Fluid Phase Equilibria最新文献

A geometric–statistical perspective on entropy and enthalpy–entropy compensation in coarse-grained free-energy landscapes 粗粒度自由能景观中熵和焓熵补偿的几何统计视角

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-07-01 Epub Date: 2026-02-07 DOI: 10.1016/j.fluid.2026.114693

Vicente Domínguez-Arca

Entropy is conventionally regarded as a scalar measure of disorder, while enthalpy is interpreted as the energetic contribution associated with microscopic interactions. This dichotomy underlies the standard decomposition of the Gibbs free energy, yet it obscures the geometric commonality of the mechanisms that produce both terms. Here, we develop a geometric–statistical reformulation of thermodynamic forces in coarse-grained landscapes in which coarse-grained variables evolve on a configuration manifold whose structure encodes the accessible microstates of the system. In isolated systems, this manifold exhibits a degeneracy of free-energy minima corresponding to a Mexican-hat landscape, reflecting maximal entropic freedom along continuous families of equivalent configurations. Coupling to an external environment lifts this degeneracy and deforms the manifold into a thermodynamic paraboloid, whose curvature quantifies the unified thermodynamic stiffness governing system response. We show that enthalpic and entropic contributions to thermodynamic forces arise as orthogonal projections of this local stiffness (Hessian) tensor

Λ_{i j} (T)

, thereby revealing a common microscopic origin. As a direct consequence, the well-known enthalpy–entropy compensation phenomenon emerges whenever the curvature of the configuration manifold remains invariant with temperature. This perspective reframes enthalpy and entropy as complementary geometric expressions of the same coarse-grained configuration-space structure. While not intended as a universal description of all thermodynamic systems, it provides a coherent and testable framework for a broad class of physico-chemical processes that admit meaningful collective coordinates and locally harmonic free-energy basins.

熵通常被认为是无序的标量度量，而焓被解释为与微观相互作用相关的能量贡献。这种二分法是吉布斯自由能标准分解的基础，但它模糊了产生这两项的机制的几何共性。在这里，我们开发了一种粗粒度景观中热力学力的几何统计重新表述，其中粗粒度变量在配置流形上演化，其结构编码系统的可访问微观状态。在孤立系统中，这种流形表现出与墨西哥帽景观相对应的自由能最小值的简并，反映了沿等效构型连续族的最大熵自由。与外部环境的耦合提升了这种退化并将流形变形为热力学抛物面，其曲率量化了控制系统响应的统一热力学刚度。我们表明，热力学力的焓和熵贡献产生于这个局部刚度（Hessian）张量Λij(T)的正交投影，从而揭示了一个共同的微观起源。直接的结果是，当构型流形的曲率随温度保持不变时，就会出现众所周知的焓熵补偿现象。这种观点将焓和熵重新定义为相同的粗粒度构型空间结构的互补几何表达式。虽然不打算作为所有热力学系统的普遍描述，但它为广泛的物理化学过程提供了一个连贯和可测试的框架，这些过程承认有意义的集体坐标和局部谐波自由能盆地。

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引用次数: 0

Thermodynamic modelling of dissociating Al2Br6 and Al2Cl6 used as reactive working fluids in thermodynamic cycles 解离Al2Br6和Al2Cl6在热力学循环中作为反应性工质的热力学建模

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-07-01 Epub Date: 2026-01-08 DOI: 10.1016/j.fluid.2026.114661

Julien Joliat , Konstantin Samukov , Rachid Hadjadj , Thijs J.H. Vlugt , Olivier Herbinet , Silvia Lasala

To enhance the efficiency of thermodynamic cycles in heat pumps and power plants, we explore a novel approach: replacing conventional inert pure fluids or mixtures with reactive fluids that undergo reversible chemical reactions. A key step towards the implementation of this concept is the development of a fully predictive framework for determining the thermodynamic properties of such reactive working fluids. In this context, the present work extends a semi-empirical methodology previously proposed by the authors, aiming to address the challenge introduced by newly developed reactive fluids for which experimental data are unavailable. The methodology presented in this work requires only the critical-point properties and acentric factor of the molecules participating in the chemical reaction. As in the earlier approach from the authors, it combines ab-initio quantum mechanics calculations to determine the ideal gas properties of each molecule, the a-thermal version of the “Peng-Robinson + EoS/

a_{r e s}^{E, γ}

mixing rules” equation of state and molecular Monte Carlo simulations to assess real fluid properties and enable cross-validation between methods. This work, however, applies a simplification to the force fields used in Monte Carlo simulations consisting in employing single-particle force fields instead of all-atom models. This strategy decreases the amount of experimental data required to parametrise the force field of each molecule contained in the reactive mixture, and allows the use of the same inputs in equation of state modelling and Monte Carlo simulations (i.e., molecular critical parameters). Indeed, this work proposes to calculate force field parameters using either the critical temperature and pressure, or the critical temperature and density of each molecule. The methodology is applied to two reactive systems, Al₂Br₆ ⇌ 2AlBr₃ and Al₂Cl₆ ⇌ 2AlCl₃. The results show that Monte Carlo predictions, although less accurate than those from the equation of state, remain acceptably close to experimental data, while the equation of state results demonstrate significantly higher accuracy.

为了提高热泵和发电厂的热力学循环效率，我们探索了一种新的方法：用经过可逆化学反应的反应性流体取代传统的惰性纯流体或混合物。实现这一概念的关键一步是开发一个完整的预测框架，以确定这种反应性工作流体的热力学性质。在此背景下，本工作扩展了作者先前提出的半经验方法，旨在解决新开发的反应性流体带来的挑战，这些流体无法获得实验数据。在这项工作中提出的方法只需要参与化学反应的分子的临界点性质和偏心因子。与作者先前的方法一样，该方法结合了从头算量子力学计算来确定每个分子的理想气体性质，结合了“Peng-Robinson + EoS/aresE，γ混合规则”状态方程的非热版本和分子蒙特卡罗模拟来评估真实流体性质，并实现方法之间的交叉验证。然而，这项工作对蒙特卡罗模拟中使用的力场进行了简化，包括使用单粒子力场而不是全原子模型。这种策略减少了将反应混合物中每个分子的力场参数化所需的实验数据量，并允许在状态方程建模和蒙特卡罗模拟中使用相同的输入（即分子临界参数）。事实上，这项工作建议使用临界温度和压力或每个分子的临界温度和密度来计算力场参数。该方法应用于Al2Br6 + 2AlBr3和Al2Cl6 + 2AlCl3两种反应体系。结果表明，蒙特卡罗预测虽然不如状态方程预测准确，但仍然可以接受地接近实验数据，而状态方程结果显示出更高的精度。

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引用次数: 0

Thermodynamic modeling of formic acid with SAFT-VR Mie DBD for energy applications: Heat pumps, Rankine cycles, and CO₂ electrochemical reduction 甲酸的热力学建模与SAFT-VR Mie DBD能源应用：热泵，朗肯循环，和CO₂电化学还原

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-07-01 Epub Date: 2026-02-05 DOI: 10.1016/j.fluid.2026.114692

Hamed Mgbatou Mounchingam, Yan Ding, Patrice Paricaud

Formic acid (HCOOH) has attracted renewed interest as a sustainable chemical intermediate, liquid hydrogen carrier, and potential working fluid for thermodynamic cycles. This work presents a comprehensive thermodynamic study of pure formic acid and its mixtures using the SAFT-VR Mie doubly bonded dimer (DBD) equation of state. The pure component parameters of formic acid were optimized against vapor pressures, liquid densities, and vaporization enthalpies, achieving an excellent description of the experimental data. Binary interaction parameters were adjusted for formic acid mixtures with water, CO₂, and acetic acid, and an accurate description of vapor-liquid equilibria and excess enthalpies is obtained. The model was applied to simulate high-temperature heat pumps and Rankine cycles using carboxylic acids as working fluids. It is found that formic and acetic acids exhibit higher coefficients of performance than conventional refrigerants at elevated temperatures, but face significant practical constraints including corrosion issues, limited temperature range, low operating pressures, and large volumetric flow rates. An integrated process for high-grade formic acid production via CO₂ electrochemical reduction is simulated, combining three-compartment electrolysis cells with pressure-swing distillation for product purification. Energy integration using a formic acid heat pump to supply the distillation reboiler duty reduces the overall electricity consumption of the process making it viable in terms of operating cost. This study provides insights into the thermodynamic feasibility and practical limitations of formic acid in both energy conversion systems and sustainable chemical production processes.

甲酸（HCOOH）作为一种可持续的化学中间体、液氢载体和热力学循环的潜在工作流体，引起了人们的重新关注。本文采用SAFT-VR Mie双键二聚体（DBD）状态方程对纯甲酸及其混合物进行了全面的热力学研究。根据蒸汽压、液体密度和汽化焓对甲酸的纯组分参数进行了优化，获得了对实验数据的良好描述。对甲酸与水、CO 2和乙酸的混合物的二元相互作用参数进行了调整，得到了气液平衡和过量焓的准确描述。将该模型应用于以羧酸为工质的高温热泵和朗肯循环的模拟。研究发现，甲酸和乙酸在高温下表现出比传统制冷剂更高的性能系数，但面临着重大的实际限制，包括腐蚀问题、有限的温度范围、低工作压力和大体积流量。模拟了三室电解池与变压蒸馏相结合的CO₂电化学还原生产高档甲酸一体化工艺。利用甲酸热泵提供蒸馏再沸器负荷的能量集成降低了该过程的总体电力消耗，使其在运行成本方面可行。本研究为甲酸在能量转换系统和可持续化学生产过程中的热力学可行性和实际局限性提供了见解。

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引用次数: 0

Evaluation of the alpha function and volume translation in the Peng-Robinson equation of state using volume-translated Helmholtz energy equations 用体积平移的亥姆霍兹能量方程评价Peng-Robinson状态方程中的alpha函数和体积平移

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-07-01 Epub Date: 2026-01-29 DOI: 10.1016/j.fluid.2026.114689

George Tasios, Vasiliki Louli, Epaminondas Voutsas

Cubic equations of state (CEoS) remain the standard tool for thermodynamic calculations in industrial applications, particularly in the oil and gas sector, due to their robustness and computational efficiency. Among them, the Peng-Robinson (PR) equation of state provides a well-established balance between accuracy in volumetric and phase-equilibrium predictions. Improvements to PR have primarily focused on two aspects: the temperature-dependent attractive term (α-function) and volume translation. While modifications of the α-function have been extensively investigated for their impact on vapor-pressure correlations and derivative properties, volume translation has largely been assessed only in terms of liquid-density predictions. In this work a consistent framework is developed to evaluate both modifications simultaneously by deriving a generalized set of Helmholtz free energy expressions and their derivatives, rigorously incorporating volume translation. First, the new formulation is presented and mathematically validated. Next, a systematic analysis is performed using several α-functions of various temperature dependencies, for the prediction of vapor pressures, isobaric and isochoric heat capacities. Overall, the Mathias-Copeman PR model provides the most accurate results for vapor pressures and isobaric heat capacities, while underperforming in isochoric heat capacities. Additionally, multiple temperature-independent and temperature-dependent volume translations are assessed against experimental saturated liquid densities, with the most reliable formulations identified. These are subsequently coupled with the Mathias Copeman α-function and the original Soave form and benchmarked against derivative-property data. The results show that combining this α-function with a linear temperature-dependent volume translation significantly enhances the predictive capability of the Peng-Robinson equation, particularly for volumetric and derivative properties.

由于其鲁棒性和计算效率，三次状态方程（ceo）仍然是工业应用中热力学计算的标准工具，特别是在石油和天然气领域。其中，Peng-Robinson （PR）状态方程在体积平衡和相平衡预测的准确性之间提供了良好的平衡。对PR的改进主要集中在两个方面：温度相关的吸引项（α-函数）和体积翻译。虽然α-函数的修饰已经被广泛地研究了它们对蒸汽压相关性和导数性质的影响，但体积平移很大程度上只在液体密度预测方面进行了评估。在这项工作中，通过推导一组广义的亥姆霍兹自由能表达式及其导数，严格地结合体积平移，开发了一个一致的框架来同时评估这两种修改。首先，提出了新的公式并进行了数学验证。接下来，利用不同温度依赖性的α-函数进行系统分析，用于预测蒸汽压、等压和等时热容。总的来说，Mathias-Copeman PR模型对蒸汽压和等压热容提供了最准确的结果，而在等压热容方面表现不佳。此外，根据实验饱和液体密度评估了多个温度无关和温度相关的体积转换，并确定了最可靠的配方。这些随后与Mathias Copeman α-函数和原始Soave形式相结合，并对衍生性数据进行基准测试。结果表明，将α-函数与温度相关的线性体积平移相结合，显著提高了Peng-Robinson方程的预测能力，特别是对体积和导数性质的预测能力。

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引用次数: 0

Understanding the thermoresponsive behavior of L61/Water mixtures via MD and DPD simulations: A two-scale approach 通过MD和DPD模拟了解L61/水混合物的热响应行为：一种双尺度方法

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-07-01 Epub Date: 2026-02-03 DOI: 10.1016/j.fluid.2026.114688

N. Lauriello , K. Sindelka , D. Marchisio , M. Casalegno

Pluronics are nonionic amphiphilic copolymers with many applications in the pharmaceutical and cosmetic industry. In water these polymers may exist as unimers, micelles, and other supramolecular aggregates. The study of such phases by means of in-silico methods, like molecular dynamics and dissipative particle dynamics, can be expected to complement existing experimental data and better understand their molecular properties. In this work, we propose a two-scale approach where these two methods are combined to allow for the efficient study of Pluronics dynamics at different temperatures. The method is applied to study the thermoresponsive behavior of L61 in water. In line with the experimental data, our simulations show that L61 does not form micelles upon heating. At the highest concentration considered, a two-phase system is observed, where small and large aggregates coexist. This outcome and the applicability of the method to other Pluronics are discussed in the light of the existing literature.

Pluronics是非离子两亲性共聚物，在制药和化妆品工业中有许多应用。在水中，这些聚合物可能以单体、胶束和其他超分子聚集体的形式存在。通过分子动力学和耗散粒子动力学等计算机方法研究这些相，可以补充现有的实验数据，更好地了解它们的分子性质。在这项工作中，我们提出了一种双尺度方法，其中这两种方法相结合，以允许在不同温度下对Pluronics动力学进行有效研究。应用该方法研究了L61在水中的热响应行为。与实验数据一致，我们的模拟表明L61在加热时不会形成胶束。在考虑的最高浓度下，观察到两相系统，其中小团聚体和大团聚体共存。根据现有文献讨论了这一结果和该方法对其他Pluronics的适用性。

引用次数: 0

Modeling flash points of biofuels using thermodynamically consistent neural networks 使用热力学一致的神经网络模拟生物燃料的闪点

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-06-01 Epub Date: 2026-01-16 DOI: 10.1016/j.fluid.2026.114673

Maurício Prado de Omena Souza , Diego Tavares Volpatto , Antonio Marinho Barbosa Neto , Mariana Conceição da Costa

The flash point (FP) is an essential property for assessing flammability and ensuring safety in combustion processes. However, its experimental measurement is resource-intensive and data in the literature remains limited, especially for biofuel mixtures. To address this, predictive modeling has emerged as a promising alternative. This study investigates the capability of thermodynamically consistent neural network models to estimate FP, as well as hybrid approach that embeds a neural network constrained by Gibbs-Duhem equation within a thermodynamic model. The performance of these models was compared with that of a purely data-driven model and a widely used thermodynamic approach. The evaluation was conducted using a dataset comprising binary mixtures of 1-butanol and fatty acid ethyl esters (FAEEs). The data-driven and physically constrained neural network approaches achieved RMSE (Root Mean Squared Error) values of 2.518 K, 1.975 K, 2.798 K, and 2.470 K, while the thermodynamic model using NRTL providing a RMSE of 0.587 K, as expected given that its binary interaction parameters were fitted to the experimental FP data. In addition, incorporating physical constraints into the neural network models for FP prediction did not improve RMSE performance compared to the purely data-driven model, despite achieving improved consistency for the embedded physics equations as expected.

在燃烧过程中，闪点（FP）是评估可燃性和确保安全的基本属性。然而，它的实验测量是资源密集型的，文献中的数据仍然有限，特别是生物燃料混合物。为了解决这个问题，预测建模已经成为一个很有前途的选择。本研究探讨了热力学一致的神经网络模型估计FP的能力，以及在热力学模型中嵌入受Gibbs-Duhem方程约束的神经网络的混合方法。将这些模型的性能与纯数据驱动模型和广泛使用的热力学方法进行了比较。使用包含1-丁醇和脂肪酸乙酯二元混合物（FAEEs）的数据集进行评估。数据驱动和物理约束的神经网络方法的RMSE（均方根误差）值分别为2.518 K、1.975 K、2.798 K和2.470 K，而使用NRTL的热力学模型的RMSE为0.587 K，因为其二元相互作用参数与实验FP数据拟合。此外，与纯粹的数据驱动模型相比，将物理约束纳入FP预测的神经网络模型并没有提高RMSE性能，尽管嵌入式物理方程的一致性如预期的那样得到了改善。

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引用次数: 0

Phase behavior of a water– hydrocarbon condensate mixture: phase diagram construction using CPA and PC-SAFT EoS, experimental design, and model validation 水-烃凝析混合物的相行为：使用CPA和PC-SAFT EoS构建相图，实验设计和模型验证

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-06-01 Epub Date: 2026-02-06 DOI: 10.1016/j.fluid.2026.114691

Mahmood Abdi, Devjyoti Nath, Shakerullah Turkman, Hassan Hassanzadeh

Phase equilibria in water–hydrocarbon mixtures are complex due to water’s strong polarity, hydrogen bonding, and the nonpolar nature of hydrocarbons. This study investigates a mixture of water and a multicomponent condensate comprising n-pentane, n-hexane, cyclohexane, n-heptane, and toluene. Phase diagrams (Tz) are constructed using CPA and PC-SAFT equations of state. Four equilibrium experiments—including vapor–aqueous (Set 1), vapor–oleic–aqueous (Set 2), and two vapor–oleic sets (Set 3 and Set 4)—are designed and conducted. Model performance is evaluated using root-mean-square deviation (RMSD). For vapor phases, PC-SAFT EoS predicts water content with RMSDs of 0.0269, 0.0194, 0.0143, and 0.0120 (Sets 1–4), while CPA EoS achieves 0.0201, 0.0099, 0.0109, and 0.0103. For the oleic phase (Sets 2–4), PC-SAFT EoS RMSDs are 0.0337, 0.0269, and 0.0122, while those of CPA EoS are 0.0512, 0.0387, and 0.0188.

由于水的强极性、氢键和碳氢化合物的非极性性质，水-烃混合物的相平衡是复杂的。本研究研究了水和多组分冷凝物的混合物，包括正戊烷、正己烷、环己烷、正庚烷和甲苯。用CPA和PC-SAFT状态方程构造相图（Tz）。设计并进行了四个平衡实验，包括汽-水（Set 1）、汽-油-水（Set 2）和两组汽-油（Set 3和Set 4）。使用均方根偏差（RMSD）评估模型性能。对于气相，PC-SAFT EoS预测水含量的rmsd分别为0.0269、0.0194、0.0143和0.0120 (set 1-4)，而CPA EoS预测水含量的rmsd分别为0.0201、0.0099、0.0109和0.0103。油酸相（set 2-4） PC-SAFT EoS的rmsd分别为0.0337、0.0269和0.0122，CPA EoS的rmsd分别为0.0512、0.0387和0.0188。

引用次数: 0

Study on solvent extraction separation of polymethyl-substituted monocyclic aromatics from FCC LCO and its interaction mechanism FCC LCO中多甲基取代单环芳烃的溶剂萃取分离及其相互作用机理研究

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-06-01 Epub Date: 2026-01-16 DOI: 10.1016/j.fluid.2026.114672

Qi Li, Jie Li, Hongli Chen, Weihua Xing, Jingxian Wang, Yingyun Qiao, Yuanyu Tian

The efficient separation of aromatics from fluid catalytic cracking light cycle oil is crucial for improving oil quality and realizing the high-value utilization of aromatics. In this study, a two-step extraction-stripping high-efficiency separation method was developed, which successfully achieved the separation of nearly 99.99% pure aromatics. Focusing on the separation characteristics of polymethyl monocyclic aromatics, the extraction performances of sulfolane, dimethyl sulfoxide, and N, N-dimethylformamide was analyzed by GC-MS. Under the conditions of 318.15 K and 101.325 kPa, the liquid-liquid equilibrium (LLE) data of the extractant-p-xylene-heptane ternary system were determined. The results of the separation factor and distribution coefficient showed that sulfoxide had the best selectivity for polymethyl monocyclic aromatics, making it a potential high-efficiency extraction solvent. Furthermore, combined with density functional theory, the mechanism of solvent extraction of p-xylene from heptane was explored at the molecular level. Analyses of electrostatic potential, interaction energy, and reduced density gradient revealed that the main interaction was the van der Waals force. The LLE data were accurately correlated using the NRTL and UNIQUAC thermodynamic models, with the root-mean-square deviation values all below 0.0098. This study not only provides an efficient process for separating but also clarifies the structure-activity relationship between solvent molecular structure and extraction performance from both experimental and theoretical perspectives, providing a theoretical basis for the design and selection of high-performance separation solvents.

催化裂化轻循环油中芳烃的高效分离是提高油品质量和实现芳烃高值利用的关键。本研究开发了一种两步萃取-汽提的高效分离方法，成功地分离出了纯度接近99.99%的芳烃。针对多甲基单环芳烃的分离特点，采用气相色谱-质谱分析了磺胺、二甲基亚砜和N， N-二甲基甲酰胺的提取性能。在318.15 K和101.325 kPa条件下，测定了萃取剂-对二甲苯-庚烷三元体系的液液平衡（LLE）数据。分离系数和分配系数结果表明，亚砜对多甲基单环芳烃具有最佳的选择性，是一种有潜力的高效萃取溶剂。并结合密度泛函理论，在分子水平上探讨了溶剂从庚烷中萃取对二甲苯的机理。静电势、相互作用能和密度梯度的分析表明，相互作用主要是范德华力。采用NRTL和UNIQUAC热力学模型对LLE数据进行了准确的相关，均方根偏差值均小于0.0098。本研究不仅提供了高效的分离工艺，而且从实验和理论两方面阐明了溶剂分子结构与萃取性能之间的构效关系，为高效分离溶剂的设计和选择提供了理论依据。

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引用次数: 0

Selective SO2 absorption using phosphonium carboxylate ionic liquids 羧酸磷离子液体选择性吸收SO2

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-06-01 Epub Date: 2026-01-24 DOI: 10.1016/j.fluid.2026.114687

Nicolas Scaglione, Agilio A.H. Padua, Margarida Costa Gomes

The properties and performance of absorbents for sulfur dioxide based on phosphonium carboxylate ionic liquids are tuned via the basicity of the anions. The SO₂ absorption capacity is reported at temperatures in the range 303–343 K up to pressures of approximately 1 bar, revealing a combination of thermodynamically favored physical and chemical absorption mechanisms. The reaction products were characterized by infrared and NMR spectroscopy. Surprisingly, both the basicity of the carboxylate anion and the length of the alkyl chains of the phosphonium cation have minimal impact on the total SO₂ uptake, but they are crucial for reversibility and also to reach a high selectivity of SO₂ over CO₂. The mechanisms of chemical sorption are distinct for the two gases, with an acid–base mechanism for CO₂ relying ion the basicity of the carboxylate anion and an addition mechanism for SO₂ directly on the carboxylate group. Low-basicity anions favor the SO₂ sorption, yielding ideal selectivity values near 200 at 1 bar and near 400 at 1 bar are obtained with the least basic carboxylate anions (aqueous

<

3.7). Upon SO₂ capture, the viscosity of the media decreases, which is a major improvement over other types of ionic liquid sorbent. Computational chemistry calculations support the favorable thermodynamics of the chemical reaction between the anion and SO₂. Molecular dynamics simulations show that the solvation environments of SO₂ are not impacted by changes in anion basicity or cation size.

基于羧酸磷离子液体的二氧化硫吸附剂的性能是通过阴离子的碱度来调整的。SO2的吸收能力在温度303-343 K到压力约1 bar的范围内被报道，揭示了热力学上有利的物理和化学吸收机制的组合。用红外光谱和核磁共振光谱对反应产物进行了表征。令人惊讶的是，羧酸阴离子的碱度和磷离子的烷基链长度对二氧化硫的总吸收率影响最小，但它们对可逆性和二氧化硫对二氧化碳的高选择性至关重要。两种气体的化学吸附机理不同，CO2的酸碱吸附机理依赖于羧酸阴离子的碱度，而SO2的加成机理直接依赖于羧酸基团。低碱度阴离子有利于SO2的吸附，在1 bar条件下产生的理想选择性值接近200，而在1 bar条件下，羧酸盐阴离子的选择性值接近400（水溶液3.7）。在捕获SO2后，介质的粘度降低，这是比其他类型的离子液体吸附剂的主要改进。计算化学计算支持阴离子和SO2之间有利的化学反应热力学。分子动力学模拟表明，SO2的溶剂化环境不受阴离子碱度和阳离子大小变化的影响。

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引用次数: 0

Molecular dynamics simulations and cubic equations of state of high-pressure CO2-hydrocarbon mixtures: compressibility factor and fugacity coefficient 高压co2 -烃混合物的分子动力学模拟和三次状态方程：可压缩系数和逸度系数

IF 2.7 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Fluid Phase Equilibria

Pub Date : 2026-06-01 Epub Date: 2026-01-24 DOI: 10.1016/j.fluid.2026.114686

Juliana J․ F․ Souza-Rêgo , Itamar Borges Jr , Leonardo S․ de B․ Alves , Luiz O․ V․ Pereira , Ligia G․ Franco , Jakler Nichele

Molecular dynamics (MD) simulations were performed to investigate high-pressure thermodynamic properties of CO₂-hydrocarbon binary mixtures using different force field strategies ‒ united atom, all atom, and hybrid combinations. Simulations were carried out in the isothermal-isobaric (NPT) ensemble to obtain molar volumes as a function of pressure and composition. As a preliminary step, four cubic equations of state were tested against available compressibility factor data, and Peng-Robinson (PR) was selected as the reference cubic framework for the subsequent analyses. MD-derived molar volumes were then coupled to PR in a hybrid workflow: compressibility factors were computed and benchmarked against experimental data, and PR-based fugacity coefficients were evaluated using either PR-predicted or MD-derived molar volumes to quantify the sensitivity of ϕ to the volume source under identical (P, T, y) conditions. The results show that force field choice significantly affects high-pressure volumetric predictions, with TraPPE-based descriptions providing the closest agreement with experimental compressibility factors for CO₂ + CH₄ over the investigated conditions. Finally, effective PR mixture parameters were inferred by nonlinear least-squares fitting of the molar-volume form of PR to volumetric datasets, demonstrating that MD-generated V_m(P, T, y) data can serve as an independent input for cubic-EoS parameter inference when experimental information or calibrated mixture parameters are limited.

采用分子动力学（MD）模拟研究了不同力场策略（统一原子、全原子和杂化组合）下co2 -烃类二元混合物的高压热力学性质。在等温-等压（NPT）系综中进行了模拟，以获得摩尔体积作为压力和组成的函数。作为初步步骤，利用现有压缩系数数据对4个三次状态方程进行了测试，并选择Peng-Robinson （PR）作为后续分析的参考三次框架。然后在混合工作流程中将md衍生的摩尔体积与PR耦合：根据实验数据计算和基准压缩系数，并使用PR预测或md衍生的摩尔体积评估基于PR的逸度系数，以量化相同（P， T, y）条件下φ对体积源的敏感性。结果表明，力场选择显著影响高压体积预测，基于trap的描述与实验条件下CO2 + CH4的压缩系数最接近。最后，通过PR的摩尔体积形式与体积数据集的非线性最小二乘拟合来推断有效的PR混合物参数，表明当实验信息或校准的混合物参数有限时，md生成的Vm（P， T, y）数据可以作为立方- eos参数推断的独立输入。

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引用次数: 0