Journal of Chemical Thermodynamics最新文献

英文中文

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

Effect of Thiazolidine as thermodynamic inhibitor on hydrate phase equilibrium conditions of carbon dioxide 噻唑烷作为热力学抑制剂对二氧化碳水合物相平衡条件的影响

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.2025.107582

Xinrui Hou, Zhigao Sun

This work first reports thiazolidine as a novel inhibitor for carbon dioxide hydrates. Hydrate equilibrium conditions of carbon dioxide with thiazolidine were experimentally determined by isochoric stepwise heating method in this paper. The testing results indicated that adding thiazolidine moved phase equilibrium curve of hydrate toward lower temperature and higher pressure area, demonstrating its effectiveness as a thermodynamic inhibitor. The inhibition effect of thiazolidine on hydrate formation increased when more thiazolidine was added. The inhibition effect was most significant at the concentration of 22.5 wt% thiazolidine within the concentration range measured in this work. Combined with the low toxicity, good biodegradability, excellent water solubility, and simple green synthesis process, thiazolidine is an environmentally friendly thermodynamic inhibitor of carbon dioxide hydrate formation.

本文首次报道了噻唑烷作为二氧化碳水合物的新型抑制剂。采用等时次逐步加热法测定了二氧化碳与噻唑烷的水合物平衡条件。实验结果表明，噻唑烷的加入使水合物的相平衡曲线向低温高压区域移动，证明了噻唑烷作为热力学抑制剂的有效性。噻唑烷对水合物形成的抑制作用随着噻唑烷添加量的增加而增强。在测定的浓度范围内，噻唑烷浓度为22.5 wt%时抑制效果最显著。噻唑烷具有低毒性、良好的生物降解性、优异的水溶性、简单的绿色合成工艺等优点，是一种环境友好型的二氧化碳水合物生成热力学抑制剂。

引用次数: 0

Research on furosemide (form I) in sixteen mono-solvents: Solubility determination and models, thermodynamic analysis, DFT calculation and molecular dynamic simulation 速尿（形式I）在16种单溶剂中的研究：溶解度测定和模型、热力学分析、DFT计算和分子动力学模拟

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-09-09 DOI: 10.1016/j.jct.2025.107579

Min Zheng , Hongkun Zhao

The comprehensive solubilities of furosemide (I) in sixteen pure solvents were ascertained using the method of shake-flask saturation, together with experimental and computational approaches. The furosemide (I) solubility increased with rising temperature. It was highest in ethyl acetate, and lowest in water. No solvation, together with crystal transition, was observed during the trial process, as indicated by X-ray powder diffraction (XRD) scans. Apelblat equation provided the best correlation results. The Wilson equation was employed to calculate the dissolving thermodynamic parameters. Furthermore, the acidity-basicity characteristics of static electricity were illustrated utilizing the minimum negative and maximum positive electrostatic potential of the furosemide molecule surface. The intermolecular interactions of furosemide with solvents were examined using molecular dynamic simulation and density functional theory (DFT) calculations, and Hirshfeld partition-based independent gradient analysis.

采用摇瓶饱和法，结合实验和计算方法，确定了速尿(I)在16种纯溶剂中的综合溶解度。随着温度的升高，速尿的溶解度增大。乙酸乙酯含量最高，水含量最低。x射线粉末衍射（XRD）扫描表明，在试验过程中没有观察到溶剂化和晶体转变。Apelblat方程提供了最好的相关结果。采用Wilson方程计算溶解热力学参数。此外，利用速尿胺分子表面的最小负静电电位和最大正静电电位来说明静电的酸碱特性。采用分子动力学模拟、密度泛函理论（DFT）计算和基于Hirshfeld分区的独立梯度分析，研究了速脲与溶剂的分子间相互作用。

引用次数: 0

Investigation of thermophysical properties and CO2 equilibrium solubility in nonaqueous mixtures of monoethanolamine (MEA) and N,N-dimethylformamide (DMF) 单乙醇胺（MEA）和N，N-二甲基甲酰胺（DMF）非水混合物中热物理性质和CO2平衡溶解度的研究

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-09-07 DOI: 10.1016/j.jct.2025.107580

Lijiao Ma , Yudong Ding , Yi Zhang , Xun Zhu , Hong Wang , Min Cheng , Qiang Liao

To reduce CO₂ emissions and address issues with conventional amine-based aqueous absorbents, a mixed nonaqueous solution of monoethanolamine (MEA) and N,N-dimethylformamide (DMF) was proposed. The density, dynamic viscosity and refractive index of fresh MEA-DMF solutions (10-50 wt% MEA) and CO₂-loaded solutions (0.10–0.51 mol CO₂·(mol MEA)⁻¹) were measured across the temperature range of 298.15–333.15 K. The values for fresh solutions were correlated with concentration and temperature using the Jouyban-Acree model (JAM) and an exponential equation. Then the results after CO₂ absorption were derived from the CO₂ loading amount. Additionally, CO₂ absorption performance of MEA-DMF with various concentrations at 303.15–333.15 K and 9.64–134.52 kPa was assessed to determine gas-liquid equilibrium and develop semi-empirical correlations. Nuclear magnetic resonance (NMR) analysis confirmed that carbamate was the primary product formed after CO₂ absorption in the nonaqueous absorbent. These studies provide essential data for equipment design and absorbent optimization. MEA-DMF solutions demonstrate favorable viscosity and CO₂ absorption performance, supporting the potential use of nonaqueous absorbents in industrial CO₂ capture technologies.

为了减少二氧化碳排放和解决传统胺基水吸附剂的问题，提出了一种单乙醇胺（MEA）和N，N-二甲基甲酰胺（DMF）的混合非水溶液。在298.15-333.15 K的温度范围内，测量了新鲜MEA- dmf溶液（10-50 wt% MEA）和CO2负载溶液（0.10-0.51 mol CO2·(mol MEA)−1）的密度、动态粘度和折射率。利用Jouyban-Acree模型（JAM）和指数方程对新鲜溶液的值与浓度和温度进行了相关性分析。然后根据CO2的负荷量得出CO2吸收后的结果。此外，在303.15 ~ 333.15 K和9.64 ~ 134.52 kPa的不同浓度条件下，对MEA-DMF的CO2吸收性能进行了评估，以确定气液平衡并建立半经验相关性。核磁共振（NMR）分析证实，氨基甲酸酯是在非水吸收剂中吸收CO2后形成的主要产物。这些研究为设备设计和吸收剂优化提供了必要的数据。MEA-DMF溶液具有良好的粘度和二氧化碳吸收性能，支持非水吸收剂在工业二氧化碳捕集技术中的潜在应用。

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引用次数: 0

Investigation of the behavior of methyl octanoate and 2-alkanol mixtures: Evaluating the friction theory 辛酸甲酯和2-烷醇混合物的行为研究：摩擦理论的评价

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-09-04 DOI: 10.1016/j.jct.2025.107578

Samaneh Heydarian, Sanaz Gharehzadeh Shirazi

This study investigated the volumetric and viscous properties of binary mixtures composed of methyl octanoate (MO) and a series of 2-alkanols (ranging from C3 to C6) across a temperature range of 293.15 to 323.15 K. Experimental analysis indicated positive excess molar volumes and negative viscosity deviations, suggesting comparatively weak intermolecular interactions between MO and the 2-alkanol molecules. The observed positive excess molar volumes suggest that the mixing process results in an expansion, potentially due to disruption of self-associated structures within the pure components. Conversely, the negative viscosity deviations indicate a decrease in resistance to flow compared to ideal mixing, further supporting the notion of reduced cohesive forces in the mixtures. To further elucidate the mixture behavior and provide a predictive capability, the Friction theory (f-theory) was employed to model the viscosity of the mixtures. The model exhibited a high degree of accuracy, with a maximum discrepancy of only 2.32 % observed for the MO + 2-hexanol system. This close agreement between the theoretical predictions and experimental data underscores the utility of the f-theory as a robust tool for predicting the rheological behavior of these binary mixtures, offering potential applications in fields such as chemical process design and optimization.

本文研究了由辛酸甲酯（MO）和一系列2-烷醇（从C3到C6）组成的二元混合物在293.15至323.15 K温度范围内的体积和粘性特性。实验分析表明，MO与2-烷醇分子之间的分子间相互作用相对较弱，过量摩尔体积为正，粘度偏差为负。观察到的正过量摩尔体积表明，混合过程导致了膨胀，这可能是由于纯组分内部自相关结构的破坏。相反，与理想混合相比，负粘度偏差表明流动阻力降低，进一步支持混合物中凝聚力降低的概念。为了进一步阐明混合物的行为并提供预测能力，采用摩擦理论（f理论）来模拟混合物的粘度。该模型具有较高的精度，MO + 2-己醇体系的最大误差仅为2.32%。理论预测和实验数据之间的这种密切一致强调了f理论作为预测这些二元混合物流变行为的强大工具的实用性，在化学过程设计和优化等领域提供了潜在的应用。

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引用次数: 0

Determination of Oxygen Activity Coefficient and Solubility in Lead Nuclear Coolant by Zirconia Solid Electrolyte 氧化锆固体电解质测定铅核冷却剂中的氧活度系数和溶解度

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-09-01 DOI: 10.1016/j.jct.2025.107568

G. Gregori , S. Bassini , A. Antonelli , A. Brunetti , M. Tarantino , L. Silvioli , F. García Ferré

Liquid lead is the chosen coolant for a GEN-IV fast reactor type, the Lead-cooled Fast Reactor (LFR). The content of oxygen dissolved in the coolant is a crucial parameter influencing the oxidation of steels, dissolved corrosion products and lead itself. In this work, we validate Electrochemical Oxygen Sensors (EOSs) and Pumps (EOPs) technology by characterizing the O-Pb-PbO liquid system. Specifically, combing potentiometry by the EOSs with the coulometry by the EOPs along with a customized analytical procedure and numerical analysis, we assessed the oxygen activity coefficient thermal trend, arriving at the following correlation (w.r.t. O_2(g) at 1 bar reference standard state for gaseous oxygen, and 1 wt% standard stated for oxygen dissolved in molten lead):

\log_{10} {(γ_{O (Pb)}^{\infty})}_{(wt . %^{- 1} units)} = 2.22 - \frac{(6517.74 \pm 0.04)}{T_{(K)}}

(621 K ≤ T ≤ 825 K).

Moreover, measuring the EOS open circuit potential in oxygen-saturated lead at different temperatures we assessed the solubility of oxygen, corresponding to the phase boundary between oxygen-saturated liquid lead and solid lead monoxide (PbO), represented by the following correlation:

\log_{10} {(S_{O (Pb)})}_{(wt . %)} = 2.95 - \frac{4909.94}{T_{(K)}}

(618 K ≤ T ≤ 824 K).

The experimental assessments are in good agreement with the most updated results in literature and cover on of the lowest temperatures ever investigated (e.g. 620 K). This work confirms the reliability EOS/EOP technology. Moreover, a detailed and standardized analytical procedure is proposed to conduct thermochemical investigations in Heavy Liquid Metals (HLMs) based on Solid-State Ionics.

液态铅是GEN-IV型快堆——铅冷快堆（LFR）所选择的冷却剂。冷却液中溶解氧的含量是影响钢的氧化、溶解的腐蚀产物和铅本身的重要参数。在这项工作中，我们通过表征O-Pb-PbO液体系统来验证电化学氧传感器（EOSs）和泵（EOPs）技术。具体来说，结合EOPs电位法和EOPs库伦法以及定制的分析程序和数值分析，我们评估了氧活度系数的热趋势，得出以下相关性（气态氧在1 bar参考标准状态下的w.r.t O2(g)，以及溶解在熔融铅中的氧规定的1 wt%标准）：log10γOPb∞wt.%−1单位=2.22−6517.74±0.04TK （621 K≤T≤825 K）。此外，通过测量氧饱和铅在不同温度下的EOS开路电位，我们评估了氧的溶解度，对应于氧饱和液体铅和固体一氧化铅（PbO）之间的相界，由以下相关性表示：log10SOPbwt.%=2.95−4909.94TK （618 K≤T≤824 K）。实验评估与文献中最新的结果很好地一致，并涵盖了迄今为止研究的最低温度（例如620 K）。这项工作证实了EOS/EOP技术的可靠性。此外，本文还提出了一种详细的、标准化的基于固态离子的重金属热化学分析方法。

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