Fluid Phase Equilibria最新文献_第7页

A MD simulation study on the influence of pressure on sodium crystal melting 压力对钠晶体熔化影响的MD模拟研究

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-09-25 DOI: 10.1016/j.fluid.2025.114598

Tingting Ma , Tongtong Liu , Yang Li , Baiheng Jing , Panrong Wu , Qinglin Cheng

The molecular dynamics (MD) method and EAM/FS potential are used to study the influence of pressure (1 kPa ∼ 500 MPa) on the non-equilibrium melting process of alkali metal sodium crystals. The changes in macroscopic physical parameters such as potential energy, volume, and heat capacity (C_p) with pressure are obtained, and the evolutions of atomic clusters during the melting process are analyzed by RDF and PTM methods. The non-equilibrium melting temperature (T'_m) and melting time (Δt_m) under different pressures are gotten by macroscopic physical parameters analysis. The pressure has a significant impact on the melting behavior of sodium, particularly at pressures below 150 MPa. The T'_m increases with the increase of pressure, ranging from 423 K to 464 K within the pressure range of 1 kPa to 500 MPa, which is consistent with the experimental data. Besides, the Δt_m first decreases and then increases with increasing pressure, and the shortest melting time is 7.6 ps at 90 MPa. Both RDF analysis and PTM analysis can describe the phase transition process of sodium melting, and also indicate that T'_m increases with increasing pressure. The PTM analysis method can effectively study the transformation of different sodium atom clusters (BCC, HCP, FCC, and Other clusters) during the sodium melting process. It is found that as the temperature increased, some BCC clusters directly transform into Other clusters, while the others first transform into intermediate FCC and HCP clusters, and then into Other clusters. The range of T'_m of sodium is determined to be 425 K ∼ 467 K using PTM analysis method, which is consistent with the results of C_p analysis. There is a good correspondence between the changes in macroscopic physical parameters and the evolution of the atomic clusters during the melting process of sodium crystals. Both of these changes can reveal the melting process of sodium. The thermodynamic parameters related to sodium melting obtained through the MD simulations can provide theoretical support for the applications and simulations of solid-liquid phase transition of sodium under relatively low-pressure conditions.

采用分子动力学（MD）方法和EAM/FS电位研究了压力（1 kPa ~ 500 MPa）对碱金属钠晶体非平衡熔融过程的影响。得到了宏观物理参数如势能、体积和热容（Cp）随压力的变化，并利用RDF和PTM方法分析了熔炼过程中原子团簇的演化。通过宏观物理参数分析，得到了不同压力下的非平衡熔化温度T m和熔化时间Δtm。压力对钠的熔化行为有显著的影响，特别是在压力低于150mpa时。T′m随压力的增大而增大，在1 kPa ~ 500 MPa压力范围内，T′m变化范围为423 ~ 464 K，与实验数据一致。随着压力的增加，Δtm先减小后增大，在90 MPa时熔化时间最短为7.6 ps。RDF分析和PTM分析都能很好地描述钠熔融的相变过程，也表明T′m随压力的增加而增大。PTM分析方法可以有效地研究不同钠原子团簇（BCC、HCP、FCC和其他团簇）在钠熔化过程中的转变。研究发现，随着温度的升高，一些BCC团簇直接转变为Other团簇，而另一些则先转变为中间FCC和HCP团簇，然后再转变为Other团簇。采用PTM分析方法测定钠的T′m范围为425 K ~ 467 K，与Cp分析结果一致。在钠晶体熔化过程中，宏观物理参数的变化与原子团簇的演化有很好的对应关系。这两种变化都能揭示钠的熔融过程。通过MD模拟得到的与钠熔融有关的热力学参数可以为相对低压条件下钠的固液相变的应用和模拟提供理论支持。

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引用次数: 0

Hydrate equilibrium conditions of a synthetic natural gas in the presence of methanol: Experimental study and thermodynamic modeling 甲醇存在下合成天然气水合物平衡条件：实验研究和热力学模型

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-09-24 DOI: 10.1016/j.fluid.2025.114595

Alireza Shariati , Ali Rasoolzadeh , Cor J. Peters

In this work, the hydrate equilibrium conditions of a synthetic natural gas (SNG) in the presence of pure water and three aqueous methanol solutions including 0.09570, 0.24805, and 0.50109 methanol mass fractions were measured in the pressure range of (5.06 to 12.56) MPa and temperature range of (256.74 to 291.41) K using the isochoric pressure-search method. Additionally, a modified van der Waals-Platteeuw (vdW-P) model was used to calculate the hydrate equilibrium conditions of the SNG hydrate. The UNIQUAC and Flory-Huggins (FH) activity coefficient models were applied to compute the water activity in the presence of methanol and the Peng-Robinson equation of state (PR EoS) was used for the vapor phase. It was determined that (vdW-P + PR + UNIQUAC) and (vdW-P + PR + FH) resulted in the average absolute deviations of 0.41 K and 0.25 K, respectively.

在压力（5.06 ~ 12.56）MPa、温度（256.74 ~ 291.41）K范围内，采用等时压力搜索法测定了合成天然气（SNG）在纯水、甲醇质量分数（0.09570、0.24805、0.50109）三种甲醇水溶液存在下的水合物平衡条件。此外，采用改进的van der Waals-Platteeuw （vdW-P）模型计算了天然气水合物的水合物平衡条件。采用UNIQUAC和Flory-Huggins （FH）活度系数模型计算甲醇存在时的水活度，采用Peng-Robinson状态方程（PR EoS）计算气相。结果表明，（vdW-P + PR + UNIQUAC）和（vdW-P + PR + FH）的平均绝对偏差分别为0.41 K和0.25 K。

引用次数: 0

Using the PC-SAFT model to represent the mixing properties of 81 binaries formed by a methyl alkanoate with an alkan-1-ol 用PC-SAFT模型表示了81个由烷烃-1-醇甲酯组成的二元化合物的混合性质

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-09-24 DOI: 10.1016/j.fluid.2025.114590

Ariel Hernández , Juan Ortega , Mustapha Maarouf , Manuel Chaar

PC-SAFT has been used as a fitted and predictive approaches for modeling the excess molar properties of 81 binary mixtures composed of methyl alkanoate and 1-alkanol at atmospheric pressure and 298.15 K; whose experimental and correlation data were obtained from the literature. Furthermore, we have compared the VLE obtained with PC-SAFT for 9 binary mixtures of methyl alkanoate (ethanoate to butanoate) + 1-alkanol (ethanol to 1-butanol) with experimental data published in the literature at 101.32 kPa. The binary interaction parameter, known as

k_{i j}

, was adjusted to correct for London dispersion forces, and excess molar volume and excess molar enthalpy data were used for the fitting. From the calculations, we have obtained a good qualitative agreement between PC-SAFT and literature data for most binary mixtures, which present predominant repulsive forces and an endothermic effect in the mixing process. Finally, it was found that PC-SAFT correctly predicts (without using adjustable parameters) the VLE of the 9 binary mixtures analyzed. The best agreement in the representation of the experimental data of excess molar volume was obtained for the group of mixtures of methyl ethanoate + 1-alkanol (18.11%), while in the case of excess molar enthalpy, the best results were obtained for methyl pentadecanoate + 1-alkanol (7.04%). On the other hand, PC-SAFT was able to correctly represent the experimental data of liquid–vapor equilibrium for 9 binary mixtures from a predictive and quantitative perspective and deviations in boiling point and mole fraction in vapor phase of 0.31% and 2.29% were obtained, respectively.

PC-SAFT作为一种拟合和预测方法，用于模拟81种由烷酸甲酯和1-烷醇组成的二元混合物在常压和298.15 K下的过量摩尔性质；其实验及相关数据来源于文献。此外，我们还将PC-SAFT获得的9种二元烷酸甲酯（乙醇酸到丁酸）+ 1-烷醇（乙醇到1-丁醇）混合物的VLE与文献中发表的101.32 kPa的实验数据进行了比较。对二元相互作用参数kij进行了调整，以校正伦敦色散力，并使用过量摩尔体积和过量摩尔焓数据进行拟合。通过计算，我们得到了PC-SAFT和文献数据在质性上很好的一致性，这些二元混合物在混合过程中表现出主要的排斥力和吸热效应。最后，发现PC-SAFT正确地预测了所分析的9种二元混合物的VLE（不使用可调参数）。在过量摩尔焓的情况下，戊酸甲酯+ 1-烷醇组的结果最符合（18.11%），而在过量摩尔焓的情况下，戊酸甲酯+ 1-烷醇组的结果最符合（7.04%）。另一方面，PC-SAFT能够从预测和定量的角度正确表征9种二元混合物的液气平衡实验数据，其沸点和气相摩尔分数的偏差分别为0.31%和2.29%。

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引用次数: 0

Study on isobaric specific heat capacity of ethyl octanoate under high pressure across 313-453 K 辛酸乙酯在313-453 K高压下等压比热容的研究

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-09-15 DOI: 10.1016/j.fluid.2025.114592

Shaohua Lv , Bo Wang , Yun Hao , Jialun Liu , Yali Su

This study experimentally determined the isobaric specific heat capacity of ethyl octanoate using flow calorimetry across 313.15 to 453.15 K at pressures up to 10 MPa, with measurement uncertainty of 0.095. Deviations from literature data were within 0.43 % at 0.1 MPa and 0.42 % under elevated pressures. By integrating literature data, a computational equation for ethyl octanoate was regressed, exhibiting deviations ≤0.42 %. Utilizing the differential relationship

{(\partial c_{p} / \partial p)}_{T} = - T {(\partial^{2} v / \partial T^{2})}_{p}

, a predictive model for isobaric specific heat capacity was established. This model extends the prediction of heat capacity to 100 MPa, achieving an average absolute deviation (AAD) of 0.28 % within the experimental range, demonstrating satisfactory accuracy.

本研究利用流动量热法测定了辛酸乙酯在313.15 ~ 453.15 K压力下的等压比热容，测量不确定度为0.095。与文献数据的偏差在0.1 MPa和升高压力下分别为0.43%和0.42%。通过整合文献资料，对辛酸乙酯的计算方程进行回归，偏差≤0.42%。利用微分关系（∂cp/∂p）T=−T(∂2v/∂T2)p，建立了等压比热容预测模型。该模型将热容的预测范围扩展到100 MPa，在实验范围内的平均绝对偏差（AAD）为0.28%，具有满意的精度。

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引用次数: 0

UNIFAC parametrization for solid-liquid equilibrium of systems containing choline chloride 含氯化胆碱体系固液平衡的UNIFAC参数化

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-09-14 DOI: 10.1016/j.fluid.2025.114591

Paula V.de A. Pontes, Ericsem Pereira, Guilherme J. Maximo, Eduardo A.C. Batista

Choline chloride has been extensively used in literature for the formulation of eutectic solvents for the extraction of biocompounds from different raw materials. The formulation of eutectic solvents should be performed through the evaluation of the Solid-Liquid Equilibrium (SLE) of the mixture and identification of its eutectic point. In this case, the eutectic point calculation through thermodynamic modeling could improve the design of solvents for extraction processes. The UNIFAC model is a group-contribution based model that could be used in this case. In this context, this study was aimed at the adjustment of new original UNIFAC interaction parameters pairs (a_mnand a_nm) for choline chloride [Ch]Cl (treated in this work as a pseudo-group) and CH₃ (CH, CH₂ and CH₃ subgroups), OH and COOH groups. A databank composed of experimental SLE data from different works in literature were built. The dataset included complete SLE data of 23 mixtures of [Ch]Cl with polyols, polycarboxylic acids, long-chain carboxylic acids (fatty acids) and long chain alcohols (fatty alcohols). Parameters adjusted showed a significant accuracy in describing the SLE profile of the mixtures, especially in the [Ch]Cl rich region, with mean relative deviation varying from 1.32 to 10.79 %. The new UNIFAC enthalpic parameters were also able to predict eutectic temperatures and eutectic compositions of [Ch]Cl mixtures with reasonable accuracy, which is quite interesting considering the design of new eutectic solvents. This study collaborates with the green chemistry literature taking into account the faster screening of new DES and ES composed of choline chloride.

在文献中，氯化胆碱被广泛用于制备共晶溶剂，用于从不同原料中提取生物化合物。共晶溶剂的配制应通过对混合物的固液平衡（SLE）的评价和共晶点的确定来进行。在这种情况下，通过热力学建模计算共晶点可以改进萃取过程溶剂的设计。UNIFAC模型是一个基于群体贡献的模型，可以在这种情况下使用。在此背景下，本研究旨在调整新的原始UNIFAC相互作用参数对（amand anm），以氯化胆碱[Ch]Cl（本文将其作为伪基团）和CH3 （Ch， CH2和CH3亚基团），OH和COOH基团。建立了一个由不同文献中SLE实验数据组成的数据库。该数据集包括23种[Ch]Cl与多元醇、多羧酸、长链羧酸（脂肪酸）和长链醇（脂肪醇）混合物的完整SLE数据。调整后的参数在描述混合物的SLE分布方面具有显著的准确性，特别是在富含[Ch]Cl的区域，平均相对偏差从1.32%到10.79%不等。新的UNIFAC焓参数还能以合理的精度预测[Ch]Cl混合物的共晶温度和共晶成分，这对于设计新的共晶溶剂来说是非常有趣的。本研究与绿色化学文献合作，考虑到更快地筛选由氯化胆碱组成的新型DES和ES。

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引用次数: 0

Modeling study on the density and viscosity of ionic liquid-ionic liquid-water ternary mixtures 离子液体-离子液体-水三元混合物密度和粘度的模拟研究

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-09-12 DOI: 10.1016/j.fluid.2025.114589

You Shu , Yang Lei , Yanfen Huang , Xinyan Liu , Yuqiu Chen

The vast diversity of ionic liquids (ILs) necessitates the development of accurate predictive models to support their industrial applications. This study combines machine learning (ML) algorithms with group contribution (GC) methods to model the density and viscosity of IL-IL-H₂O ternary mixtures. Three ML algorithms (i.e., ANN, XGBoost, and LightGBM) were employed to develop robust predictive models, which were trained on a large experimental dataset. The effect of dataset partitioning on the prediction results is analyzed, and the generalizability of the models is validated through 5-fold cross-validation. The ANN-GC model performs well in predicting both density and viscosity properties, with a mean absolute error (MAE) of 1.7909 and a correlation coefficient (R²) of 0.9933 for density, and an MAE of 0.0329 and an R² of 0.9813 for viscosity. Furthermore, hyperparameters for the ANN model were optimized using Bayesian optimization, while XGBoost and LightGBM were optimized via grid search. After optimization, the prediction accuracies of all three models improved, with ANN-GC maintaining the highest prediction accuracy. Specifically, the optimized ANN-GC model achieves an MAE of 1.5834 and an R² of 0.9963 for density prediction, and an MAE of 0.0279 and an R² of 0.9924 for viscosity prediction. Further insights were obtained through SHAP (SHapley Additive exPlanations) analysis, which clarified the contributions of different features to the model predictions. Additionally, the validity of the density and viscosity prediction models was confirmed by calculating the fluid flow unit process case.

离子液体（ILs）的巨大多样性需要开发准确的预测模型来支持其工业应用。本研究将机器学习（ML）算法与群贡献（GC）方法相结合，对IL-IL-H2O三元混合物的密度和粘度进行了建模。采用三种机器学习算法（即ANN、XGBoost和LightGBM）开发鲁棒预测模型，并在大型实验数据集上进行训练。分析了数据集划分对预测结果的影响，并通过5次交叉验证验证了模型的泛化性。ANN-GC模型对密度和粘度均有较好的预测效果，密度的平均绝对误差（MAE）为1.7909，相关系数（R2）为0.9933，粘度的平均绝对误差（MAE）为0.0329，相关系数（R²）为0.9813。采用贝叶斯优化方法对人工神经网络模型进行超参数优化，采用网格搜索方法对XGBoost和LightGBM模型进行优化。优化后，3种模型的预测精度均有提高，ANN-GC保持最高的预测精度。其中，优化后的ANN-GC模型预测密度的MAE为1.5834，R2为0.9963；预测粘度的MAE为0.0279，R2为0.9924。通过SHapley加性解释（SHapley Additive exPlanations）分析获得了进一步的见解，该分析澄清了不同特征对模型预测的贡献。通过对流体流动单元过程实例的计算，验证了密度和粘度预测模型的有效性。

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引用次数: 0

Viscosity, thermal conductivity and self-diffusion coefficient of the Lennard-Jones spline fluid: Evaluation of theories for a short-ranged potential Lennard-Jones样条流体的黏度、热导率和自扩散系数：短程势理论的评价

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-09-10 DOI: 10.1016/j.fluid.2025.114584

Johannes S. Løken, Vegard G. Jervell, Morten Hammer, Bjørn Hafskjold, Thuat T. Trinh, Øivind Wilhelmsen

The Lennard-Jones/spline (LJ/s) potential is truncated and splined such that the potential and its first derivative continuously approach zero at

\approx 1.74 σ

, making it short-ranged. In this work, we present a systematic study of the thermal conductivity, shear viscosity, and self-diffusion coefficient of the LJ/s fluid. Four theories are evaluated by comparing to results from equilibrium and non-equilibrium molecular dynamics simulations for temperatures in the range

0.7 \leq T^{*} \leq 10

and densities in the range

0.1 \leq ρ^{*} \leq 0.8

. After regressing two parameters for each transport property in extended corresponding state theory with argon as reference fluid, the Average Absolute Relative Deviations (AARDs) with respect to the simulation data are 4.7% and 2.8% for the viscosity and thermal conductivity respectively. Using 4-6 regression parameters, residual entropy scaling yields AARDs of 5.7%, 2.6%, and 2.5% for the viscosity, thermal conductivity and self-diffusion coefficient respectively. A new method called corresponding entropic states theory is presented, which combines the concept of entropy scaling with the extended corresponding states formalism. Without any fitting parameters and with argon as reference fluid, the viscosity and thermal conductivity from the method have AARDs of 5.2% and 2.6%. For residual entropy scaling, extended corresponding states, and corresponding entropic states, the largest deviations are for the viscosity near the critical point, which can be explained by inaccuracies in the equation of state. Revised Enskog Theory, which is fully predictive, gives AARDs below 10% for

T^{*} \geq 3

, up to

ρ^{*} = 0.4

. More work is needed to increase the accuracy of Revised Enskog theory at lower temperatures and higher densities.

Lennard-Jones/spline （LJ/s）势被截断和样条化，使得势和它的一阶导数在≈1.74σ处连续趋近于零，使得它是短距离的。在这项工作中，我们提出了一个系统的研究热导率，剪切粘度和自扩散系数的LJ/s流体。通过比较温度在0.7≤T∗≤10范围内和密度在0.1≤ρ∗≤0.8范围内的平衡和非平衡分子动力学模拟结果，对四种理论进行了评价。在以氩气为基准流体的扩展对应态理论中，对每个输运性质的两个参数进行回归后，粘度和导热系数与模拟数据的平均绝对相对偏差（AARDs）分别为4.7%和2.8%。使用4-6个回归参数，残余熵标度对黏度、导热系数和自扩散系数的误差分别为5.7%、2.6%和2.5%。将熵标度的概念与扩展的对应态形式化相结合，提出了一种新的方法——对应熵态理论。在没有任何拟合参数的情况下，以氩气为基准流体，该方法得到的黏度和导热系数的aard分别为5.2%和2.6%。对于剩余熵标度、扩展对应态和对应熵态，最大的偏差是在临界点附近的粘度，这可以用状态方程的不准确性来解释。修正的Enskog理论是完全可预测的，它给出了T∗≥3的AARDs低于10%，直到ρ∗=0.4。要提高修正的Enskog理论在较低温度和较高密度下的准确性，还需要做更多的工作。

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引用次数: 0

Influence of the molar mass of PEGs on the miscibility of paracetamol: Study of binary phase diagrams. Application for FDM 3D printing 聚乙二醇摩尔质量对扑热息痛混相的影响：二元相图的研究。FDM 3D打印应用

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-09-08 DOI: 10.1016/j.fluid.2025.114588

Veronica Ianno’, Philippe Espeau

PEGs are often used as plasticizers in filaments formulated for FDM 3D printing. Here, we present the behavior of paracetamol in solid dispersions based on PEG 4000 and 6000 via the determination of binary phase diagrams. It is shown, as was already the case with PEG 1500, that paracetamol is present, almost obviously, in its polymorphic Form II during the second heating. This metastable form remains stable in the presence of PEG, and its solubility appears to be independent of the molar mass of PEG, as is the case for Form I. This work aims to mimic the behavior of paracetamol in the presence of PEG during an extrusion process by HME then coupled with 3D printing by FDM.

聚乙二醇通常用作FDM 3D打印的长丝中的增塑剂。在这里，我们提出了对乙酰氨基酚在固体分散基于peg4000和6000二元相图的测定行为。这表明，就像peg1500的情况一样，在第二次加热期间，扑热息痛几乎明显地以其多态形式II存在。这种亚稳态形式在PEG存在下保持稳定，其溶解度似乎与PEG的摩尔质量无关，就像形式i的情况一样。这项工作的目的是在HME挤压过程中模拟扑热息痛在PEG存在下的行为，然后通过FDM进行3D打印。

引用次数: 0

High-pressure phase behaviour and modelling of the 1‑nonanol + n‑hexadecane + supercritical CO2 system 1 -壬醇+正十六烷+超临界CO2体系的高压相行为和建模

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-09-06 DOI: 10.1016/j.fluid.2025.114587

Corine Mouton, Cara E. Schwarz

This work presents measured high-pressure phase transition data for mixtures containing 1‑nonanol + n‑hexadecane (solute + solute) with supercritical CO₂ (solvent) and thermodynamic modelling of the measured data. The data was measured using the static synthetic visual phase method for four (1‑nonanol + n‑hexadecane) mixtures with CO₂ as well as 1‑nonanol + CO₂ at temperatures between 308.2 K and 358.2 K and solute mass fractions ranging from 0.008 to 0.65 g·g^-1. Solute-solute interactions strongly influence the observed phase behaviour, resulting in complex phenomena such as cosolvency effects and temperature inversions. The measured data revealed distinct cosolvency effects and exhibited temperature inversions at 308.2 K and 318.2 K for solvent-free alcohol compositions of 0 g·g^-1, 0.8 g·g^-1 and 1 g·g^-1.

A modified version of the Soave-Redlich-Kwong (SRK) equation of state implemented in Aspen Plus®, RK‑Aspen, was used to correlate experimental pure component and binary data, and to predict the high-pressure phase transition data for the ternary system. Incorporating polar parameters, solute-solvent binary interaction parameters (BIPs), and solute-solute BIPs in the RK-Aspen model provided reasonably accurate descriptions of the measured data in the dew- and bubble point composition ranges at moderate temperatures. However, future work should focus on improving the model's performance at temperatures near the solvent's critical temperature and compositions near the mixture critical region. Additionally, an in-house thermodynamic model can be developed to better describe complex phase behaviour.

这项工作提出了含有1 -壬醇+正十六烷（溶质+溶质）和超临界CO2（溶剂）的混合物的高压相变数据和测量数据的热力学建模。在温度为308.2 K ~ 358.2 K，溶质质量分数为0.008 ~ 0.65 g·g-1的条件下，采用静态合成目测相法测量了四种（1 -壬醇+正十六烷）与CO2以及1 -壬醇+ CO2的混合物的数据。溶质-溶质相互作用强烈影响观察到的相行为，导致复杂的现象，如共溶效应和温度反转。无溶剂酒精组分0 g·g-1、0.8 g·g-1和1 g·g-1在308.2 K和318.2 K温度下呈现出明显的共溶效应。在Aspen Plus®中实现的Soave-Redlich-Kwong （SRK）状态方程的改进版本RK - Aspen用于关联实验纯组分和二元数据，并预测三元体系的高压相变数据。在RK-Aspen模型中加入极性参数、溶质-溶剂二元相互作用参数（BIPs）和溶质-溶质二元相互作用参数（BIPs），可以合理准确地描述中温露点和泡点组成范围内的测量数据。然而，未来的工作应该集中在提高模型在溶剂临界温度附近的性能和混合物临界区域附近的成分。此外，可以开发内部热力学模型来更好地描述复杂的相行为。

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引用次数: 0

Measurements of infinite dilution binary diffusion coefficient and partial molar volume of piperine in supercritical carbon dioxide 超临界二氧化碳中胡椒碱无限稀释、二元扩散系数和部分摩尔体积的测量

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2025-09-04 DOI: 10.1016/j.fluid.2025.114574

Mami Inagaki , Kazuki Tsubaki , Sota Kawakami , Chang Yi Kong , Toshitaka Funazukuri

Piperine is one of key components of peppers, and supercritical fluid extraction has been applied to isolate such heat-sensitive natural substances. The diffusion coefficient (D₁₂) of piperine in supercritical (sc) carbon dioxide is essential for the process design, but no data are available in the literature. In the present study the infinite dilution binary diffusion coefficient (D₁₂) of piperine in scCO₂ was measured at temperatures from 308.2 K to 343.2 K and at pressures from 12 MPa to 30 MPa by the chromatographic impulse response method, and those in methanol, ethanol, 1-propanol and 1-butanol were measured at atmospheric pressure and at temperatures from 303.2 K to 343.2 K by the Taylor dispersion method. The hydrodynamic equation, D₁₂/T =αη^β, T is the temperature and η is the CO₂ and alcohol viscosity, was found to well represent all of the D₁₂ values measured in both scCO₂ and atmospheric liquid alcohols, with a single set of two constants α = 3.655 × 10^–15 kg^-βm^β+2s^β-1K^-1 and β = -0.9145 with the average absolute relative deviation of 4.41 % and maximum deviation of 14.0 % with 72 measurement conditions. Partial molar volumes(PMV) of piperine determined from the retention factors were negative and decreased substantially closer to the CO₂ critical point, as observed for various solutes in scCO₂ reported in the literature. To evaluate the accuracy of the determined PMV values new reliable models and reliable solubility data are needed to describe the PMV values, especially near the critical region.

胡椒碱是辣椒的关键成分之一，超临界流体萃取法已被用于分离这种热敏性天然物质。胡椒碱在超临界（sc）二氧化碳中的扩散系数（D12）对工艺设计至关重要，但文献中没有相关数据。用色谱脉冲响应法测定了胡椒碱在scCO2中的无限稀释二元扩散系数（D12），温度为308.2 K ~ 343.2 K，压力为12 MPa ~ 30 MPa，在常压和温度为303.2 K ~ 343.2 K时，用Taylor色散法测定了胡椒碱在甲醇、乙醇、1-丙醇和1-丁醇中的无限稀释二元扩散系数（D12）。在72种测量条件下，流体动力学方程D12/T =αηβ， T为温度，η为CO2和醇粘度，可以很好地代表scCO2和常压液体醇的所有D12值，其中α = 3.655 × 10-15 kg-βm -β +2s -β - 1k -1和β = -0.9145，平均绝对相对偏差为4.41%，最大偏差为14.0%。根据保留系数测定的胡椒碱的偏摩尔体积（PMV）为负，并且在接近CO2临界点时大幅下降，这与文献中报道的scCO2中各种溶质的观察结果一致。为了评估所确定的PMV值的准确性，需要新的可靠模型和可靠的溶解度数据来描述PMV值，特别是在临界区域附近。

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引用次数: 0