分子动力学方法预测二元有机混合物的粘度-浓度相关性

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-15 DOI: 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。

引用次数: 0

Effect of Ion Specificity on Thermodynamic Inhibition of CH4 and CO2 Hydrates: An Experimental and Modeling Study 离子特异性对 CH4 和 CO2 水合物热力学抑制作用的影响：实验与模型研究

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-15 DOI: 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。

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引用次数: 0

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