Journal of Chemical Thermodynamics最新文献

{"title":"Relationship between enthalpy and volume changes on melting: a case study of eight cyclic organic compounds","authors":"Andrey A. Sokolov,&nbsp;Boris N. Solomonov,&nbsp;Mikhail I. Yagofarov","doi":"10.1016/j.jct.2025.107589","DOIUrl":"10.1016/j.jct.2025.107589","url":null,"abstract":"<div><div>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 <em>T</em>_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 <em>RMS</em> 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.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"213 ","pages":"Article 107589"},"PeriodicalIF":2.2,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145278067","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular interactions of butyric and L(+)-lactic acids in water-soluble potassium benzoate solutions: An acoustic and thermodynamic study","authors":"Ashpinder Kaur Gill ,&nbsp;Nabaparna Chakraborty ,&nbsp;K.C. Juglan","doi":"10.1016/j.jct.2025.107586","DOIUrl":"10.1016/j.jct.2025.107586","url":null,"abstract":"<div><div>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) <span><math><mi>mol</mi><mo>∙</mo><msup><mi>kg</mi><mrow><mo>−</mo><mn>1</mn></mrow></msup></math></span>, 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 O<img>H 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.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107586"},"PeriodicalIF":2.2,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145267316","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recovery of refolded aggregated proteins from ionic liquids via biphasic systems","authors":"Kyoko Fujita,&nbsp;Daigo Sasaki","doi":"10.1016/j.jct.2025.107588","DOIUrl":"10.1016/j.jct.2025.107588","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"213 ","pages":"Article 107588"},"PeriodicalIF":2.2,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145278068","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ethylene glycol methyl ether and 1,2-Propylenediamine deep eutectic solvents for CO2 sequestration: Physicochemical properties and intermolecular interactions","authors":"Yifan Yang ,&nbsp;Zhengtong Zhu ,&nbsp;Zhaojun Wu ,&nbsp;Bo Zhang ,&nbsp;Rui Cao ,&nbsp;Wenjie Zhai ,&nbsp;Guojun Ji ,&nbsp;Jianbin Zhang","doi":"10.1016/j.jct.2025.107584","DOIUrl":"10.1016/j.jct.2025.107584","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107584"},"PeriodicalIF":2.2,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145267317","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Liquid-liquid equilibrium of systems containing acylglycerols from olive oil, glycerol and tert-butanol","authors":"Larissa Madureira Pacholak do Espírito Santo ,&nbsp;Ana Maura Novak ,&nbsp;Maria Clara Corrêa Gomes Palma ,&nbsp;Guilherme Lanzi Sassaki ,&nbsp;Giulia Herbst ,&nbsp;Luis Ricardo Shigueyuki Kanda ,&nbsp;Fernando Augusto Pedersen Voll","doi":"10.1016/j.jct.2025.107583","DOIUrl":"10.1016/j.jct.2025.107583","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107583"},"PeriodicalIF":2.2,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145121276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of Thiazolidine as thermodynamic inhibitor on hydrate phase equilibrium conditions of carbon dioxide","authors":"Xinrui Hou,&nbsp;Zhigao Sun","doi":"10.1016/j.jct.2025.107582","DOIUrl":"10.1016/j.jct.2025.107582","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107582"},"PeriodicalIF":2.2,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145121277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Research on furosemide (form I) in sixteen mono-solvents: Solubility determination and models, thermodynamic analysis, DFT calculation and molecular dynamic simulation","authors":"Min Zheng ,&nbsp;Hongkun Zhao","doi":"10.1016/j.jct.2025.107579","DOIUrl":"10.1016/j.jct.2025.107579","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107579"},"PeriodicalIF":2.2,"publicationDate":"2025-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145105837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigation of thermophysical properties and CO2 equilibrium solubility in nonaqueous mixtures of monoethanolamine (MEA) and N,N-dimethylformamide (DMF)","authors":"Lijiao Ma ,&nbsp;Yudong Ding ,&nbsp;Yi Zhang ,&nbsp;Xun Zhu ,&nbsp;Hong Wang ,&nbsp;Min Cheng ,&nbsp;Qiang Liao","doi":"10.1016/j.jct.2025.107580","DOIUrl":"10.1016/j.jct.2025.107580","url":null,"abstract":"<div><div>To reduce CO₂ emissions and address issues with conventional amine-based aqueous absorbents, a mixed nonaqueous solution of monoethanolamine (MEA) and <em>N</em>,<em>N</em>-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.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107580"},"PeriodicalIF":2.2,"publicationDate":"2025-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145049506","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigation of the behavior of methyl octanoate and 2-alkanol mixtures: Evaluating the friction theory","authors":"Samaneh Heydarian,&nbsp;Sanaz Gharehzadeh Shirazi","doi":"10.1016/j.jct.2025.107578","DOIUrl":"10.1016/j.jct.2025.107578","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107578"},"PeriodicalIF":2.2,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145049507","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Determination of Oxygen Activity Coefficient and Solubility in Lead Nuclear Coolant by Zirconia Solid Electrolyte","authors":"G. Gregori ,&nbsp;S. Bassini ,&nbsp;A. Antonelli ,&nbsp;A. Brunetti ,&nbsp;M. Tarantino ,&nbsp;L. Silvioli ,&nbsp;F. García Ferré","doi":"10.1016/j.jct.2025.107568","DOIUrl":"10.1016/j.jct.2025.107568","url":null,"abstract":"<div><div>Liquid lead is the chosen coolant for a GEN-IV fast reactor type, the <em><u>L</u>ead-cooled <u>F</u>ast <u>R</u>eactor</em> (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 <em><u>E</u>lectrochemical <u>O</u>xygen <u>S</u>ensors</em> (EOSs) and <em><u>P</u>umps</em> (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 (<em>w.r.t.</em> O_2(g) at 1 bar reference standard state for gaseous oxygen, and 1 wt% standard stated for oxygen dissolved in molten lead): <span><math><msub><mi>log</mi><mn>10</mn></msub><msub><mfenced><msubsup><mi>γ</mi><mrow><mi>O</mi><mfenced><mi>Pb</mi></mfenced></mrow><mo>∞</mo></msubsup></mfenced><mfenced><mrow><mi>wt</mi><mo>.</mo><msup><mo>%</mo><mrow><mo>−</mo><mn>1</mn></mrow></msup><mspace></mspace><mtext>units</mtext></mrow></mfenced></msub><mo>=</mo><mn>2.22</mn><mo>−</mo><mfrac><mfenced><mrow><mn>6517.74</mn><mo>±</mo><mn>0.04</mn></mrow></mfenced><msub><mi>T</mi><mfenced><mi>K</mi></mfenced></msub></mfrac></math></span> (621 K ≤ T ≤ 825 K).</div><div>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: <span><math><msub><mi>log</mi><mn>10</mn></msub><msub><mfenced><msub><mi>S</mi><mrow><mi>O</mi><mfenced><mi>Pb</mi></mfenced></mrow></msub></mfenced><mfenced><mrow><mi>wt</mi><mo>.</mo><mo>%</mo></mrow></mfenced></msub><mo>=</mo><mn>2.95</mn><mo>−</mo><mfrac><mn>4909.94</mn><msub><mi>T</mi><mfenced><mi>K</mi></mfenced></msub></mfrac></math></span> (618 K ≤ T ≤ 824 K).</div><div>The experimental assessments are in good agreement with the most updated results in literature and cover on of the lowest temperatures ever investigated (<em>e.g.</em> 620 K). This work confirms the reliability EOS/EOP technology. Moreover, a detailed and standardized analytical procedure is proposed to conduct thermochemical investigations in <em><u>H</u>eavy <u>L</u>iquid <u>M</u>etals</em> (HLMs) based on Solid-State Ionics.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107568"},"PeriodicalIF":2.2,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145004616","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}