Journal of Chemical Thermodynamics最新文献

{"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}

{"title":"Molecular interaction and esterase activity of bovine serum albumin with Pazopanib using multi-spectroscopic techniques and molecular docking","authors":"Ankita Jalan,&nbsp;Madhumita Patar,&nbsp;N. Shaemningwar Moyon","doi":"10.1016/j.jct.2025.107503","DOIUrl":"10.1016/j.jct.2025.107503","url":null,"abstract":"<div><div>This work delves into the binding dynamics of a promising anti-cancer drug Pazopanib (PZB) with bovine serum albumin (BSA), a mammalian plasma protein carrier with incredible ligand-binding properties. PZB is a tyrosine kinase inhibitor (TKI) used as a monotherapy against advanced renal cell carcinoma, soft tissue sarcoma, and liver fibrosis. Drug-albumin interactions vary with concentration, affecting drug efficacy and toxicity. Herein, we have investigated the binding mechanism of PZB with BSA at higher drug concentrations (5 × 10⁻⁶ mol/kg - 4 × 10⁻⁵ mol/kg) than albumin (3 × 10⁻⁶ mol/kg) using techniques like absorption, steady-state fluorescence, FRET, FT-IR, synchronous fluorescence, CD, and molecular docking. The intrinsic BSA fluorescence quenches with gradual increase in concentration of PZB via static quenching. The binding constant was found to be moderate (6.497 × 10⁴ mol ⁻¹.kg) and it has only one binding site. The Förster distance (<em>r</em>) indicated probable transfer of energy between the donor BSA and acceptor PZB. The major interacting forces are hydrophobic forces and hydrogen bonding. Conformational change in the protein framework was revealed from synchronous fluorescence, FT-IR, and CD studies. Competitive binding experiments as well as docking studies suggest that PZB binds to site I (subdomain IIA) of BSA. The increase in kinetic parameters reveals that the catalytic efficiency of BSA is enhanced on PZB interaction.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"208 ","pages":"Article 107503"},"PeriodicalIF":2.2,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888210","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 properties modeling of unsaturated solutions in the Li–Na–K–Cl–H2O system from 288.15 to 323.15 K and at 101.3 kPa using the Pitzer equations","authors":"Aldo N. Fuentes ,&nbsp;José D. Arriagada ,&nbsp;Yecid P. Jiménez ,&nbsp;Jesús M. Casas ,&nbsp;Francisca J. Justel","doi":"10.1016/j.jct.2025.107501","DOIUrl":"10.1016/j.jct.2025.107501","url":null,"abstract":"<div><div>This work presents a modeling approach to describe the volumetric properties of unsaturated solutions in the quaternary Li–Na–K–Cl–H₂O system from 288.15 to 323.15 K and at 101.3 kPa using the Pitzer equations. This system is a key component of the electrolytic environment found in brines extracted from the Salar de Atacama in Chile, which are used to produce lithium compounds.</div><div>The densities measured in this study, validated against data from the literature, showed trends consistent with changes in concentration and temperature, where KCl(aq) exerts the greatest influence on solution density.</div><div>New volumetric parameters for the LiCl – H₂O system at 323.15 K were obtained, and volumetric interaction coefficients in ternary mixtures were determined as a function of temperature, thereby expanding the existing database. The resulting standard deviations were low (below 1 %), demonstrating the model robustness in predicting volumetric properties for complex multi–component systems.</div><div>The volumes of mixing analysis revealed significant structural changes in these solutions: NaCl(aq) and LiCl(aq) act as structure breakers of water, while KCl(aq) exhibits dual behavior depending on the solution composition and total ionic strength. This information is valuable for understanding the structural nature of concentrated solutions and their impact on industrial processes to produce lithium compounds from brines.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107501"},"PeriodicalIF":2.2,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876518","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":"Freezing point depression in the binary NaVO3–H2O and NH4VO3–H2O Systems at p=0.1MPa","authors":"Mikael A.E. Manninen,&nbsp;Tuomas J. Vielma,&nbsp;Ulla M. Lassi","doi":"10.1016/j.jct.2025.107491","DOIUrl":"10.1016/j.jct.2025.107491","url":null,"abstract":"<div><div>The freezing point depressions in the <figure><img></figure> and <figure><img></figure> systems have been determined at <span><math><mrow><mi>p</mi><mo>=</mo><mn>0</mn><mo>.</mo><mn>1</mn><mspace></mspace><mstyle><mi>M</mi><mi>P</mi><mi>a</mi></mstyle></mrow></math></span> from molalities of ca. <span><math><mrow><mn>0</mn><mo>.</mo><mn>005</mn><mspace></mspace><msup><mrow><mstyle><mi>m</mi><mi>o</mi><mi>l</mi><mspace></mspace><mi>k</mi><mi>g</mi></mstyle></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></mrow></math></span> up to near saturation. The present data significantly expand the almost non-existent database of excess thermodynamic properties of binary <figure><img></figure> systems. The data could be explained within their experimental uncertainties by a thermodynamic model considering the association of the dihydrogenvanadate ion ( <figure><img></figure> ) to <figure><img></figure> and representing the excess Gibbs free energy (<span><math><msup><mrow><mi>G</mi></mrow><mrow><mi>Ex</mi></mrow></msup></math></span>) by the Pitzer equations with two adjustable parameters. The magnitudes of the determined parameters for the second virial coefficient of <figure><img></figure> - <figure><img></figure> interaction were typical for 4-1 electrolytes. The same model could describe also the data for the <figure><img></figure> system as even the saturated solution is sufficiently dilute that the contribution of short range interactions to <span><math><msup><mrow><mi>G</mi></mrow><mrow><mi>Ex</mi></mrow></msup></math></span> is small.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107491"},"PeriodicalIF":2.2,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143876517","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":"Thermodynamic studies of binary liquid mixtures of 2-(2-butoxyethoxy) ethanol with diisopropylamine, di-n-butylamine and tri-n-butylamine at 298.15, 303.15 and 308.15 K","authors":"Likhish Dhingra,&nbsp;Gyan Prakash Dubey","doi":"10.1016/j.jct.2025.107488","DOIUrl":"10.1016/j.jct.2025.107488","url":null,"abstract":"<div><div>Present discussion embodies the studies on binary mixtures containing 2-(2-butoxyethoxy) ethanol with secondary amines (diisopropylamine, di-n-butylamine) and tertiary amine (tri-n-butylamine).<em>ρ</em>, <em>u</em> and <em>η</em> of these binary mixtures were measured at temperatures <em>T</em> = 298.15, 303.15 and 308.15 K and at atmospheric pressure. Various excess, deviation and thermo acoustic parameters were calculated using the experimentally measured data. Results were investigated for type and ease of intermolecular interactions among unlike molecules in these mixtures. Presence of strong interactions among unlike molecules has been confirmed by the calculated parameters. Excess and deviation parameters were fitted to Redlich-Kister polynomial. Ability of this equation was tested using the standard deviation calculated with the help of least square method.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107488"},"PeriodicalIF":2.2,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143874163","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":"Investigating ethyl laurate and 2-alkanol systems: Application of significant structure theory","authors":"Mohammad Almasi","doi":"10.1016/j.jct.2025.107502","DOIUrl":"10.1016/j.jct.2025.107502","url":null,"abstract":"<div><div>The study examines the liquid density and viscosity behavior of ethyl laurate (EL) mixed with different 2-alkanols (2-propanol, 2-butanol, 2-pentanol, and 2-hexanol) over the temperature range of 293.15 to 323.15 K, with the goal of clarifying the intermolecular interactions and deviations from ideality. Our experimental observations showed that all tested mixtures displayed positive excess molar volumes and negative viscosity deviations, implying that the forces between EL and each 2-alkanol are relatively weak. The significant structure theory was then utilized to represent the pure-component viscosities, yielding a maximum viscosity discrepancy of 1.691 % for 2-pentanol. For the binary systems, we introduced a new correlation whose calculated values aligned closely with the measurements, demonstrating a maximum variation of only 2.01 % for the EL + 2-hexanol mixture, which highlights the predictive capability of the proposed model. The performance of this model was compared to earlier models such as Nissan-Grunberg, Hind, Kendall-Monroe, Arrhenius, and other models. Our results demonstrate that the new model offers improved accuracy, albeit with more complex parameters.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107502"},"PeriodicalIF":2.2,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143852085","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":"Ionic speciation and volumetric properties modeling of the ternary system CuCl2 – HCl – H2O from 273.15 to 373.15 K and at 101.3 kPa using the Pitzer equations","authors":"Aldo N. Fuentes ,&nbsp;Jesús M. Casas ,&nbsp;Francisca J. Justel ,&nbsp;Yecid P. Jiménez","doi":"10.1016/j.jct.2025.107500","DOIUrl":"10.1016/j.jct.2025.107500","url":null,"abstract":"<div><div>This work develops a thermodynamic model for ionic speciation and volumetric properties of the ternary system CuCl₂ – HCl – H₂O from 273.15 to 373.15 K and at 101.3 kPa, a system relevant to chalcopyrite leaching in chloride media and hydrogen production via the copper–chlorine thermochemical cycle. The Pitzer equations were used to estimate water activities, CuCl₂·2H₂O(cr) solubilities, and densities, calibrated using published experimental data. The speciation model includes Cu²⁺, H⁺, CuCl⁺, Cl^–, <span><math><msubsup><mi>CuCl</mi><mn>2</mn><mn>0</mn></msubsup></math></span>, and HCl⁰, showing reasonable species distribution results as a function of temperature and total concentration. Based on volume of mixing calculations at 298.15 K, CuCl₂ acts as a structure breaker of water, while HCl behaves as a structure maker. New Pitzer parameters and the solubility product constant of CuCl₂·2H₂O(cr) are provided as temperature–dependent functions. The model demonstrates high accuracy in reproducing experimental data and offers insights into the physicochemical behavior of concentrated CuCl₂ + HCl + H₂O solutions.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107500"},"PeriodicalIF":2.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143843673","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":"Apparent molar volumes of methanol, ethanol, and 2-propanol in dense phase CO2","authors":"Safeer S. Nanji,&nbsp;Connor E. Deering,&nbsp;Kevin L. Lesage,&nbsp;Robert A. Marriott","doi":"10.1016/j.jct.2025.107499","DOIUrl":"10.1016/j.jct.2025.107499","url":null,"abstract":"<div><div>Despite the increasing importance of CO₂ processing and the use of aliphatic alcohols as cosolvents in supercritical fluid extraction, there is an apparent lack of densimetric or volumetric data for dilute alcohols in near-critical CO₂ within the literature. To this end, apparent molar volumes of binary solutions for methanol, ethanol, and 2-propanol in CO₂ were calculated from measured density differences (<em>δΔρ =</em> 0.01–1.60 kg m⁻³) determined from <em>T</em> = 298–313 K and <em>p</em> = 8–13 MPa using a flow densimeter modified for high pressure measurement. This temperature and pressure range was chosen for the proximity to the critical point of pure CO₂, where volumetric changes are very sensitive and allow for better calibration of binary parameters. The apparent molar volumes of the mixtures were then used to optimize mixing coefficients with reference quality pure component Helmholtz equations-of-state and Fluctuation Solution Theory. Apparent molar volumes of these alcohol solutes resulted in poorer fits of the binary mixing coefficients for reference quality reduced Helmholtz Equations of State when compared to Fluctuation Solution Theory; however, excess functions with more parameters may be developed by future researchers. With the Fluctuation Solution Theory equations, Krichevskii parameters were determined for each alcohol in CO₂. These values were similar to a previous study of H₂O in CO₂; however, variance was noted from literature values with different methods of extrapolation.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107499"},"PeriodicalIF":2.2,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143848713","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":"Comments regarding “Solubility determination, model evaluation, molecular simulation and thermodynamic analysis of sulfentrazone (form I) in single and binary solvents”","authors":"Bradley Lin,&nbsp;Saikiran Motati,&nbsp;William E. Acree","doi":"10.1016/j.jct.2025.107490","DOIUrl":"10.1016/j.jct.2025.107490","url":null,"abstract":"<div><div>A polemic is given regarding the van't Hoff curve-fit parameters and apparent thermodynamic properties of solution of sulfentrazone (form I) that Mao and coworkers reported in their recently published paper. The van't Hoff parameters were found to be inconsistent with the tabulated thermodynamic quantities. New sets of curve-fit parameters were determined by reanalysis of the authors' published mole fraction solubility data.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107490"},"PeriodicalIF":2.2,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143786303","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 the solvent H/D isotope substitution on enthalpy-interaction parameters for the pharmaceutical urotropine (hexamethylenetetramine) in aqueous solutions at 298.15 K","authors":"Evgeniy V. Ivanov ,&nbsp;Dmitriy V. Batov ,&nbsp;Andrey V. Kustov ,&nbsp;Alexander F. Syschenko","doi":"10.1016/j.jct.2025.107489","DOIUrl":"10.1016/j.jct.2025.107489","url":null,"abstract":"<div><div>The enthalpies of dilution of solutions of hexamethylenetetramine (HMTA), the well-known pharmaceutical <em>urotropine</em>, in water (H₂O) and heavy water (D₂O) were determined with a new heat conduction calorimeter at 298.15 K. The enthalpy-related homotactic coefficients of pairwise, <span><math><msub><mi>h</mi><mn>22</mn></msub></math></span>, and triplet, <span><math><msub><mi>h</mi><mn>222</mn></msub></math></span>, interactions between hydrated solute molecules were computed using the excess thermodynamic function concept (based on the McMillan-Mayer theory formalism). The <span><math><msub><mi>h</mi><mn>22</mn></msub></math></span> and <span><math><msub><mi>h</mi><mn>222</mn></msub></math></span> values were found to be large and positive in both H₂O and D₂O due to a partial overlapping of solute hydrophobic hydration shells and appearance of solute – solute correlations at rather large distances. This phenomenon is stronger pronounced in heavy water both for pairwise and for triplet HMTA – HMTA interactions indicating a highly ordered hydration structure in D₂O. The established correlation between the <span><math><msub><mi>h</mi><mn>22</mn></msub></math></span> values and the corresponding solvent isotope effects, <span><math><msub><mi>δh</mi><mn>22</mn></msub></math></span>(H₂O → D₂O), for HMTA and tetramethylurea mono- and bicyclic derivatives as solute species confirms the hypothesis of the differentiating effect of a solvent isotopic substitution on both the energetics of solvation and solute – solute interactions in aqueous solutions of proton-accepting non-electrolytes. In other words, the more negative or positive the <span><math><msub><mi>h</mi><mn>22</mn></msub></math></span> value due to stronger homo- and heterocomponent D-bonds, the more negative or positive the corresponding isotopic effect is.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107489"},"PeriodicalIF":2.2,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783793","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}