Fluid Phase Equilibria最新文献_第10页

Thermodynamic modelling of systems involved in natural gas dehydration with triethylene glycol using a group contribution association model 利用群体贡献关联模型建立天然气与三甘醇脱水系统的热力学模型

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-05 DOI: 10.1016/j.fluid.2024.114241

George Tasios , Vasiliki Louli , Efstathios Skouras , Even Solbraa , Epaminondas Voutsas

Natural gas (NG) dehydration through absorption into Triethylene Glycol (TEG) is one of the most important applications in the NG industry. The optimal design of the TEG dehydration process requires a deep understanding of the thermodynamic behavior of mixtures containing TEG, water, hydrocarbons, and other compounds present in natural gas. In this work, the recently developed Universal Mixing Rule – Cubic Plus Association (UMR-CPA) group contribution equation of state (EoS) is extended to these systems. UMR-CPA combines the PR-CPA EoS with the UNIFAC group contribution activity coefficient model through the Universal Mixing Rules. Parameters for pure water, TEG and NG components were determined by accurately fitting vapor pressure, density and heat capacity data. For non-associating compounds, the model leads to overall deviations of 1.2 % in vapor pressures and 6.1 % in isobaric heat capacities. Water properties are also quite accurately described, with overall deviations of approximately 0.4 %, 1.2 % and 5.7 % in vapor pressures, liquid densities and isobaric heat capacities, respectively. The model was then applied to mixtures of water and TEG with gases and hydrocarbons by correlating the proper group interaction parameters. Very satisfactory results were obtained for both vapor-liquid and liquid-liquid phase equilibria in these systems, where also an adequate reproduction of the minimum of hydrocarbon solubility in water was noted. Finally, the UMR-CPA EoS was further validated through the prediction of the phase behavior of ternary systems including TEG and/or water and NG compounds. Very good predictions were achieved for the low TEG and water content in the vapor phase of the TEG-H₂O-CH₄ ternary system, with absolute deviations of around 0.05 and 23.26 ppm, respectively. Overall, the model yields accurate predictions, suggesting its suitability for designing the TEG dehydration process.

通过吸收三乙二醇 (TEG) 实现天然气 (NG) 脱水是 NG 工业中最重要的应用之一。要优化 TEG 脱水工艺的设计，就必须深入了解天然气中含有 TEG、水、碳氢化合物和其他化合物的混合物的热力学行为。在这项工作中，最近开发的通用混合规则-立方加联结（UMR-CPA）组贡献状态方程（EoS）被扩展到这些系统中。UMR-CPA 通过通用混合规则将 PR-CPA EoS 与 UNIFAC 群体贡献活动系数模型相结合。通过精确拟合蒸汽压力、密度和热容量数据，确定了纯水、TEG 和 NG 成分的参数。对于非缔合化合物，该模型导致的蒸汽压总体偏差为 1.2%，等压热容总体偏差为 6.1%。水的性质也得到了相当准确的描述，蒸气压、液体密度和等压热容的总体偏差分别约为 0.4%、1.2% 和 5.7%。然后，通过关联适当的基团相互作用参数，将该模型应用于水和 TEG 与气体和碳氢化合物的混合物。在这些系统中，气-液相和液-液相平衡都得到了非常令人满意的结果，同时还注意到碳氢化合物在水中的最小溶解度也得到了充分的再现。最后，通过预测包括 TEG 和/或水和 NG 化合物在内的三元系统的相行为，进一步验证了 UMR-CPA EoS。对 TEG-H2O-CH4 三元体系气相中较低的 TEG 和水含量进行了非常好的预测，绝对偏差分别约为 0.05 和 23.26 ppm。总体而言，该模型能得出准确的预测结果，表明其适用于设计 TEG 脱水过程。

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引用次数: 0

Co-sorption of volatile components in polymer-based pharmaceutical formulations 聚合物基药物制剂中挥发性成分的共吸附作用

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-05 DOI: 10.1016/j.fluid.2024.114247

Jana Kerkhoff , Dominik Borrmann , Gabriele Sadowski

Amorphous Solid Dispersions (ASDs) are mixtures of active pharmaceutical ingredients (APIs) and polymers aiming to increase API aqueous solubility and bioavailability. ASDs are often produced using solvent-based manufacturing, such as spray drying. Due to solubility or miscibility limitations in one solvent, solvent mixtures are frequently used for this purpose. Drying solvents or solvent mixtures from polymer-based products like ASDs is an energy-intensive and time-consuming process. Designing and optimising this drying process requires knowledge of the sorption isotherms of the solvent(s) in these polymer-based products. In this work, we developed a novel approach for measuring the simultaneous absorption/desorption of two solvents in a polymer. Combining classical dynamic vapour sorption (DVS) measurements with Raman spectroscopy, this innovative approach provides a more detailed and accurate measurement of the sorption isotherms than common methods. Moreover, we developed an approach for precisely predicting the sorption equilibria in three-component systems just based on sorption data of the corresponding binary subsystems. Our modelling approach combines the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) with the Non-Equilibrium Thermodynamics of Glassy Polymers (NET-GP). Building on the description of the sorption isotherms of either water or ethanol in poly(vinylpyrrolidone-co-vinyl acetate) (PVPVA64) and in indomethacin (IND), we were able to quantitatively predict the simultaneous sorption of water and ethanol in PVPVA64 and the one of ethanol in an IND/PVPVA64 ASD.

无定形固体分散体（ASD）是活性药物成分（API）和聚合物的混合物，旨在提高 API 的水溶性和生物利用度。ASD 通常采用喷雾干燥等溶剂型生产工艺。由于在一种溶剂中的溶解度或混溶性受到限制，因此经常使用混合溶剂。从 ASD 等聚合物基产品中干燥溶剂或溶剂混合物是一个耗能耗时的过程。设计和优化这种干燥工艺需要了解这些聚合物基产品中溶剂的吸附等温线。在这项工作中，我们开发了一种测量聚合物中两种溶剂同时吸收/解吸的新方法。这种创新方法将经典的动态蒸汽吸附 (DVS) 测量与拉曼光谱相结合，提供了比普通方法更详细、更精确的吸附等温线测量。此外，我们还根据相应二元子系统的吸附数据，开发了一种精确预测三组分系统吸附平衡的方法。我们的建模方法结合了扰动链统计关联流体理论（PC-SAFT）和玻璃聚合物非平衡热力学（NET-GP）。基于水或乙醇在聚（乙烯基吡咯烷酮-醋酸乙烯酯）（PVPVA64）和吲哚美辛（IND）中的吸附等温线描述，我们能够定量预测水和乙醇在 PVPVA64 中的同时吸附以及乙醇在 IND/PVPVA64 ASD 中的吸附。

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引用次数: 0

Assessment of dissociation enthalpies of methane hydrates in the absence and presence of ionic liquids using the Clausius-Clapeyron approach 利用克劳修斯-克拉皮隆方法评估无离子液体和有离子液体时甲烷水合物的解离焓

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-02 DOI: 10.1016/j.fluid.2024.114245

Mohammad Arshad , Tausif Altamash , Anastasiia Keba , Mohd Sajid Ali , Johan Jacquemin , José M.S.S. Esperança , Mohammad Tariq

The Clausius-Clapeyron (CC) equation is generally preferred to obtain dissociation enthalpies (ΔH) of hydrate-forming systems due to its ease of use. The application of other direct and indirect methods becomes more problematic if complex additives such as ionic liquids (ILs) are also present in the system. In this work, around 400 equilibrium data points for methane hydrates in the presence of over 80 ILs were collected from the literature in the temperature and pressure ranges of (272.10 – 306.07) K and (2.48 – 100.34) MPa, respectively. The ΔH of methane hydrates in the absence and presence of ionic liquids (ILs) have been calculated using the CC equation. The compressibility factor (z), required to calculate ΔH at each phase equilibrium condition has been obtained from three different approaches viz., Peng-Robinson (PR) equation of state, Soave-Redlich-Kwong (SRK) equation of state and Pitzer (Pz) correlation. The results were compared to the experimentally reported dissociation enthalpy (54.5 ± 1.5 kJ.mol⁻¹) of methane hydrates. The role of the compressibility factor along with the slope of the equilibrium data set and the temperature/pressure range in determining the outcome of the CC equation has been discussed. The effect of molar mass, molar volume, and hydrate suppression temperature of the ILs on the ΔH of methane hydrates has been explored. The tested ILs do not show a systematic and significant influence on enthalpies, rather they show a large scattering in the ΔH values, which might mask any existing subtle effect of the ILs on the dissociation enthalpies. Therefore, this approach should be dealt with care to obtain molecular-level insights.

克劳修斯-克拉皮隆（CC）方程由于易于使用，通常被优先用于获取水合物形成体系的解离焓（ΔH）。如果体系中还存在离子液体（IL）等复杂添加剂，则其他直接和间接方法的应用就会变得更加困难。在这项工作中，从文献中收集了约 400 个甲烷水合物在 80 多种 IL 存在下的平衡数据点，温度和压力范围分别为 (272.10 - 306.07) K 和 (2.48 - 100.34) MPa。使用 CC 方程计算了没有离子液体 (IL) 和有离子液体 (IL) 时甲烷水合物的 ΔH。计算每个相平衡条件下 ΔH 所需的可压缩因子 (z) 是通过三种不同的方法获得的，即彭-罗宾逊 (PR) 状态方程、索夫-雷德里希-邝 (SRK) 状态方程和皮策 (Pz) 相关性。研究结果与实验报告的甲烷水合物解离焓（54.5 ± 1.5 kJ.mol-1 ）进行了比较。讨论了可压缩因子、平衡数据集斜率和温度/压力范围在决定 CC 方程结果中的作用。还探讨了 IL 的摩尔质量、摩尔体积和水合物抑制温度对甲烷水合物 ΔH 的影响。测试结果表明，ILs 对焓值的影响并不系统且不明显，相反，它们在 ΔH 值上表现出很大的分散性，这可能会掩盖 ILs 对解离焓值的任何微妙影响。因此，应谨慎处理这种方法，以获得分子层面的见解。

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引用次数: 0

Predictive potentialities of the Quasi-Random Lattice model for electrolyte solutions, discussion and improvement strategies 电解质溶液准随机晶格模型的预测潜力、讨论和改进策略

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-10-01 DOI: 10.1016/j.fluid.2024.114243

Elsa Moggia

This article focuses on the predictive potentialities of the Quasi-Random Lattice (QRL) model, developed for describing the activity behaviour of electrolytic solutions, and elaborates strategies for their improvement.

First, the study critically discusses the computational-experimental procedure (previously published) for determining the QRL parameterization, whose convergence within few iterations is counterbalanced by known experimental issues concerning, in particular, the mean activity coefficient. An alternative procedure is proposed, that makes use of osmotic data at medium-high concentrations, so as to make QRL more interesting from a practical point of view.

Second, the study explores the applicability of the model beyond the concentration ranges earlier considered. To this purpose, the solution density is evaluated in detail. Its thermodynamic relationship with the mean activity coefficient yields a parametric Abel Equation of the Second Kind valid in the medium-high range of concentrations. A further density equation is formulated, useful in the low-medium range, based on a classical power-series combined with appropriate analytical constraints to improve estimation and prediction methods.

QRL theory, methods and procedures are applied to binary aqueous solutions at 25°C.

首先，研究对确定 QRL 参数化的计算-实验程序（之前已发表）进行了批判性讨论，该程序在少数迭代中收敛，但由于已知的实验问题，特别是平均活性系数的问题而受到抵消。本研究提出了一个替代程序，利用中高浓度下的渗透数据，使 QRL 从实用角度看更有意义。其次，本研究探讨了模型在先前考虑的浓度范围之外的适用性。为此，我们对溶液密度进行了详细评估。它与平均活性系数之间的热力学关系产生了一个在中高浓度范围内有效的参数阿贝尔第二类方程。在经典幂级数的基础上，结合适当的分析约束条件，进一步制定了适用于中低浓度范围的密度方程，以改进估计和预测方法。QRL 理论、方法和程序适用于 25°C 的二元水溶液。

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引用次数: 0

Determination and correlation of liquid-liquid equilibrium data for the extraction of glycerol carbonate from glycerol using 2-pentanone, cyclohexanone, and 4-methyl-2-pentanone 使用 2-戊酮、环己酮和 4-甲基-2-戊酮从甘油中萃取碳酸甘油酯的液液平衡数据的测定和相关性研究

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-09-30 DOI: 10.1016/j.fluid.2024.114242

Hui Shi , Jiazuo Wei , Tiantian Xu , Yulei Guan , Jingjun Liu

Glycerol carbonate, a high-value derivative of glycerol, finds extensive applications in the cosmetics, pharmaceuticals, and food industries, as well as in plasticizers and battery electrolytes. This study assessed the feasibility of extracting glycerol carbonate from glycerol using three solvents: 2-pentanone, cyclohexanone, and 4-methyl-2-pentanone. The extraction performance of these solvents was evaluated through liquid-liquid equilibrium (LLE) measurements at atmospheric pressure and temperatures of 303.2 K, 313.2 K, and 323.2 K. Although 4-methyl-2-pentanone exhibited high extraction selectivity, the distribution coefficient of glycerol carbonate in it was less than one. Conversely, while cyclohexanone provided a high distribution coefficient, its extraction selectivity was low. In contrast, 2-pentanone demonstrated a relatively balanced extraction selectivity and capacity. The Non-Random Two-Liquid (NRTL) model was used as an activity model in the equilibrium data correlation, and the corresponding binary interaction parameters were estimated. The regressed parameters of the NRTL model successfully reproduced the phase equilibrium trends observed for all systems investigated, facilitating process design and solvent screening for glycerol carbonate extraction from glycerol.

碳酸甘油酯是甘油的一种高价值衍生物，在化妆品、药品和食品工业以及增塑剂和电池电解液中都有广泛的应用。本研究评估了使用三种溶剂从甘油中提取碳酸甘油酯的可行性：2-戊酮、环己酮和 4-甲基-2-戊酮。虽然 4-甲基-2-戊酮表现出较高的萃取选择性，但碳酸甘油酯在其中的分配系数小于 1。相反，虽然环己酮的分配系数较高，但其萃取选择性较低。相比之下，2-戊酮的萃取选择性和萃取能力相对平衡。在平衡数据关联中，使用了非随机双液（NRTL）模型作为活性模型，并估算了相应的二元相互作用参数。NRTL 模型的回归参数成功地再现了所有研究体系的相平衡趋势，有助于从甘油中萃取碳酸甘油酯的工艺设计和溶剂筛选。

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引用次数: 0

Vapor-liquid equilibria of the ternary system of methane + n-decane + n-octacosane at high pressures 高压下甲烷 + 正癸烷 + 正二十八烷三元体系的汽液平衡

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-09-28 DOI: 10.1016/j.fluid.2024.114239

Kian Shariati , Sona Raeissi , Cor.J. Peters

Alkane mixture phase equilibria is required for a range of industrial applications, most particularly for the petroleum industries. Mixtures containing light and heavy normal alkanes are of even further significance due to their non-ideal thermodynamic behavior. In this work, for the first time, the ternary system of C₁ + C₁₀ + C₂₈ was investigated experimentally to obtain bubble point pressures at various concentrations and temperatures ranging from 373 up to 445 K. The synthetic method of phase equilibrium measurements was utilized, which is known to have high accuracy. The resulting bubble points for the mixtures ranged in pressure from about 3 MPa up to 6 MPa. The data indicated that methane concentrations had the greatest impact, not only on the magnitude of the bubble point pressure, but also on the slope of its temperature trend. The relative concentrations of n-decane and n-octacosane had far less impact on the bubble point curves. The results were also modelled using the Peng–Robinson equation of state, and it was found that this equation has the capability to predict the data with an AARD% of 5.1 %. When temperature-independent binary interaction parameters were optimized to the data, the AARD% reduced to 2.4 %. Although the components vary greatly in size, perhaps the success of the Peng–Robinson equation of state for this mixture could be attributed to the fact that it was developed for hydrocarbon mixtures, and so, a reason for its popularity in the petroleum industries, alongside its simplicity and ease of use.

一系列工业应用，尤其是石油工业，都需要烷烃混合物相平衡。含有轻重正烷烃的混合物由于其非理想的热力学行为而更加重要。在这项工作中，首次对 C1 + C10 + C28 三元体系进行了实验研究，以获得在不同浓度和 373 至 445 K 温度范围内的气泡点压力。混合物的气泡点压力从 3 兆帕到 6 兆帕不等。数据表明，甲烷浓度不仅对气泡点压力的大小影响最大，而且对其温度趋势的斜率影响也最大。正癸烷和正二十八烷的相对浓度对气泡点曲线的影响要小得多。我们还使用彭-罗宾逊状态方程对结果进行了模拟，发现该方程能够预测数据，AARD%为 5.1%。当根据数据优化与温度无关的二元相互作用参数时，AARD% 降至 2.4%。虽然各组分的大小差异很大，但彭-罗宾逊状态方程之所以能成功用于该混合物，可能是因为它是针对碳氢化合物混合物而开发的，因此，除了简单易用之外，它在石油工业中也很受欢迎。

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引用次数: 0

Kinetic modeling of palmitic acid hydrodeoxygenation incorporating phase-equilibria predictions from the GC-PC-SAFT equation of state 结合 GC-PC-SAFT 状态方程的相平衡预测建立棕榈酸加氢脱氧的动力学模型

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-09-25 DOI: 10.1016/j.fluid.2024.114236

Mariana Afonso Pinto Pedroza , Iuri Soter Viana Segtovich , Mônica Antunes Pereira da Silva

In this work, we investigated the phase equilibria and the kinetics of palmitic acid hydrodeoxygenation over Pt/C to produce liquid hydrocarbons as drop-in biofuels. To describe the reaction mixture in detail, the binary interaction parameters of water/hydrogen, water/palmitic acid, water/n-hexadecane, and water/hexadecan-1-ol were estimated for a group contribution model based on the PC-SAFT equation of state using experimental solubility data taken from literature. Kinetic modeling using a power law model based on concentrations, a power law model based on fugacities, and a coupled VLE/power-law model were conducted to evaluate the effects of considering the non-ideality and the phase equilibria of the system. Under the operational conditions studied, the power law model based on concentrations was deemed more suitable to describe the process since it provided a faster implementation and similar outcomes compared to the fugacity-based and the VLE coupled models.

在这项工作中，我们研究了棕榈酸在 Pt/C 上加氢脱氧生成液态烃作为滴入式生物燃料的相平衡和动力学。为了详细描述反应混合物，我们根据 PC-SAFT 状态方程，利用文献中的实验溶解度数据，估算了水/氢、水/棕榈酸、水/正十六烷和水/正十六烷-1-醇的二元相互作用参数。使用基于浓度的幂律模型、基于逸度的幂律模型和 VLE/ 幂律耦合模型进行了动力学建模，以评估考虑系统的非理想性和相平衡的影响。在所研究的运行条件下，基于浓度的幂律模型被认为更适合描述过程，因为与基于逸散度的模型和 VLE 耦合模型相比，该模型的实施速度更快，结果相似。

引用次数: 0

Thermodynamic phase equilibria of binary SF6–N2O hydrates and their structural analysis for the hydrate-based greenhouse gas capture 二元 SF6-N2O 水合物的热力学相平衡及其基于水合物的温室气体捕获结构分析

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-09-24 DOI: 10.1016/j.fluid.2024.114238

Wonhyeong Lee , Jeongwoo Lee , Kwangbum Kim , Yun-Ho Ahn , Jae W. Lee

The increasing greenhouse gas (GHG) emissions from industrial activities have driven the development of efficient and environmentally safe GHG capture technologies. Clathrate hydrates, primarily composed of water, have attracted significant attention for their potential in GHG capture due to their ability to manage large emissions and their environmental advantages over materials like amine-based sorbents and metal-organic frameworks. This study investigates the hydrate-based capture of SF₆ and N₂O, two potent GHGs, to develop an effective GHG capture process. Phase equilibrium measurements demonstrate that binary SF₆-N₂O hydrates can form under moderate thermodynamic conditions, even with a small proportion of SF₆, highlighting the feasibility of using hydrate-based methods to capture GHG mixtures. Furthermore, the formation of binary SF₆-N₂O hydrates enhances GHG volumetric storage capacity compared to pure SF₆ hydrates. The guest compositions calculated for each binary SF₆-N₂O hydrate phase, along with spectroscopic analyses (Powder X-Ray Diffraction and Raman spectroscopy), confirm that the high GHG uptake in binary hydrates results from N₂O molecules occupying the small cages of structure II hydrates, which are inaccessible to the larger SF₆ molecules. These findings suggest that both the small and large cages of sII hydrates can be practically utilized for efficient capture of GHG mixture (SF₆ and N₂O) under mild conditions, thereby increasing the storage density of GHGs within the hydrate structure.

工业活动产生的温室气体（GHG）排放量不断增加，推动了高效且环保安全的温室气体捕集技术的发展。以水为主要成分的水合物因其管理大量排放的能力，以及与胺基吸附剂和金属有机框架等材料相比具有的环境优势，在温室气体捕获方面的潜力备受关注。本研究调查了基于水合物的 SF6 和 N2O（两种强效温室气体）捕集方法，以开发一种有效的温室气体捕集工艺。相平衡测量结果表明，即使 SF6 的比例很小，在中等热力学条件下也能形成 SF6-N2O 二元水合物，这突出表明了使用基于水合物的方法捕获温室气体混合物的可行性。此外，与纯 SF6 水合物相比，二元 SF6-N2O 水合物的形成提高了温室气体的体积储存能力。计算出的每种二元 SF6-N2O 水合物相的客体成分以及光谱分析（粉末 X 射线衍射和拉曼光谱）证实，二元水合物中的高温室气体吸收率是由于 N2O 分子占据了结构 II 水合物的小笼子，而较大的 SF6 分子无法进入这些笼子。这些发现表明，在温和的条件下，可实际利用 sII 水合物的小笼和大笼有效捕获温室气体混合物（SF6 和 N2O），从而提高水合物结构中温室气体的储存密度。

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引用次数: 0

Prediction of pure and mixture thermodynamic properties and phase equilibria using an optimized equation of state – part 1: Parameter estimation 利用优化状态方程预测纯净物和混合物的热力学性质和相平衡--第 1 部分：参数估计

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-09-24 DOI: 10.1016/j.fluid.2024.114240

Allan Paolo L. Almajose , Maria Lourdes P. Dalida

This study presents a novel three-parameter equation of state (EOS) wherein attraction parameter polynomial coefficients are optimized to enhance predictive capabilities. The performance of the proposed EOS is systematically compared with established models including Peng-Robinson, Patel-Teja, and Twu-Coon-Cunningham equations. Through comprehensive evaluation, it is demonstrated that the proposed EOS exhibits superior accuracy in vapor pressure and latent enthalpy predictions, while maintaining comparable precision in liquid density estimations. Notably, the fugacity expression of the proposed EOS closely resembles that of a two-parameter equation, resulting in significantly reduced computational overhead. Additionally, a comprehensive table of equation of state parameters for all four equations is available in an online repository, facilitating easy implementation and comparison. Furthermore, a reliable generalized polynomial correlation is provided for the proposed EOS parameters against the true compressibility factor and acentric factor, leveraging data accessibility and enhancing its applicability and versatility. These findings underscore the potential of the optimized attraction parameter polynomial coefficients approach in advancing the accuracy and efficiency of EOS modeling, thereby offering promising avenues for diverse applications in thermodynamics and process engineering.

本研究提出了一种新颖的三参数状态方程（EOS），其中对吸引参数多项式系数进行了优化，以提高预测能力。将所提出的状态方程的性能与彭-罗宾逊方程、帕特尔-特加方程和特武-库恩-坎宁安方程等已有模型进行了系统比较。通过综合评估，证明了所提出的 EOS 在蒸气压和潜焓预测方面具有更高的精度，同时在液体密度估算方面也保持了相当的精度。值得注意的是，拟议 EOS 的逸度表达式与双参数方程的逸度表达式非常相似，从而大大降低了计算开销。此外，所有四个方程的状态方程参数综合表都可在在线资料库中找到，便于实施和比较。此外，还提供了可靠的广义多项式相关性，用于将所提出的状态方程参数与真实的压缩系数和中心系数进行比较，从而充分利用数据的可获取性，提高其适用性和通用性。这些发现强调了优化吸引参数多项式系数方法在提高 EOS 建模的准确性和效率方面的潜力，从而为热力学和过程工程中的各种应用提供了前景广阔的途径。

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引用次数: 0

Quasi-universally modeling of interfacial properties for saturated liquids using a dimensionless calorimetric parameter 利用无量纲量热参数建立饱和液体界面特性的准通用模型

IF 2.8 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2024-09-21 DOI: 10.1016/j.fluid.2024.114237

Nian Li , Xuehui Wang , Shenghan Jin , Neng Gao , Guangming Chen

In this work, the interfacial property of surface tension has been observed to be quasi-universally linked to a dimensionless calorimetric parameter (DCP) for saturated simple liquids. This parameter, derived from thermodynamic calorimetric properties and exclusively influenced by molecular interactions, holds promise for predicting interfacial property and displaying universal behavior. Similar to the excess entropy scaling, empirical evidence indicates linear relations between interfacial properties with the DCP, when appropriate scaling is applied. Based on this observation, formulas for calculating these properties through DCP has been be developed. For fluids with strong molecular interactions, we have also identified their deviations from universality and have proposed a new DCP based modification strategy. These new DCP-based models were evaluated and validated by comparing them with experimental data for 19 pure fluids from different molecular structure catalogues. The average absolute deviations (AADs) were within 2.04 %.

在这项工作中，观察到表面张力的界面特性与饱和简单液体的无量纲量热参数（DCP）具有准普遍联系。该参数源自热力学量热特性，仅受分子相互作用的影响，有望预测界面特性并显示出普遍行为。与过量熵缩放类似，经验证据表明，如果采用适当的缩放，界面特性与 DCP 之间存在线性关系。基于这一观察结果，我们开发了通过 DCP 计算这些属性的公式。对于具有强分子相互作用的流体，我们还确定了它们与普遍性的偏差，并提出了基于 DCP 的新修正策略。通过将这些基于 DCP 的新模型与来自不同分子结构目录的 19 种纯流体的实验数据进行比较，对其进行了评估和验证。平均绝对偏差（AADs）在 2.04 %以内。

引用次数: 0