Journal of Chemical Thermodynamics最新文献

{"title":"Thermodynamics of hydroxylbastnaesite","authors":"G.A. Agbanga ,&nbsp;M. Scharrer ,&nbsp;C.G. White ,&nbsp;B.F. Woodfield ,&nbsp;A. Navrotsky","doi":"10.1016/j.jct.2025.107529","DOIUrl":"10.1016/j.jct.2025.107529","url":null,"abstract":"<div><div>The mineral bastnaesite, REECO₃[F, OH] (REE = rare earth elements), is a major source of rare earth elements and can be found in commercial deposits such as Mountain Pass, California, and Bayan Obo, China. In addition, its natural and synthetic forms have been explored for applications in optical devices, phosphors, batteries, ceramics, and magnets, accounting for 41 % of the world's consumption of rare earth elements. Therefore, investigating and analyzing thermodynamic properties of REE minerals are crucial for understanding origin, improving extraction processes, and optimizing industrial applications. This study presents a detailed reevaluation of structural and thermodynamic properties of well-characterized synthetic hydroxyl bastnaesite compounds: LaCO₃OH, PrCO₃OH, NdCO₃OH, SmCO₃OH, and EuCO₃OH. Their standard enthalpies of formation (ΔH⁰_f) were determined by high temperature oxide melt solution calorimetry and standard entropy (S⁰) was obtained from low temperature heat capacity (c_p) measurement from 1.8 to 300 K, extrapolated to 600 K combined the Einstein and Debye models. These allowed calculation of the Gibbs energy of formation (ΔG⁰_f). Extrapolation of thermodynamic properties to the heavy REEs by relation to the ionic radius of the REE³⁺ cation and to higher temperatures using the experimental c_p fit provides stability constraints for hydroxylcarbonates allowing for modelling REE-H₂O-CO₂ systems.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"209 ","pages":"Article 107529"},"PeriodicalIF":2.2,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144231766","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 and correlation of liquid-liquid equilibrium data for separation of cyclohexane + isopropyl alcohol systems with different extractants","authors":"Fangfang Dai,&nbsp;Meiyuan Peng,&nbsp;Chen Wang,&nbsp;Kang Zhang","doi":"10.1016/j.jct.2025.107525","DOIUrl":"10.1016/j.jct.2025.107525","url":null,"abstract":"<div><div>In this work, ethylene glycol (EG), formamide, and 1, 2-propanediol were identified as potential extractants for separating cyclohexane + isopropanol (IPA) azeotropic system. The σ-profile was analyzed using the Dmol³ module of Materials Studio, and the interaction energy between the components was calculated, indicating that EG is the most promising extractant. The liquid-liquid equilibrium (LLE) data for the cyclohexane + IPA + extractants system were measured at 303.15 K, 313.15 K and 323.15 K. When the temperature increases, the extraction capacities of EG and formamide decrease. Meanwhile, the temperature has less impact on the capacity of 1, 2-propanediol. EG has higher value of the distribution coefficient (D) and separation factor (S), indicating its superior effectiveness for separation. Othmer-Tobias and Hand equations were used to estimate the reliability and consistency of the LLE data. The nonrandom two-liquid (NRTL) and universal quasi-chemical (UNIQUAC) thermodynamic model in Aspen Plus 11 software were used to regress the LLE data, and the binary interaction parameters were calculated. The root mean square deviation (RMSD) values were all less than 0.02, indicating that the NRTL and UNIQUAC models can correlate experimental data well. Finally, the regressed binary interaction parameters were further validated using GUI-MATLAB software, confirming the reliability of the data regression.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"209 ","pages":"Article 107525"},"PeriodicalIF":2.2,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144271428","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":"Volumetric, FT-IR, and optical properties of 2–amino-1-butanol with isomeric butanol at 298.15 K–318.15 K using PFP theory and graph theoretical approach","authors":"Sweety Verma ,&nbsp;Kavitha Kumari ,&nbsp;Suman Gahlyan ,&nbsp;Ji Hoon Kim ,&nbsp;Juwon Min ,&nbsp;Sanjeev Maken","doi":"10.1016/j.jct.2025.107524","DOIUrl":"10.1016/j.jct.2025.107524","url":null,"abstract":"<div><div>The density and optical properties of binary mixtures containing 2–amino 1–butanol (2AB) and isomeric butanol were measured over a temperature range (298.15–318.15) K and 0.1 MPa pressure. Using these measurements, excess molar volume (<span><math><msup><msub><mi>V</mi><mi>m</mi></msub><mi>E</mi></msup></math></span>) and deviation in refractive index (<span><math><mi>Δ</mi><msub><mi>n</mi><mi>D</mi></msub></math></span>) were computed. The negative <span><math><msup><msub><mi>V</mi><mi>m</mi></msub><mi>E</mi></msup></math></span>values, at equimolar composition, follow the order: tert-butanol &gt; sec-butanol &gt; isobutanol &gt; n-butanol, while the <span><math><mi>Δ</mi><msub><mi>n</mi><mi>D</mi></msub></math></span> exhibit the opposite trend. The Prigogine–Flory–Patterson theory and the Graph theoretical approach were applied to interpret the <span><math><msup><msub><mi>V</mi><mi>m</mi></msub><mi>E</mi></msup></math></span> data at 298.15 K, respectively. Moreover, the molecular species of various components are predicted to exist in both pure and mixed states by the GTA. Furthermore, FT–IR spectroscopy confirmed the formation of hydrogen bonding between the molecules of the components. The <span><math><msup><msub><mi>V</mi><mi>m</mi></msub><mi>E</mi></msup></math></span> values decrease with increasing temperature, while the <span><math><mi>Δ</mi><msub><mi>n</mi><mi>D</mi></msub></math></span> values increase with increasing temperature. Various mixing rules were applied to calculate <span><math><msub><mi>n</mi><mi>D</mi></msub></math></span> theoretically. This study aims to expand the database of thermophysical properties for amine-alcohol mixtures, providing a reference for engineers and scientists developing advanced CO₂ capture technologies.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"209 ","pages":"Article 107524"},"PeriodicalIF":2.2,"publicationDate":"2025-05-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144212267","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":"A simplified method for enhanced accuracy in calculating adsorption thermodynamic parameters","authors":"Tijana Ivanović ,&nbsp;Tijana Tomović ,&nbsp;Daniela Popović ,&nbsp;Jelena Miladinović ,&nbsp;Mouad Arrad ,&nbsp;Zoran Miladinović","doi":"10.1016/j.jct.2025.107517","DOIUrl":"10.1016/j.jct.2025.107517","url":null,"abstract":"<div><div>This study investigates the thermodynamic parameters of phosphate adsorption on activated carbon using the Pitzer ion-interaction model. The adsorption data were analyzed using the Langmuir and Sips models, both providing satisfactory fits. Maximum adsorption (plateau) occurred at an equilibrium phosphate concentration of 60.8 mmol⋅ dm⁻³ (pH = 5.1), with an adsorption capacity of 7.03 mmol⋅g⁻¹. The Pitzer model was used to calculate the activity coefficient of phosphates, considering the influence of all ions in the solution on the adsorption plateau. The maximum degree of dissociation of H₂PO₄^-(aq) ions was determined to be <em>x</em>_d(2) = 0.0026, taking hydrolysis into account. The activity coefficient of KH₂PO₄ in the mixed solution {K₂HPO₄ + KH₂PO₄ + H₃PO₄}(aq) was found to be <em>γ</em>_± = 0.7788, while in a pure KH₂PO₄ solution at the same ionic strength corresponding to the plateau, it is <em>γ</em>_± = 0.7790. Given the minor difference in activity coefficient, the mixed solution could be approximated as a pure KH₂PO₄(aq) for thermodynamic analysis, which greatly simplified the calculations. The Gibbs free energy was Δ<em>G</em>_L <!--> = − 8.6200 ± 0.0004 (kJ⋅mol⁻¹) using the Langmuir equilibrium constant shifting to Δ<em>G</em>_a = − 9.240 ± 0.006 (kJ⋅mol⁻¹) when accounting for activity coefficient and the thermodynamic equilibrium constant. With the Sips model, the Gibbs free energy was Δ<em>G</em>_<em>S</em> <!--> = − 9.620 ± 0.004 (kJ⋅mol⁻¹) and further refinement using phosphate activity coefficient gave Δ<em>G</em>_a <!--> = −10.235 ± 0.007 (kJ⋅mol⁻¹). The absolute differences in adsorption energy were approximately 7 % (Langmuir) and 6 % (Sips), highlighting the importance of considering ionic activities.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"208 ","pages":"Article 107517"},"PeriodicalIF":2.2,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144138152","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":"Impact of viscosity index modifiers with different architectures and functionalities on the thermophysical properties and viscosity of a mineral base oil","authors":"Katrina Avery ,&nbsp;Melanie Lindblom ,&nbsp;Liza Peoples ,&nbsp;Erdogan Kiran ,&nbsp;Mark T. Devlin","doi":"10.1016/j.jct.2025.107516","DOIUrl":"10.1016/j.jct.2025.107516","url":null,"abstract":"<div><div>This study examines the influence of viscosity index modifiers on the high-pressure and temperature thermophysical and rheological properties of a mineral base oil, Ultra S4. The viscosity index modifiers tested included polymethacrylates, ethylene-propylene block copolymers and star-styrene butadiene copolymers. Densities were determined at pressures in the range of 10–35 MPa and at 298, 323, 348, 373, and 398 K using a high-pressure variable-volume view-cell. The density data were then correlated with the Sanchez-Lacombe Equation of State from which the thermodynamic properties of isothermal compressibility, isobaric expansivity and internal pressure were derived. Viscosities were determined at pressures in the range of 10–45 MPa and at 298, 323, 348 and 373 K using a uniquely designed high-pressure rotational viscometer. High pressure density and viscosity results were correlated with free volume and density-scaling equations to provide further insight into molecular packing and interactions. Additionally, intrinsic viscosity measurements were performed to evaluate the semi-dilute regime and the radius of gyration at 30 °C and 50 °C.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"210 ","pages":"Article 107516"},"PeriodicalIF":2.2,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144298567","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":"Revealing the dissolution behavior of letrozole (form I) in four binary solvent systems: Solubility determination, thermodynamic analysis and molecular simulations","authors":"Yadi Bai,&nbsp;Chong Wang,&nbsp;Fukang Song,&nbsp;Yu Li,&nbsp;Tao Li,&nbsp;Lingbo Qu,&nbsp;Baozeng Ren","doi":"10.1016/j.jct.2025.107515","DOIUrl":"10.1016/j.jct.2025.107515","url":null,"abstract":"<div><div>Letrozole is a new aromatase inhibitor with extremely selective, which is widely used in the treatment of advanced postmenopausal breast cancer. This study focused on measuring the solubility of letrozole (form I) in four binary solvent systems (methanol + water, acetone + water, acetonitrile + water, methyl acetate + n-hexane) by the laser dynamic method at 0.1 MPa. The measured temperature ranged between 273.15 K and 323.15 K. It can be observed that when the composition of the binary solvents is constant, the solubility has a positive correlation with temperature. For methanol + water, acetone + water and methyl acetate + n-hexane binary solvent systems, a higher mass fraction of the positive solvent leads to an improvement in solubility. However, in the binary solvent system of acetonitrile + water, the co-solvency phenomena were detected. Five different models were applied to correlate the solubility data. The modified Apelblat equation demonstrated the most accurate fitting performance. The investigation of the Hirshfeld surface uncovered the intermolecular interactions in molecular crystals. For the sake of simulations, the electrostatic potentials (ESP) of the solvent and solute molecules were analyzed. The interactions between solute and solvent, as well as between the solvent and solvent, are crucial in determining the dissolution behavior, as demonstrated by the radial distribution function (RDF) analysis. The calculation of solvation free energy provides us a better insight into the dissolving characteristics of letrozole (form I). Furthermore, the apparent thermodynamic properties of the dissolution process of letrozole (form I) in four binary solvent systems were calculated, which indicates that the dissolution process is entropy-increasing and endothermic. Simple crystallization experiments were carried out, suggesting that acetone + water mixed solvent is the suitable solvent for letrozole anti-solvent crystallization. In summary, fundamental thermodynamic data for the design and optimization of the crystallization processes can be obtained from this study.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"209 ","pages":"Article 107515"},"PeriodicalIF":2.2,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144231097","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":"Quaternary and its sub-ternary systems of 4-formylbenzoic acid + p-toluic acid + p-phthalic acid + N,N-dimethylformamide: Phase diagrams and DFT studies on adduct of p-phthalic acid with N,N-dimethylformamide","authors":"Min Zheng ,&nbsp;Hongkun Zhao","doi":"10.1016/j.jct.2025.107514","DOIUrl":"10.1016/j.jct.2025.107514","url":null,"abstract":"<div><div>The equilibrated solubility of the three systems <em>p</em>-phthalic acid (PTA) + <em>p</em>-toluic acid (<em>p</em>-TLA) + <em>N,N</em>-dimethylformamide (DMF), PTA + 4-formylbenzoic acid (4-FBA) + DMF, and <em>p</em>-TLA + 4-FBA + DMF at 298.15 K, 323.15 K and 353.15 K, as well as the quaternary system PTA + <em>p</em>-TLA + 4-FBA + DMF at 298.15 K, was ascertained through experimentation by a Schreinemakers' wet residue method under <em>p</em> = 101.0 kPa. One quaternary isothermal phase diagram and nine ternary isothermal phase diagrams were developed based on the solubility obtained herein. Two distinct neat compounds were produced in ternary systems, comprising the PTA·2DMF adduct (mole ratio of PTA to DMF, 1:2) at 323.15 K and 298.15 K, or PTA at a temperature of 353.15 K, along with <em>p</em>-TLA in the PTA + <em>p</em>-TLA + DMF system; 4-FBA and <em>p</em>-TLA in the 4-FBA + <em>p</em>-TLA + DMF system; and the PTA·2DMF adduct at 298.15 K and 323.15 K, or PTA at 353.15 K, combined with 4-FBA in the PTA + 4-FBA + DMF system. The adduct PTA·2DMF was observed at temperatures below 323.15 K for PTA in DMF. Each diagram for ternary systems comprised two cosaturated point curves, one cosaturated point, and three crystalline regions. The ternary and quaternary phase diagrams presented in this study may serve as a foundation for the separation of PTA from <em>p</em>-TLA, 4-FBA, and PTA mixtures. The formation of the PTAˑ2DMF adduct involves favorable weak interactions, specifically hydrogen bonds and van der Waals forces, as analyzed through the Hirshfeld partitions-based independent gradient model, electron density difference maps, density differences, ELF difference maps, and 2D fingerprint plot analysis.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"208 ","pages":"Article 107514"},"PeriodicalIF":2.2,"publicationDate":"2025-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144089731","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":"Equilibrium solubilities, model analysis, solvent effect, and thermodynamic properties of 5-amino-1,3,4-thiadiazole-2-thiol in thirteen organic mono-solvents","authors":"Maoyuan Liu ,&nbsp;Chenru Pei ,&nbsp;Liwen Wu ,&nbsp;Yaqi Han ,&nbsp;Yifan Zhang ,&nbsp;Wenguo Xing ,&nbsp;Shuai Yu ,&nbsp;Fumin Xue","doi":"10.1016/j.jct.2025.107513","DOIUrl":"10.1016/j.jct.2025.107513","url":null,"abstract":"<div><div>The solubility of 5-Amino-1,3,4-thiadiazole-2-thiol (AMTD) in 13 kinds of mono- solvents (including methanol, ethanol, <em>n</em>-propanol, <em>i</em>-propanol, <em>n</em>-butanol, <em>i</em>-butanol, <em>s</em>-butanol, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetone and cyclohexanone) were measured by a gravimetric method at different temperatures. The solubility of AMTD in different solvents increases with the increase of temperature. AMTD solubility sequence in the alcohol solvent is: methanol &gt; ethanol &gt; <em>s</em>-butanol &gt; <em>i</em>-propanol &gt; <em>n</em>-propanol &gt; <em>n</em>-butanol &gt; <em>i</em>-butanol. In the ester reagent, the solubility order is: methyl acetate &gt; ethyl acetate &gt; propyl acetate &gt; butyl acetate. In keto solvents, AMTD is more soluble. The solubility data were fitted with the modified Apelblat model, Yaws model, and van't Hoff model. <em>RAD</em> and <em>RMSD</em> are all less than 0.86 × 10⁻² and 9.84 × 10⁻³, respectively. Hansen solubility parameters and KAT-LSER model were used to study the solute-solvent interaction and solvent effect. Hirshfeld surface analysis and molecular electrostatic potential surface analysis were selected to investigate the intermolecular interactions of solute and solvent. The thermodynamic data of AMTD dissolution process were calculated according to the van't Hoff model.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"208 ","pages":"Article 107513"},"PeriodicalIF":2.2,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143947433","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":"Accurate density measurements of CO2 at the vicinity of the critical point by a single-sinker densimeter","authors":"Kang Qing ,&nbsp;Liu Xu ,&nbsp;Erqi Wang ,&nbsp;Zhen Yang ,&nbsp;Zhe Wang ,&nbsp;Xiaoxian Yang ,&nbsp;Yuanyuan Duan","doi":"10.1016/j.jct.2025.107512","DOIUrl":"10.1016/j.jct.2025.107512","url":null,"abstract":"<div><div>This study presents a renovated single-sinker magnetic suspension densimeter system for density measurements at temperature from 298.15 to 423.15 K and pressure up to 35 MPa. The expanded uncertainties (<em>k</em> = 2) are 25 mK for temperature, 4 kPa for pressure, and 0.05 % for density. The system was first used to measure density of nitrogen at temperature from 308.15 to 423.15 K and pressure up to 20 MPa, yielding an average absolute relative deviation of 0.05 % compared to the reference multi-parameter equation of state (EoS) of Span and Wagner. Density of carbon dioxide was then measured mainly at the vicinity of the critical point, where the reference EoS deviates from data in literature. Vapor pressure and liquid density at saturated conditions were also determined. The new experimental data were compared to data from literature, the reference EoS of Span and Wagner and the crossover EoS with strict asymptotic singular behavior and critical exponent at critical point by Yang et al. The results shows that the new data generally yield good agreement with most of literature data, while both EoS underestimate density at the vicinity of the critical point. The EoS of Yang et al., as compared to EoS of Span and Wagner, provides a more accurate description of critical-point behavior while yielding similar accuracy in density and pressure calculation.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"208 ","pages":"Article 107512"},"PeriodicalIF":2.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143929054","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":"VLE of binary mixtures of tri-substituted imidazolium ionic liquids with ethanol or water: Experimental and molecular-level insights","authors":"Jingli Han ,&nbsp;Yu Cui ,&nbsp;Alexandra Elena Plesu Popescu ,&nbsp;Jordi Bonet Ruiz ,&nbsp;Joan Llorens Llacuna","doi":"10.1016/j.jct.2025.107504","DOIUrl":"10.1016/j.jct.2025.107504","url":null,"abstract":"<div><div>This study investigates the vapor-liquid equilibrium behavior of binary mixtures comprising tri-substituted imidazolium ionic liquids with either ethanol or water, combining experimental analysis with molecular-level insights. The ionic liquids used in this research are 1-ethyl-2,3-dimethylimidazolium bromide ([C₂MMIm][Br]) and 1-ethyl-2,3-dimethylimidazolium chloride ([C₂MMIm][Cl]). The investigation focuses on the effects of temperature, the type of ionic liquid, and the amount of ionic liquid added on the vapor pressure of these binary systems. The experimental data are fitted using the NRTL, Electrolyte NRTL and Wilson models to determine the binary interaction parameters. Furthermore, this study evaluates the influence of different ionic liquids on the vapor pressure of the binary systems to assess the strength of intermolecular interactions between the ionic liquids and ethanol or water. Molecular-level analyses, including surface charge density, dipole moment, and excess enthalpy, are conducted using the COSMO-RS model to explore the interactions between the ionic liquids and solvents, thereby providing theoretical insights into the phase equilibrium behavior. These investigations offer fundamental data essential for the engineering design and large-scale application of ionic liquid extractive distillation processes.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"208 ","pages":"Article 107504"},"PeriodicalIF":2.2,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898598","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}