Journal of Chemical Thermodynamics最新文献

英文中文

Solubility determination and dissolution mechanism of dimethyl 2,6-pyridinedicarboxylate in organic solvents: Experimental and simulation studies 2,6-吡啶二羧酸二甲酯在有机溶剂中的溶解度测定和溶解机理：实验和模拟研究

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-10-21 DOI: 10.1016/j.jct.2025.107601

Wenju Liu, Bin Li, Han Wang, Peiya Cheng, Yuting Zhou, Shuanglin Zhang, Yanmin Shen, Shaofeng Wang

In this work, the equilibrium solubility of dimethyl 2,6-pyridinedicarboxylate (DMPD) was experimentally determined in twelve organic solvents (methyl acetate, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, isopentyl acetate, methanol, ethanol, n-propanol, isopropanol) under atmospheric pressure (P = 0.1 MPa) at a temperature range of 278.15 K–323.15 K by static gravimetric method. Experimental measurements revealed a consistent positive correlation between temperature and solubility, demonstrating that the solubility of DMPD increased monotonically with temperature in all twelve investigated solvent systems. It was found that at a temperature of T = 323.15 K, the general order of DMPD solubility was as follows: dimethyl sulfoxide > methyl acetate > tetrahydrofuran > ethyl acetate > isopropyl acetate > butyl acetate > amyl acetate > isopentyl acetate > methanol > ethanol > n-propanol > isopropanol. Five models (Apelblat model, Yaws model, Wilson model, NRTL model, and Two-Suffix Margules Model) were applied to fit the solubility data. All five thermodynamic models were capable of achieving basically accurate simulations of DMPD solubility. Among them, the Yaws model exhibited an excellent simulation effect on the solubility results of DMPD. Through comprehensive molecular simulations, including Hirshfeld surface (HS) analysis and molecular electrostatic potential surface (MEPs) mapping, complemented by density functional theory (DFT) calculations, we demonstrate that the solvation mechanism of DMPD molecules primarily involves the facile formation of intermolecular hydrogen bonds between DMPD and solvent molecules. This process facilitates the disruption of intrinsic “N⋯H”, “O⋯H” and “H⋯H” hydrogen bonding networks within the crystalline lattice. Combined with van't Hoff calculations, the formation of hydrogen bonds leads to a lowering of the Gibbs free energy of the system, resulting in a more spontaneous solubilization of the DMPD molecule in solution. Finally, the dissolution process of DMPD was analyzed and visualised using molecular dynamics simulations.

在278.15 K - 323.15 K的常压（P = 0.1 MPa）条件下，用静态重量法测定了2,6-吡啶二羧酸二甲酯（DMPD）在12种有机溶剂（乙酸甲酯、二甲亚砜、四氢呋喃、乙酸乙酯、乙酸异丙酯、乙酸丁酯、乙酸戊酯、乙酸异戊酯、甲醇、乙醇、正丙醇、异丙醇）中的平衡溶解度。实验结果表明，温度与溶解度之间存在一致的正相关关系，表明DMPD的溶解度在所有12种溶剂体系中均随温度单调增加。结果发现，在T = 323.15 K时，DMPD溶解度的一般顺序为：二甲亚砜>；乙酸甲酯>；四氢呋喃>；乙酸乙酯>；乙酸异丙酯>；乙酸丁酯>；乙酸戊酯>；乙酸异戊酯>；甲醇>；乙醇>；正丙醇>；异丙醇。采用Apelblat模型、Yaws模型、Wilson模型、NRTL模型和双后缀Margules模型5种模型对溶解度数据进行拟合。所有五种热力学模型都能够基本准确地模拟DMPD的溶解度。其中，雅司模型对DMPD溶解度的模拟效果较好。通过全面的分子模拟，包括Hirshfeld表面（HS）分析和分子静电势表面（MEPs）作图，并辅以密度泛函数理论（DFT）计算，我们证明了DMPD分子的溶剂化机制主要涉及DMPD分子与溶剂分子之间容易形成的分子间氢键。这一过程促进了晶格内固有的“N⋯H”、“O⋯H”和“H⋯H”氢键网络的破坏。结合van't Hoff计算，氢键的形成导致体系的吉布斯自由能降低，导致DMPD分子在溶液中的溶解更加自发。最后，利用分子动力学模拟对DMPD的溶解过程进行了分析和可视化。

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引用次数: 0

Measurement and correlation of compressed liquid density for the CO2 + R1234yf and CO2 + R1243zf binary mixture by isochoric method CO2 + R1234yf和CO2 + R1243zf二元混合物压缩液体密度等时线法测定及相关性研究

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-10-21 DOI: 10.1016/j.jct.2025.107598

Xueqiang Dong , Bo Tang , Bowen Sheng , Xiongwei Wang , Yanxing Zhao , Maoqiong Gong

In this work, compressed liquid density for the CO₂ + R1234yf and CO₂ + R1243zf binary mixture was measured based on a newly established isochoric apparatus. The measured density data of propane in the compressed liquid phase are used to calibrate the volume of the sample container, and the liquid phase density data of R1234yf are used to verify the reliability of the volume measurement. 18 data points for the CO₂ + R1234yf mixture (x_R1234yf = 0.747) and 17 data points for the CO₂ + R1243zf mixture (x_R1243zf = 0.827) are obtained, which cover the temperature and pressure ranges of 233.15–313.15 K and 1–15 MPa. The combined standard uncertainties of temperature, pressure, density, and composition are 90 mK, 25 kPa, 0.2 %, and 0.006. The experimental density data for the compressed liquid phase were correlated using the Peng-Robinson equation of state (EoS) with van der Waals (vdW) mixing rules. Compared with PR + vdW model and REFPROP 10.0, the average absolute relative deviation (AARD) for the CO₂ + R1243zf mixture is 1.12 % and 0.86 %, and the AARD for the CO₂ + R1234yf mixture is 0.21 % and 0.18 %. The data from other literature is used to compare the PR + vdW model based on experimental data from this work, and shows good consistency.

本文利用新建立的等时仪测量了CO2 + R1234yf和CO2 + R1243zf二元混合物的压缩液体密度。用压缩液相中丙烷的测量密度数据对样品容器的体积进行校准，用R1234yf的液相密度数据对体积测量的可靠性进行验证。CO2 + R1234yf混合物（xR1234yf = 0.747）得到18个数据点，CO2 + R1243zf混合物（xR1243zf = 0.827）得到17个数据点，覆盖了233.15 ~ 313.15 K和1 ~ 15 MPa的温度和压力范围。温度、压力、密度和成分的标准不确定度分别为90 mK、25 kPa、0.2%和0.006。利用Peng-Robinson状态方程（EoS）与van der Waals （vdW）混合规则对压缩液相的实验密度数据进行了关联。与PR + vdW模型和REFPROP 10.0相比，CO2 + R1243zf混合物的平均绝对相对偏差（AARD）分别为1.12%和0.86%，CO2 + R1234yf混合物的平均绝对相对偏差（AARD）分别为0.21%和0.18%。在本文实验数据的基础上，利用其他文献的数据对PR + vdW模型进行比较，结果一致性较好。

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引用次数: 0

Thermodynamic and physicochemical properties of aqueous solutions of dimethyl phosphate – based ionic liquids as working pairs in absorption refrigeration: Experimental study and modeling 磷酸二甲酯基离子液体作为吸收式制冷工作对水溶液的热力学和物理化学性质：实验研究和模拟

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-10-21 DOI: 10.1016/j.jct.2025.107590

Marta Królikowska , Marta Skorupa , Michał Skonieczny , Kamil Paduszyński

This research aims to identify new working fluids for absorption chillers by presenting experimental data on the thermodynamic properties of pure 1-methylpyridinium dimethyl phosphate ([C₁Py][DMP]) and N,N,N-triethyl-N-methylammonium dimethyl phosphate ([N_1,2,2,2][DMP]), as well as their aqueous solutions. The study includes measurements of vapor-liquid equilibrium (VLE), liquid density, and dynamic viscosity. VLE was measured using an ebulliometric method at temperatures ranging from 338.15 to 368.15 K and pressures up to 85 kPa. A vapor absorption refrigeration cycle was modelled using experimental and literature VLE data for similar ionic liquids, enabling the calculation of performance coefficients and circulation ratios. Additionally, liquid density and viscosity were measured as a function of concentration and temperature. Empirical equations were used to correlate these physicochemical properties. The impact of the IL structure on the system's thermodynamic properties is discussed, contributing to the advancement of knowledge in this field.

本研究旨在通过对纯1-甲基磷酸二甲基吡啶（[C1Py][DMP]）和N，N，N-三乙基-N-甲基磷酸二甲基铵（[N1,2,2,2][DMP]）及其水溶液的热力学性质的实验数据，寻找新的吸收式冷水机组工作流体。该研究包括气液平衡（VLE），液体密度和动态粘度的测量。在温度范围为338.15至368.15 K，压力高达85 kPa的条件下，使用气泡法测量了VLE。利用类似离子液体的实验和文献VLE数据，建立了蒸汽吸收式制冷循环模型，计算了性能系数和循环比。此外，测量了液体密度和粘度作为浓度和温度的函数。经验方程式被用来把这些物理化学性质联系起来。讨论了IL结构对系统热力学性质的影响，促进了该领域知识的进步。

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引用次数: 0

Solid-phase equilibria in the FeS-In2S3-S system, thermodynamic properties of the FеIn2S4 compound and (FeS)1-x(In2S3)x solid solutions FeS-In2S3- s体系的固相平衡，fnot_in2s4化合物和（FeS）1-x(In2S3)x固溶体的热力学性质

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-10-13 DOI: 10.1016/j.jct.2025.107585

F.M. Mammadov , D.M. Babanly , S.Z. Imamaliyeva , G.S. Zeynalova , E.I. Ahmadov , M.B. Babanly

In this paper, the results of a comprehensive study of solid-phase equilibria in the FeS-In₂S₃-S system and thermodynamic properties of intermediate phases using DTA, XRD, and EMF methods are presented. Based on the experimental results and literature data, the character of solid-phase equilibria in the Fe-In-S system in the FeS-In₂S₃-S composition range is established.

From the EMF measurements of the concentration cells of the type (−) FeS(solid) | glycerol + KCl + FeCl₂ | (Fe in alloy) (+) in the 300–390 K temperature interval, the relative partial thermodynamic functions of FeS and Fe in alloys were determined. By integrating the Gibbs-Duhem equation from the obtained partial molar quantities of iron, using the thermodynamic data for In₂S₃, the standard Gibbs free energy of formation and the enthalpy of formation, as well as the standard entropy of the FeIn₂S₄ compound and solid solutions (FeS)_1-x(In₂S₃)_x (x = 0.6; 0.8; 0.9) were calculated.

本文采用DTA、XRD和EMF等方法对FeS-In2S3-S体系的固相平衡和中间相的热力学性质进行了综合研究。根据实验结果和文献数据，建立了Fe-In-S体系在FeS-In2S3-S组成范围内固相平衡的特征。从（−）FeS（固体）|甘油+ KCl + FeCl2 |（合金中铁）（+）型浓度池在300-390 K温度区间的电动势测量中，确定了FeS和合金中铁的相对偏热力学函数。利用In2S3的热力学数据，对得到的铁的偏摩尔量积分Gibbs- duhem方程，计算出FeIn2S4化合物和固溶体（FeS）1-x(In2S3)x （x = 0.6; 0.8; 0.9）的标准生成自由能和生成焓。

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引用次数: 0

Relationship between enthalpy and volume changes on melting: a case study of eight cyclic organic compounds 熔融过程中焓与体积变化的关系：以八种环状有机化合物为例

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-10-11 DOI: 10.1016/j.jct.2025.107589

Andrey A. Sokolov, Boris N. Solomonov, Mikhail I. Yagofarov

The study of structural parameters that influence the thermodynamics of melting of organic compounds is many decades old. Our recent work revealed a relationship between fusion enthalpy, molar volume change on melting, and molecular structure. In this paper, we continued to analyze the relationship between the shape of the molecule and the thermodynamic properties of melting through a comprehensive study of eight cyclic organic compounds. The fusion enthalpies were determined by DSC, and the densities in the liquid state in the temperature range from T_m to 343 K were measured using a high-precision density meter. The predictive capability of the previously established linear correlation between the molecular sphericity parameter and the ratio between the enthalpy and molar volume changes on melting was confirmed using the experimental data in combination with literature values of crystal phase densities. The above ratios were predicted with RMS of 9 %, which is comparable with the combined experimental accuracy and beyond the known predictive approaches. In addition, the reliability of the molecular dynamics method in the evaluation of the liquid density at the melting temperature was tested and confirmed, which enables the replacement of the experimental procedure for the liquid density measurement when calculating the enthalpy-to-volume changes ratio according to the correlation found.

影响有机化合物熔化热力学的结构参数的研究已有几十年的历史。我们最近的工作揭示了熔化焓、熔化时摩尔体积变化和分子结构之间的关系。在本文中，我们通过对八种环状有机化合物的综合研究，继续分析分子形状与熔融热力学性质之间的关系。用DSC法测定了熔合焓，用高精度密度计测定了熔合焓在Tm ~ 343 K范围内的液态密度。用实验数据结合文献中晶体相密度的数值，证实了先前建立的分子球度参数与熔化时焓与摩尔体积变化之比的线性关系的预测能力。上述比率的预测RMS为9%，与综合实验精度相当，超出了已知的预测方法。此外，测试并证实了分子动力学方法在熔融温度下评价液体密度的可靠性，从而可以根据发现的相关性计算焓容变化比时替代实验方法进行液体密度测量。

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引用次数: 0

Molecular interactions of butyric and L(+)-lactic acids in water-soluble potassium benzoate solutions: An acoustic and thermodynamic study 水溶性苯甲酸钾溶液中丁酸和L(+)-乳酸的分子相互作用：声学和热力学研究

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-10-09 DOI: 10.1016/j.jct.2025.107586

Ashpinder Kaur Gill , Nabaparna Chakraborty , K.C. Juglan

The densities and sound velocities were investigated to study the molecular dynamics between potassium benzoate in water-soluble solutions of butyric and L(+)-lactic acids at (0.000, 0.010, 0.020, 0.030)

mol ∙ {kg}^{- 1}

, across a temperature from 288.15 K to 318.15 K. Numerous acoustical and volumetric characteristics such as apparent and partial molar parameters, transfer properties, expansibility coefficient, temperature-dependent derivatives, and the thermal expansion coefficient were evaluated from the experimentally attained densities and sound speeds data. The results are estimated by analyzing the nature of molecular interactions within the liquid system with insights derived from the co-sphere overlap approach. The use of Hepler's thermodynamic relation serves as a reliable method for defining the structural role (structure-form or disrupt) of the ternary mixture. Interaction coefficients were computed to characterize the solute as well as solvent interactions in the ternary combinations. The hydration number has been calculated for the liquid systems using compressibility data based on Passynski's equation. The shifts detected in the OH stretching band through FTIR analysis indicate the creation of hydrogen bonds in the investigated systems. These findings have practical applications in several industries, aiding in the growth of stable formulations and improved product performance.

在288.15 K至318.15 K温度范围内，研究了密度和声速在（0.000,0.010,0.020,0.030）mol∙kg - 1丁酸和L(+)-乳酸水溶液中苯甲酸钾的分子动力学。根据实验获得的密度和声速数据，评估了许多声学和体积特性，如表观和部分摩尔参数、传递特性、膨胀系数、温度相关导数和热膨胀系数。结果是通过分析液体系统内分子相互作用的性质，以及来自共球重叠方法的见解来估计的。使用海普勒热力学关系是确定三元混合物的结构作用（结构-形式或破坏）的可靠方法。通过计算相互作用系数来表征三元组合中溶质和溶剂的相互作用。根据Passynski方程，利用可压缩性数据计算了液体体系的水化数。通过FTIR分析在OH拉伸带中检测到的位移表明在所研究的体系中产生了氢键。这些发现在几个行业有实际应用，有助于稳定配方的增长和提高产品性能。

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引用次数: 0

Recovery of refolded aggregated proteins from ionic liquids via biphasic systems 通过双相系统从离子液体中回收再折叠聚集蛋白

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-10-08 DOI: 10.1016/j.jct.2025.107588

Kyoko Fujita, Daigo Sasaki

We demonstrate that the refolding and activity recovery of aggregated proteins can be achieved simply and efficiently using two-phase systems of hydrophobic ionic liquids (ILs)/buffer. The high solubility of thermally aggregated concanavalin A (Con A) was observed in the hydrated tetra-n-octylammonium dihydrogen phosphate ([N8888][dhp]). Upon adding a buffer solution, the two-phase separation of the IL and buffer was confirmed, with the upper layer consisting of the IL phase and the lower layer consisting of the aqueous phase. Dissolved Con A was transferred to the buffer phase. Transfer efficiency of Con A into the buffer phase increased as the water content of the IL phase decreased, which was influenced by the buffer concentration and temperature. Con A transferred into the buffer phase exhibited a recovery of sugar chain-binding activity to levels comparable to that of native Con A.

我们证明，使用疏水离子液体(ILs)/缓冲液的两相系统可以简单有效地实现聚集蛋白的重折叠和活性恢复。在水合磷酸四正辛二氢铵（[N8888][dhp]）中观察到热聚集的豆豆蛋白A （Con A）的高溶解度。加入缓冲溶液后，确认IL和缓冲液的两相分离，上层为IL相，下层为水相。溶解的Con A转移到缓冲相。Con A向缓冲相的转移效率随着IL相含水量的降低而增加，这受缓冲液浓度和温度的影响。转移到缓冲期的Con A显示糖链结合活性恢复到与天然Con A相当的水平。

引用次数: 0

Ethylene glycol methyl ether and 1,2-Propylenediamine deep eutectic solvents for CO2 sequestration: Physicochemical properties and intermolecular interactions 用于CO2封存的乙二醇甲基醚和1,2-丙二胺深共晶溶剂：物理化学性质和分子间相互作用

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-10-06 DOI: 10.1016/j.jct.2025.107584

Yifan Yang , Zhengtong Zhu , Zhaojun Wu , Bo Zhang , Rui Cao , Wenjie Zhai , Guojun Ji , Jianbin Zhang

This work introduces the deep eutectic solvents (DESs) composed of ethylene glycol monomethyl ether (EGME) and 1,2-propylenediamine (1,2-PDA) for enhanced CO₂ sequestration. Initially, physicochemical properties, encompassing solution density and viscosity, are systemically investigated, while concurrently delving into the intermolecular forces that govern these properties. The DESs demonstrate significantly improved CO₂ absorption, overcoming the limitations of traditional amine-based solvents. A detailed analysis reveals that an optimal molar ratio of DESs maximize CO₂ absorption, outperforming the individual components. Spectroscopic and quantum chemical calculations were employed to elucidate the mechanisms, which showed that -OH···N (H₂) hydrogen bonding plays a critical role in enhancing the efficiency of solvent absorption. The results indicate that at a 65 % EGME molar fraction, the system achieves the most stable physicochemical properties and strongest hydrogen bonding. Notably, DESs with 85 % EGME can achieve an optimal capture performance of up to 1.14 mol CO₂/mol 1,2-PDA, nearly doubling 1,2-PDA's adsorption capacity.

本文介绍了由乙二醇单甲醚（EGME）和1,2-丙二胺（1,2- pda）组成的深度共晶溶剂（DESs），用于增强CO2的固载。首先，系统地研究了包括溶液密度和粘度在内的物理化学性质，同时深入研究了控制这些性质的分子间作用力。DESs的CO2吸收量显著提高，克服了传统胺基溶剂的局限性。详细的分析表明，最佳的DESs摩尔比最大化CO2吸收，优于单个组分。利用光谱和量子化学方法对其机理进行了分析，结果表明-OH···N （H2）氢键对提高溶剂吸收效率起着关键作用。结果表明，当EGME摩尔分数为65%时，体系的物理化学性质最稳定，氢键最强。值得注意的是，含有85% EGME的DESs可以达到1.14 mol CO2/mol 1,2- pda的最佳捕获性能，几乎是1,2- pda吸附量的两倍。

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引用次数: 0

Liquid-liquid equilibrium of systems containing acylglycerols from olive oil, glycerol and tert-butanol 含有橄榄油、甘油和叔丁醇的酰基甘油体系的液-液平衡

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-09-21 DOI: 10.1016/j.jct.2025.107583

Larissa Madureira Pacholak do Espírito Santo , Ana Maura Novak , Maria Clara Corrêa Gomes Palma , Guilherme Lanzi Sassaki , Giulia Herbst , Luis Ricardo Shigueyuki Kanda , Fernando Augusto Pedersen Voll

Studies indicate that consuming oils rich in diacylglycerol instead of triacylglycerol can prevent health problems commonly related to the consumption of fats, such as obesity and cardiovascular disease. For that reason, production and purification of diacylglycerol have received great attention. This work reports experimental results and thermodynamic modeling of liquid-liquid equilibrium of systems containing mono-, di-, and triacylclycerols from olive oil, glycerol and tert-butanol. UNIQUAC and NRTL models were used to calculate the phase equilibria and were well fitted to experimental data with root mean square deviations below 2 wt% for all studied systems. The results obtained in this work indicate the feasibility of diacylglycerol separation from other acylglycerols through liquid-liquid extraction using glycerol and tert-butanol as solvents.

研究表明，食用富含二酰基甘油的油，而不是富含三酰基甘油的油，可以预防通常与脂肪消耗有关的健康问题，如肥胖和心血管疾病。因此，二酰基甘油的生产和提纯一直受到人们的高度重视。这项工作报告了橄榄油、甘油和叔丁醇中含有一、二、三酰基甘油的系统的实验结果和液-液平衡的热力学建模。UNIQUAC和NRTL模型用于计算相平衡，并与所有研究系统的实验数据很好地拟合，均方根偏差低于2 wt%。研究结果表明，以甘油和叔丁醇为溶剂，采用液-液萃取法分离二酰基甘油和其他酰基甘油是可行的。

引用次数: 0

Corrigendum to “Isobaric vapour-liquid equilibrium for systems of propionic acid, butanoic acid and 1,4-butyrolactone at 15.0 kPa” [J. Chem. Thermodyn. 186 (2023) 107143 15.0 kPa时丙酸、丁酸和1,4-丁内酯体系的等压汽液平衡的勘误表[J]。化学。热力学报，186 (2023)107143

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-09-12 DOI: 10.1016/j.jct.2025.107581

Jun Wang , JiaRui Sun , Ming Shang , Chunxiang Huang , XinSheng Rui

引用次数: 0

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