Pub Date : 2025-07-31DOI: 10.1016/j.jct.2025.107551
Bo Wang , Bo Li , Jun Chen , Hong-xia Pan , Chong Li , Li-zhen Chen , Jian-long Wang
The solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven pure solvents (acetone, cyclohexanone, 2-butanone, methyl acetate, ethyl acetate, benzene, chlorobenzene, pyridine, acetonitrile, 1,2-dichloroethane and 1,4-dioxane) was measured by laser dynamic method at the temperature range from 293.15 K to 333.15 K under the pressure of 101.3 kPa. The study found that the solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl is positively correlated with increasing temperature. The experimental data were correlated using four thermodynamic models: the modified Apelblat model, van't Hoff model, NRTL model, and Wilson model. The modified Apelblat model demonstrated superior correlation performance. Hirshfeld surface and molecular electrostatic potential surface analysis were also conducted to investigate the solvent-solute interaction sites and the effects of interactions on the solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven selected pure solvents. Additionally, the thermodynamic properties of the dissolution process were calculated using the van't Hoff model, and the results indicated that the dissolution of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven selected pure solvents is an endothermic and entropy-increasing process.
{"title":"Solubility determination, model evaluation and thermodynamic analysis of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven pure solvents","authors":"Bo Wang , Bo Li , Jun Chen , Hong-xia Pan , Chong Li , Li-zhen Chen , Jian-long Wang","doi":"10.1016/j.jct.2025.107551","DOIUrl":"10.1016/j.jct.2025.107551","url":null,"abstract":"<div><div>The solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven pure solvents (acetone, cyclohexanone, 2-butanone, methyl acetate, ethyl acetate, benzene, chlorobenzene, pyridine, acetonitrile, 1,2-dichloroethane and 1,4-dioxane) was measured by laser dynamic method at the temperature range from 293.15 K to 333.15 K under the pressure of 101.3 kPa. The study found that the solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl is positively correlated with increasing temperature. The experimental data were correlated using four thermodynamic models: the modified Apelblat model, van't Hoff model, NRTL model, and Wilson model. The modified Apelblat model demonstrated superior correlation performance. Hirshfeld surface and molecular electrostatic potential surface analysis were also conducted to investigate the solvent-solute interaction sites and the effects of interactions on the solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven selected pure solvents. Additionally, the thermodynamic properties of the dissolution process were calculated using the van't Hoff model, and the results indicated that the dissolution of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven selected pure solvents is an endothermic and entropy-increasing process.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107551"},"PeriodicalIF":2.2,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144767225","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}
Pub Date : 2025-07-29DOI: 10.1016/j.jct.2025.107549
Alexis Gibson , Shuhao Yang , Richard E. Riman , Alexandra Navrotsky , Brian F. Woodfield
This work investigates the heat capacity and thermodynamic properties of three rare earth oxychlorides (REOCl), TmOCl, NdOCl, and YOCl. To understand their thermodynamic landscapes, we measured their heat capacities from 1.8 to 300 K. Our results indicate the presence of several Schottky anomalies at low temperatures (below 7 K), and TmOCl had an additional Schottky anomaly centered around 25 K, which we attribute to a contribution from f-block electrons. We fitted the data to theoretical functions and used these models to derive the standard entropy, enthalpy, and Gibbs energy. Using previously published enthalpy of formation data, we determined the Gibbs energies of formation from the elements and the oxides and chlorides at selected temperatures. At 298.15 K, the Gibbs energy of formation relative to oxides and chlorides was calculated to be −59.4 kJ·mol−1, −41.0 kJ·mol−1, and − 11.1 kJ·mol−1 for NdOCl, YOCl, and TmOCl, respectively. The Gibbs energy of formation of REOCl relative to the elements at 298.15 K was calculated to be −952.3 kJ·mol−1, −967.4 kJ·mol−1, and − 938.9 kJ·mol−1 for NdOCl, YOCl, and TmOCl, respectively. These results confirm the stability of REOCl relative to the elements and the binary chlorides and oxides.
{"title":"Heat capacity and thermodynamic functions of stoichiometric rare earth oxychlorides (REOCl)","authors":"Alexis Gibson , Shuhao Yang , Richard E. Riman , Alexandra Navrotsky , Brian F. Woodfield","doi":"10.1016/j.jct.2025.107549","DOIUrl":"10.1016/j.jct.2025.107549","url":null,"abstract":"<div><div>This work investigates the heat capacity and thermodynamic properties of three rare earth oxychlorides (REOCl), TmOCl, NdOCl, and YOCl. To understand their thermodynamic landscapes, we measured their heat capacities from 1.8 to 300 K. Our results indicate the presence of several Schottky anomalies at low temperatures (below 7 K), and TmOCl had an additional Schottky anomaly centered around 25 K, which we attribute to a contribution from f-block electrons. We fitted the data to theoretical functions and used these models to derive the standard entropy, enthalpy, and Gibbs energy. Using previously published enthalpy of formation data, we determined the Gibbs energies of formation from the elements and the oxides and chlorides at selected temperatures. At 298.15 K, the Gibbs energy of formation relative to oxides and chlorides was calculated to be −59.4 kJ·mol<sup>−1</sup>, −41.0 kJ·mol<sup>−1</sup>, and − 11.1 kJ·mol<sup>−1</sup> for NdOCl, YOCl, and TmOCl, respectively. The Gibbs energy of formation of REOCl relative to the elements at 298.15 K was calculated to be −952.3 kJ·mol<sup>−1</sup>, −967.4 kJ·mol<sup>−1</sup>, and − 938.9 kJ·mol<sup>−1</sup> for NdOCl, YOCl, and TmOCl, respectively. These results confirm the stability of REOCl relative to the elements and the binary chlorides and oxides.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107549"},"PeriodicalIF":2.2,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144749987","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}
Pub Date : 2025-07-28DOI: 10.1016/j.jct.2025.107548
Clara M. Dixon , Mina Aziziha , Amir Mofrad , Jorge Paz Soldan Palma , Ronald E. Booth , Aiswarya Padinhare Manissery , Jack A. Wilson , Hans-Conrad zur Loye , Hunter B. Tisdale , Juliano Schorne-Pinto , Theodore M. Besmann
Gibbs energy models necessary to describe the thermochemical behavior of cesium and iodine in molten FLiNaK (46.5LiF-11.5NaF-42KF mol%), a proposed molten salt reactor coolant and fuel solvent, have been developed as they are of concern due to their high radiotoxicity and volatility. The six constituent pseudo-binary systems LiI-CsI, LiI-KI, LiI-NaI, NaI-KI, KI-CsI and NaI-CsI were evaluated using available phase equilibria and mixing enthalpy measurements. The models for the ternary reciprocal salt systems Li,Cs|F,I, Li,K|F,I, Li,Na|F,I, Na,K|F,I, Na,Cs|F,I and K,Cs|F,I were obtained by interpolation of the optimized pseudo-binary systems and parameters fit as necessary based on observed behavior. The additive (common cation) pseudo-ternary system representations were obtained by interpolation of the optimized pseudo-binary systems, and parameters for those as well modified as necessary to best fit observations. Together, the evaluated systems contain the necessary thermochemical models to generate quaternary and higher order reciprocal salt system descriptions, with the representations of the Li,Na,Cs|F,I, Li,K,Cs|F,I and Na,K,Cs|F,I quaternary reciprocal salt systems largely well-reproducing reported behavior. These salt system representations have subsequently been incorporated in the Molten Salt Thermal Properties Database – Thermochemical (MSTDB-TC).
{"title":"Thermodynamic assessment of the Li, Na, K, Cs | F, I reciprocal salt for MSR applications","authors":"Clara M. Dixon , Mina Aziziha , Amir Mofrad , Jorge Paz Soldan Palma , Ronald E. Booth , Aiswarya Padinhare Manissery , Jack A. Wilson , Hans-Conrad zur Loye , Hunter B. Tisdale , Juliano Schorne-Pinto , Theodore M. Besmann","doi":"10.1016/j.jct.2025.107548","DOIUrl":"10.1016/j.jct.2025.107548","url":null,"abstract":"<div><div>Gibbs energy models necessary to describe the thermochemical behavior of cesium and iodine in molten FLiNaK (46.5LiF-11.5NaF-42KF mol%), a proposed molten salt reactor coolant and fuel solvent, have been developed as they are of concern due to their high radiotoxicity and volatility. The six constituent pseudo-binary systems LiI-CsI, LiI-KI, LiI-NaI, NaI-KI, KI-CsI and NaI-CsI were evaluated using available phase equilibria and mixing enthalpy measurements. The models for the ternary reciprocal salt systems Li,Cs|F,I, Li,K|F,I, Li,Na|F,I, Na,K|F,I, Na,Cs|F,I and K,Cs|F,I were obtained by interpolation of the optimized pseudo-binary systems and parameters fit as necessary based on observed behavior. The additive (common cation) pseudo-ternary system representations were obtained by interpolation of the optimized pseudo-binary systems, and parameters for those as well modified as necessary to best fit observations. Together, the evaluated systems contain the necessary thermochemical models to generate quaternary and higher order reciprocal salt system descriptions, with the representations of the Li,Na,Cs|F,I, Li,K,Cs|F,I and Na,K,Cs|F,I quaternary reciprocal salt systems largely well-reproducing reported behavior. These salt system representations have subsequently been incorporated in the Molten Salt Thermal Properties Database – Thermochemical (<em>MSTDB-TC</em>).</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107548"},"PeriodicalIF":2.2,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144852766","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}
Pub Date : 2025-07-23DOI: 10.1016/j.jct.2025.107550
Houchun Yan, He Ma, Xuqiang Li, Shaolong Dong, Qingsong Li
To separate higher-rank phenols from the coal tar, the model oil was constructed, and the separation efficiency of various solvents was analyzed using solvent power, selectivity, and performance index. The liquid-liquid equilibrium data of cumene + {4-ethylphenol, 4-propylphenol, 2-allylphenol, and 2-isopropylphenol} + ethanolamine was measured at 298.2 K and 101.3 kPa, and the distribution coefficient and separation factor were calculated. Furthermore, the NRTL and UNIQUAC models were correlated with the LLE data, and the model parameters were tested by the GMcal_TieLinesLL tool, which shows that the results meet the Gibbs stability criteria. The separation mechanism was explored by analyzing σ-profile, deformation charge density, interaction energy, and RDG analysis.
{"title":"Separation of higher-rank phenols from coal tar models: a combination of experiment and mechanism analysis","authors":"Houchun Yan, He Ma, Xuqiang Li, Shaolong Dong, Qingsong Li","doi":"10.1016/j.jct.2025.107550","DOIUrl":"10.1016/j.jct.2025.107550","url":null,"abstract":"<div><div>To separate higher-rank phenols from the coal tar, the model oil was constructed, and the separation efficiency of various solvents was analyzed using solvent power, selectivity, and performance index. The liquid-liquid equilibrium data of cumene + {4-ethylphenol, 4-propylphenol, 2-allylphenol, and 2-isopropylphenol} + ethanolamine was measured at 298.2 K and 101.3 kPa, and the distribution coefficient and separation factor were calculated. Furthermore, the NRTL and UNIQUAC models were correlated with the LLE data, and the model parameters were tested by the GMcal_TieLinesLL tool, which shows that the results meet the Gibbs stability criteria. The separation mechanism was explored by analyzing σ-profile, deformation charge density, interaction energy, and RDG analysis.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107550"},"PeriodicalIF":2.2,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144713685","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}
Pub Date : 2025-07-18DOI: 10.1016/j.jct.2025.107547
Na Di, Yu Liu, Chao Liu
Octamethyltrisiloxane (MDM)/Decamethyltetrasiloxane (MD2M) mixtures are considered one of the most suitable working fluids for high temperature Organic Rankine Cycle (ORC) systems and heat pump. As a critical thermophysical property, thermal conductivities of liquid siloxanes are important to understand heat transfer characteristics. In this study, thermal conductivities of MDM/MD2M mixtures (with MDM mass fraction wMDM = 0, 0.30, 0.50, 0.70, 1.00) were measured using a transient hot-wire method over a temperature range of 263.15–343.15 K and pressures up to 8 MPa. Then, an empirical model was proposed to reproduce the thermal conductivity regarding temperature and pressure, yielding an average absolute deviation of less than 1 %. In addition, the thermal conductivities of the MDM/MD2M systems were studied using the non-equilibrium molecular dynamics (NEMD) simulation. The predicted values show good consistency with the experimental results, confirming both the accuracy of the established model and the suitability of the selected force field, while offering a dependable computational method for predicting thermal conductivity. This work provides essential data and theoretical support for evaluating the heat transfer performance and selecting working fluids in MDM/MD2M-based ORC systems.
{"title":"Experimental and molecular dynamics study on the thermal conductivity of Octamethyltrisiloxane (MDM)/Decamethyltetrasiloxane (MD2M) mixtures","authors":"Na Di, Yu Liu, Chao Liu","doi":"10.1016/j.jct.2025.107547","DOIUrl":"10.1016/j.jct.2025.107547","url":null,"abstract":"<div><div>Octamethyltrisiloxane (MDM)/Decamethyltetrasiloxane (MD<sub>2</sub>M) mixtures are considered one of the most suitable working fluids for high temperature Organic Rankine Cycle (ORC) systems and heat pump. As a critical thermophysical property, thermal conductivities of liquid siloxanes are important to understand heat transfer characteristics. In this study, thermal conductivities of MDM/MD<sub>2</sub>M mixtures (with MDM mass fraction <em>w</em><sub>MDM</sub> = 0, 0.30, 0.50, 0.70, 1.00) were measured using a transient hot-wire method over a temperature range of 263.15–343.15 K and pressures up to 8 MPa. Then, an empirical model was proposed to reproduce the thermal conductivity regarding temperature and pressure, yielding an average absolute deviation of less than 1 %. In addition, the thermal conductivities of the MDM/MD<sub>2</sub>M systems were studied using the non-equilibrium molecular dynamics (NEMD) simulation. The predicted values show good consistency with the experimental results, confirming both the accuracy of the established model and the suitability of the selected force field, while offering a dependable computational method for predicting thermal conductivity. This work provides essential data and theoretical support for evaluating the heat transfer performance and selecting working fluids in MDM/MD<sub>2</sub>M-based ORC systems.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107547"},"PeriodicalIF":2.2,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144679391","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}
Pub Date : 2025-07-17DOI: 10.1016/j.jct.2025.107546
Maxwell Risseli Laurentino da Silva, Alanderson Arthu Araújo Alves, Lucas Henrique Gomes de Medeiros, Hugo Andersson Dantas Medeiros, Hosiberto Batista de Sant'Ana, Filipe Xavier Feitosa
The phase equilibria of two hexadecane + butylcyclohexane mixtures were investigated by adding carbon dioxide, for which no data are available in the literature, using a variable-volume high-pressure view cell. Five isopleths ranging from 13 to 85 mol% carbon dioxide were studied at five different temperature conditions. In addition, high-pressure density data were obtained for three different hexadecane + butylcyclohexane mixtures at five temperatures and pressures up to 100 MPa. The classical Peng-Robinson equation of state (PR EoS) was applied with a fully predictive mixing rule incorporating a temperature-dependent binary interaction parameter () to model the experimentally measured phase equilibria. The two ternary mixtures exhibited classical behavior across all global compositions investigated, presenting only simple liquid-vapor equilibrium. The PR EoS approach qualitatively captured the experimental phase behavior of both systems. Moreover, the experimental density data were correlated using the Tammann–Tait equation, and the following thermodynamic derivative properties were calculated: isothermal compressibility (), isobaric thermal expansivity (, thermal pressure coefficient (), and internal pressure ().
{"title":"High-pressure phase equilibria and volumetric properties of the CO2 + hexadecane + butylcyclohexane system: Experimental and modeling study","authors":"Maxwell Risseli Laurentino da Silva, Alanderson Arthu Araújo Alves, Lucas Henrique Gomes de Medeiros, Hugo Andersson Dantas Medeiros, Hosiberto Batista de Sant'Ana, Filipe Xavier Feitosa","doi":"10.1016/j.jct.2025.107546","DOIUrl":"10.1016/j.jct.2025.107546","url":null,"abstract":"<div><div>The phase equilibria of two hexadecane + butylcyclohexane mixtures were investigated by adding carbon dioxide, for which no data are available in the literature, using a variable-volume high-pressure view cell. Five isopleths ranging from 13 to 85 mol% carbon dioxide were studied at five different temperature conditions. In addition, high-pressure density data were obtained for three different hexadecane + butylcyclohexane mixtures at five temperatures and pressures up to 100 MPa. The classical Peng-Robinson equation of state (PR EoS) was applied with a fully predictive mixing rule incorporating a temperature-dependent binary interaction parameter (<span><math><mrow><msub><mi>k</mi><mi>ij</mi></msub></mrow></math></span>) to model the experimentally measured phase equilibria. The two ternary mixtures exhibited classical behavior across all global compositions investigated, presenting only simple liquid-vapor equilibrium. The PR EoS approach qualitatively captured the experimental phase behavior of both systems. Moreover, the experimental density data were correlated using the Tammann–Tait equation, and the following thermodynamic derivative properties were calculated: isothermal compressibility (<span><math><mrow><msub><mi>κ</mi><mi>T</mi></msub></mrow></math></span><em>)</em>, isobaric thermal expansivity (<span><math><mrow><msub><mi>α</mi><mi>P</mi></msub><mo>)</mo></mrow></math></span>, thermal pressure coefficient (<span><math><mrow><msub><mi>γ</mi><mi>v</mi></msub></mrow></math></span>), and internal pressure (<span><math><mrow><msub><mi>P</mi><mi>i</mi></msub></mrow></math></span>).</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107546"},"PeriodicalIF":2.2,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144672174","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}
Pub Date : 2025-07-10DOI: 10.1016/j.jct.2025.107545
Aarthi Sai Meghana Munnangi , Hara Krishna Reddy Koppolu , Sk Md Nayeem , Prathap Koppolu , Srinivasa Reddy Munnangi
Binary solvent mixtures are increasingly significant due to their ability to enhance reaction rates, modify solubility, and optimize technological separation processes. Among such mixtures, γ-butyrolactone (GBL) and dimethylformamide (DMF) are noteworthy for their versatility in various applicative fields, including pharmaceuticals, coatings, and adhesives. This study integrates experimental methods with molecular dynamics simulations and machine learning techniques to investigate the physicochemical properties and intermolecular interactions of the GBL-DMF binary system across different temperatures and compositions. The measured densities (ρ), speeds of sound (u), and refractive indices (nD) of the binary mixtures were used to calculate excess molar volume (), excess isentropic compressibility (), and refractive index deviations (), which together give an overview of how the molecules interact with each other, suggesting the presence of strong molecular interactions such as hydrogen bonding and dipole-dipole forces. These observations are further corroborated by molecular dynamics simulations, which align well with the experimental data. Additionally, machine learning algorithms, including Random Forest, Gradient Boosting, XGBoost, and H2O AutoML, were employed to predict density. Among these, H2O AutoML demonstrated superior precision with an R2 value of 0.984. This multifaceted approach, combining experimental, computational, and predictive methodologies, offers valuable insights into the design of solvent systems for industrial applications and supports sustainable development efforts.
{"title":"Experimental and molecular dynamics study of molecular interactions in γ-butyrolactone – dimethyl formamide systems with machine learning based density predictions","authors":"Aarthi Sai Meghana Munnangi , Hara Krishna Reddy Koppolu , Sk Md Nayeem , Prathap Koppolu , Srinivasa Reddy Munnangi","doi":"10.1016/j.jct.2025.107545","DOIUrl":"10.1016/j.jct.2025.107545","url":null,"abstract":"<div><div>Binary solvent mixtures are increasingly significant due to their ability to enhance reaction rates, modify solubility, and optimize technological separation processes. Among such mixtures, γ-butyrolactone (GBL) and dimethylformamide (DMF) are noteworthy for their versatility in various applicative fields, including pharmaceuticals, coatings, and adhesives. This study integrates experimental methods with molecular dynamics simulations and machine learning techniques to investigate the physicochemical properties and intermolecular interactions of the GBL-DMF binary system across different temperatures and compositions. The measured densities (<em>ρ</em>), speeds of sound (<em>u</em>), and refractive indices (<em>n</em><sub>D</sub>) of the binary mixtures were used to calculate excess molar volume (<span><math><msubsup><mi>V</mi><mi>m</mi><mi>E</mi></msubsup></math></span>), excess isentropic compressibility (<span><math><msubsup><mi>κ</mi><mi>s</mi><mi>E</mi></msubsup></math></span>), and refractive index deviations (<span><math><msub><mo>∆</mo><mo>∅</mo></msub><msub><mi>n</mi><mi>D</mi></msub></math></span>), which together give an overview of how the molecules interact with each other, suggesting the presence of strong molecular interactions such as hydrogen bonding and dipole-dipole forces. These observations are further corroborated by molecular dynamics simulations, which align well with the experimental data. Additionally, machine learning algorithms, including Random Forest, Gradient Boosting, XGBoost, and H2O AutoML, were employed to predict density. Among these, H2O AutoML demonstrated superior precision with an R<sup>2</sup> value of 0.984. This multifaceted approach, combining experimental, computational, and predictive methodologies, offers valuable insights into the design of solvent systems for industrial applications and supports sustainable development efforts.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"210 ","pages":"Article 107545"},"PeriodicalIF":2.2,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144656268","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}
In this study, we explored the thermophysical properties of a mixture composed of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][NTf2]) ionic liquid (IL) and the organic solvent 2-ethoxyethanol (2-EE). We meticulously measured the density, speed of sound, and refractive index across the full range of mixture compositions at temperatures of 298.15, 303.15, 308.15, 313.15, and 318.15 K under atmospheric pressure. Additionally, we calculated various excess parameters, such as excess molar volume, excess isentropic compressibility, excess isobaric thermal expansion coefficient, deviation in refractive index, and partial molar quantities, based on our experimental data. These parameters were then analyzed using the Redlich-Kister polynomial equation to understand the mixture's behavior better. Our findings revealed strong attractive forces within the IL-rich areas of the [Emim][NTf2] and 2-EE binary mixture, indicating significant intermolecular interactions. The strength and nature of these interactions were further supported and illuminated through ATR-FTIR and Molecular Dynamics (MD) simulation studies, providing a comprehensive insight into the molecular dynamics within these mixtures.
{"title":"Exploring molecular interactions through thermophysical properties and molecular dynamics simulations in [Emim][NTf2] and 2-EE mixtures","authors":"Nagarjuna Babu Etukuri , Sreenivasa Rao Aangothu , Sowjanya Prathipati , Srinivasa Reddy Munnangi , Bala Murali Krishna Khandapu , J.N. Pavan Kumar Chintala , Hari Babu Bollikolla","doi":"10.1016/j.jct.2025.107536","DOIUrl":"10.1016/j.jct.2025.107536","url":null,"abstract":"<div><div>In this study, we explored the thermophysical properties of a mixture composed of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][NTf<sub>2</sub>]) ionic liquid (IL) and the organic solvent 2-ethoxyethanol (2-EE). We meticulously measured the density, speed of sound, and refractive index across the full range of mixture compositions at temperatures of 298.15, 303.15, 308.15, 313.15, and 318.15 K under atmospheric pressure. Additionally, we calculated various excess parameters, such as excess molar volume, excess isentropic compressibility, excess isobaric thermal expansion coefficient, deviation in refractive index, and partial molar quantities, based on our experimental data. These parameters were then analyzed using the Redlich-Kister polynomial equation to understand the mixture's behavior better. Our findings revealed strong attractive forces within the IL-rich areas of the [Emim][NTf<sub>2</sub>] and 2-EE binary mixture, indicating significant intermolecular interactions. The strength and nature of these interactions were further supported and illuminated through ATR-FTIR and Molecular Dynamics (MD) simulation studies, providing a comprehensive insight into the molecular dynamics within these mixtures.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"210 ","pages":"Article 107536"},"PeriodicalIF":2.2,"publicationDate":"2025-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144596390","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}
Densities, speeds of sound and viscosities for the binary liquid mixtures containing Triethylamine with 1-propanol, 1-butanol and 1-pentanol are reported in this article. Densities and speeds of sound were measured at (293.15, 298.15, 303.15 and 308.15) K and 0.1 MPa over the entire range of compositions. Viscosities were measured at (298.15, 303.15 and 308.15) K and 0.1 MPa over whole composition range. The measured data were processed to obtain a number of thermodynamic parameters viz. excess molar volume (), excess isentropic compressibility (), deviation in speed of sound (uD), deviation in viscosity (Δη), excess Gibb’s free energy of activation for viscous flow (). The parameters were analyzed in the light of intermolecular interactions and various effects on these. Spectroscopic investigations (FTIR) were performed to get more information about happenings at molecular level and to find more support for the results. The computed data along with experimental data were also correlated to compositions using Redlich-Kister type polynomial and Jouyben-Acree model respectively. Some existing models of viscosity (Gurunberg-Nissan model, Tamura-Kurata model, Hind-McLaughlin et al. model, Katti-Chaudhri model, McAllister’s three-body interaction model, Heric-Brewer three-parameters model, McAllister’s four-body interaction model) were tested for their application to studied mixtures.
{"title":"Volumetric, acoustic, viscometric and spectroscopic studies of binary liquid mixtures containing triethylamine with 1-propanol, 1-butanol and 1-pentanol","authors":"Seema Rani , Gyan Prakash Dubey , Suvercha Chauhan , Prabjot Kaur","doi":"10.1016/j.jct.2025.107532","DOIUrl":"10.1016/j.jct.2025.107532","url":null,"abstract":"<div><div>Densities, speeds of sound and viscosities for the binary liquid mixtures containing Triethylamine with 1-propanol, 1-butanol and 1-pentanol are reported in this article. Densities and speeds of sound were measured at (293.15, 298.15, 303.15 and 308.15) K and 0.1 MPa over the entire range of compositions. Viscosities were measured at (298.15, 303.15 and 308.15) K and 0.1 MPa over whole composition range. The measured data were processed to obtain a number of thermodynamic parameters viz. excess molar volume (<span><math><msubsup><mi>V</mi><mi>m</mi><mi>E</mi></msubsup></math></span>), excess isentropic compressibility (<span><math><msubsup><mi>κ</mi><mi>S</mi><mi>E</mi></msubsup></math></span>), deviation in speed of sound (<em>u</em><sup><em>D</em></sup>), deviation in viscosity (<em>Δη</em>), excess Gibb’s free energy of activation for viscous flow (<span><math><mo>∆</mo><msup><mi>G</mi><mrow><mo>∗</mo><mi>E</mi></mrow></msup></math></span>). The parameters were analyzed in the light of intermolecular interactions and various effects on these. Spectroscopic investigations (FTIR) were performed to get more information about happenings at molecular level and to find more support for the results. The computed data along with experimental data were also correlated to compositions using Redlich-Kister type polynomial and Jouyben-Acree model respectively. Some existing models of viscosity (Gurunberg-Nissan model, Tamura-Kurata model, Hind-McLaughlin et al. model, Katti-Chaudhri model, McAllister’s three-body interaction model, Heric-Brewer three-parameters model, McAllister’s four-body interaction model) were tested for their application to studied mixtures.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"210 ","pages":"Article 107532"},"PeriodicalIF":2.2,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144366497","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}
Pub Date : 2025-06-16DOI: 10.1016/j.jct.2025.107535
Manale El Bachtioui , Ilham Abala , Mohamed Lifi , Mohamed Dakkach , Mohamed Allouch , Fernando Aguilar
New experimental data on density (), dynamic and kinematic viscosities, for the following ternary mixtures: 2-butanol (Belale and F.E. M'hamdi Alaoui, M. Lifi, Y.Chhiti, M. Elkhouakhi, L., 2020 (1)) + isopropyl ether (Alaoui et al., 2015 (2)) + 1-hexene (Abala and Lifi, 2021 (3)) and 2-propanol (Belale and F.E. M'hamdi Alaoui, M. Lifi, Y.Chhiti, M. Elkhouakhi, L., 2020 (1)) + isopropyl ether (Alaoui et al., 2015 (2)) + 1-hexene (Abala and Lifi, 2021 (3)) are presented in this work at four temperatures between 298.15 and 313.15 K and = 0.1 MPa. Additionally, the speed of sound () and refractive index () for the same ternary mixtures were measured at 298.15 K and 313.15 K. Various derived properties were calculated from the experimental results of these thermophysical properties, including excess volume, deviation in refractive index, , deviation in dynamic viscosity, deviations in speed of sound, isentropic compressibility, and deviation in isentropic compressibility, The Redlich-Kister equation and the typical semi-empirical Cibulka equations were used to correlate all of these derived properties. Moreover, the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) equation of state was employed to fit the experimental density data, and good agreement between the experimental and modeled density results for the binary mixtures studied.
下列三元混合物的密度（ρ），动态和运动粘度，ημ的新实验数据：2-丁醇（Belale和F.E. M'hamdi Alaoui， M. Lifi， Y.Chhiti， M. Elkhouakhi， L., 2020(1)） +异丙基醚（Alaoui等，2015(2)）+ 1-己烯（Abala和Lifi， 2021(3)）和2-丙醇（Belale和F.E. M'hamdi Alaoui， M. Lifi， Y.Chhiti， M. Elkhouakhi， L., 2020(1)） +异丙基醚（Alaoui等，2015(2)）+ 1-己烯（Abala和Lifi， 2021(3)）在298.15至313.15 K和p = 0.1 MPa之间的四种温度下进行了研究。此外，在298.15 K和313.15 K下测量了相同三元混合物的声速(u)和折射率（nD）。根据这些热物理性质的实验结果计算了各种衍生性质，包括多余体积，VE，折射率偏差，∆nD，动态粘度偏差，∆η，声速偏差，∆u，等熵可压缩性，ks和等熵可压缩性偏差，∆ks。Redlich-Kister方程和典型的半经验Cibulka方程被用来关联所有这些导出的性质。采用微扰链统计关联流体理论（PC-SAFT）状态方程对实验密度数据进行拟合，实验结果与模型结果吻合较好。
{"title":"Measurement, correlation, and modeling of volumetric, viscosimetric, acoustic, and optical properties in ternary mixtures of alcohols, ethers, and hydrocarbons between 298.15 and 313.15 K","authors":"Manale El Bachtioui , Ilham Abala , Mohamed Lifi , Mohamed Dakkach , Mohamed Allouch , Fernando Aguilar","doi":"10.1016/j.jct.2025.107535","DOIUrl":"10.1016/j.jct.2025.107535","url":null,"abstract":"<div><div>New experimental data on density (<span><math><mrow><mi>ρ</mi></mrow></math></span>), dynamic and kinematic viscosities, <span><math><mrow><mfenced><mi>η</mi><mi>μ</mi></mfenced></mrow></math></span> for the following ternary mixtures: 2-butanol (Belale and F.E. M'hamdi Alaoui, M. Lifi, Y.Chhiti, M. Elkhouakhi, L., 2020 (1)) + isopropyl ether (Alaoui et al., 2015 (2)) + 1-hexene (Abala and Lifi, 2021 (3)) and 2-propanol (Belale and F.E. M'hamdi Alaoui, M. Lifi, Y.Chhiti, M. Elkhouakhi, L., 2020 (1)) + isopropyl ether (Alaoui et al., 2015 (2)) + 1-hexene (Abala and Lifi, 2021 (3)) are presented in this work at four temperatures between 298.15 and 313.15 K and <span><math><mrow><mi>p</mi></mrow></math></span> = 0.1 MPa. Additionally, the speed of sound (<span><math><mrow><mi>u</mi></mrow></math></span>) and refractive index (<span><math><mrow><msub><mi>n</mi><mi>D</mi></msub></mrow></math></span>) for the same ternary mixtures were measured at 298.15 K and 313.15 K. Various derived properties were calculated from the experimental results of these thermophysical properties, including excess volume, <span><math><mrow><msup><mi>V</mi><mi>E</mi></msup><mo>,</mo></mrow></math></span> deviation in refractive index, <span><math><mrow><mo>∆</mo><msub><mi>n</mi><mi>D</mi></msub></mrow></math></span>, deviation in dynamic viscosity, <span><math><mrow><mo>∆</mo><mi>η</mi><mo>,</mo></mrow></math></span> deviations in speed of sound, <span><math><mrow><mo>∆</mo><mi>u</mi><mo>,</mo></mrow></math></span> isentropic compressibility, <span><math><mrow><msub><mi>k</mi><mi>s</mi></msub><mo>,</mo></mrow></math></span> and deviation in isentropic compressibility, <span><math><mrow><mo>∆</mo><msub><mi>k</mi><mi>s</mi></msub><mo>.</mo></mrow></math></span> The Redlich-Kister equation and the typical semi-empirical Cibulka equations were used to correlate all of these derived properties. Moreover, the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) equation of state was employed to fit the experimental density data, and good agreement between the experimental and modeled density results for the binary mixtures studied.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"210 ","pages":"Article 107535"},"PeriodicalIF":2.2,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144306992","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}
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