Journal of Chemical Thermodynamics最新文献

英文中文

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

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-23 DOI: 10.1016/j.jct.2025.107501

Aldo N. Fuentes , José D. Arriagada , Yecid P. Jiménez , Jesús M. Casas , Francisca J. Justel

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.

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.

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.

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.

{"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 , José D. Arriagada , Yecid P. Jiménez , Jesús M. Casas , 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–H<sub>2</sub>O 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 – H<sub>2</sub>O 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}

引用次数: 0

Freezing point depression in the binary NaVO3–H2O and NH4VO3–H2O Systems at p=0.1MPa

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-22 DOI: 10.1016/j.jct.2025.107491

Mikael A.E. Manninen, Tuomas J. Vielma, Ulla M. Lassi

The freezing point depressions in the

and

systems have been determined at

p = 0.1 M P a

from molalities of ca.

0.005 {m o l k g}^{- 1}

up to near saturation. The present data significantly expand the almost non-existent database of excess thermodynamic properties of binary

systems. The data could be explained within their experimental uncertainties by a thermodynamic model considering the association of the dihydrogenvanadate ion (

) to

and representing the excess Gibbs free energy (

G^{Ex}

) by the Pitzer equations with two adjustable parameters. The magnitudes of the determined parameters for the second virial coefficient of

interaction were typical for 4-1 electrolytes. The same model could describe also the data for the

system as even the saturated solution is sufficiently dilute that the contribution of short range interactions to

G^{Ex}

is small.

{"title":"Freezing point depression in the binary NaVO3–H2O and NH4VO3–H2O Systems at p=0.1MPa","authors":"Mikael A.E. Manninen, Tuomas J. Vielma, 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}

引用次数: 0

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

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-21 DOI: 10.1016/j.jct.2025.107488

Likhish Dhingra, Gyan Prakash Dubey

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).ρ, u and η of these binary mixtures were measured at temperatures T = 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.

引用次数: 0

Investigating ethyl laurate and 2-alkanol systems: Application of significant structure theory 研究月桂酸乙酯和 2-烷醇体系：重要结构理论的应用

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-17 DOI: 10.1016/j.jct.2025.107502

Mohammad Almasi

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.

{"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}

引用次数: 0

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

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-15 DOI: 10.1016/j.jct.2025.107500

Aldo N. Fuentes , Jesús M. Casas , Francisca J. Justel , Yecid P. Jiménez

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^–,

{CuCl}_{2}^{0}

, 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.

{"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 , Jesús M. Casas , Francisca J. Justel , 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 CuCl<sub>2</sub> – HCl – H<sub>2</sub>O 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, CuCl<sub>2</sub>·2H<sub>2</sub>O(cr) solubilities, and densities, calibrated using published experimental data. The speciation model includes Cu<sup>2+</sup>, H<sup>+</sup>, CuCl<sup>+</sup>, Cl<sup>–</sup>, <span><math><msubsup><mi>CuCl</mi><mn>2</mn><mn>0</mn></msubsup></math></span>, and HCl<sup>0</sup>, showing reasonable species distribution results as a function of temperature and total concentration. Based on volume of mixing calculations at 298.15 K, CuCl<sub>2</sub> acts as a structure breaker of water, while HCl behaves as a structure maker. New Pitzer parameters and the solubility product constant of CuCl<sub>2</sub>·2H<sub>2</sub>O(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 CuCl<sub>2</sub> + HCl + H<sub>2</sub>O 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}

引用次数: 0

Apparent molar volumes of methanol, ethanol, and 2-propanol in dense phase CO2

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-15 DOI: 10.1016/j.jct.2025.107499

Safeer S. Nanji, Connor E. Deering, Kevin L. Lesage, Robert A. Marriott

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 (δΔρ = 0.01–1.60 kg m⁻³) determined from T = 298–313 K and p = 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.

{"title":"Apparent molar volumes of methanol, ethanol, and 2-propanol in dense phase CO2","authors":"Safeer S. Nanji, Connor E. Deering, Kevin L. Lesage, 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 CO<sub>2</sub> 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 CO<sub>2</sub> within the literature. To this end, apparent molar volumes of binary solutions for methanol, ethanol, and 2-propanol in CO<sub>2</sub> were calculated from measured density differences (<em>δΔρ =</em> 0.01–1.60 kg m<sup>−3</sup>) 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 CO<sub>2</sub>, 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 CO<sub>2</sub>. These values were similar to a previous study of H<sub>2</sub>O in CO<sub>2</sub>; 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}

引用次数: 0

Comments regarding “Solubility determination, model evaluation, molecular simulation and thermodynamic analysis of sulfentrazone (form I) in single and binary solvents”

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-04-03 DOI: 10.1016/j.jct.2025.107490

Bradley Lin, Saikiran Motati, William E. Acree

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.

引用次数: 0

Effect of the solvent H/D isotope substitution on enthalpy-interaction parameters for the pharmaceutical urotropine (hexamethylenetetramine) in aqueous solutions at 298.15 K 在 298.15 K 的水溶液中，溶剂 H/D 同位素置换对药物乌洛托品（六亚甲基四胺）焓-相互作用参数的影响

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-03-28 DOI: 10.1016/j.jct.2025.107489

Evgeniy V. Ivanov , Dmitriy V. Batov , Andrey V. Kustov , Alexander F. Syschenko

The enthalpies of dilution of solutions of hexamethylenetetramine (HMTA), the well-known pharmaceutical urotropine, 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,

h_{22}

, and triplet,

h_{222}

, interactions between hydrated solute molecules were computed using the excess thermodynamic function concept (based on the McMillan-Mayer theory formalism). The

h_{22}

and

h_{222}

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

h_{22}

values and the corresponding solvent isotope effects,

{δh}_{22}

(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

h_{22}

value due to stronger homo- and heterocomponent D-bonds, the more negative or positive the corresponding isotopic effect is.

{"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 , Dmitriy V. Batov , Andrey V. Kustov , 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 (H<sub>2</sub>O) and heavy water (D<sub>2</sub>O) 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 H<sub>2</sub>O and D<sub>2</sub>O 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 D<sub>2</sub>O. 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>(H<sub>2</sub>O → D<sub>2</sub>O), 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}

引用次数: 0

Exploring molecular interactions between methyl Myristate and 2-alcohols: Free volume theory perspective

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-03-27 DOI: 10.1016/j.jct.2025.107485

Sanaz Gharehzadeh Shirazi, Samaneh Heydarian, Hassan Moghanian, Mohamad Naseh

This study investigates the thermophysical properties of binary mixtures consisting of methyl myristate (MM) and a homologous series of 2-alkanols (ranging from 2-propanol to 2-hexanol) over a temperature range of 293.15 to 323.15 K. Experimental measurements of liquid densities and viscosities reveal significant deviations from ideal behavior, characterized by positive excess molar volumes and negative viscosity deviations across all examined mixtures. The observed positive deviations in excess molar volume suggest weak intermolecular interactions between MM and the 2-alkanols. Furthermore, both an increase in the alkyl chain length of the 2-alkanols and temperature rise were found to reduce these molecular interactions, leading to more pronounced excess volumes. To better understand the viscosity behavior of both pure components and their mixtures, we applied free volume theory. This theoretical approach demonstrated excellent agreement with experimental data, with a maximum deviation of only 2.41 % observed in the MM/2-propanol system.

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引用次数: 0

The 2,2,4-trimethylpentane + ethyl propanoate binary system: density, Bancroft point and vapor–liquid equilibrium at 30, 60 and 101.3 kPa

IF 2.2 3区工程技术 Q3 CHEMISTRY, PHYSICAL

Journal of Chemical Thermodynamics

Pub Date : 2025-03-26 DOI: 10.1016/j.jct.2025.107486

Stéphane Vitu , Kaoutar Berkalou , Jean-Louis Havet , Vincent Caqueret

The 2,2,4-trimethylpentane (isooctane) – ethyl ethanoate binary system was experimentally investigated. The density of the mixture was measured using a vibrating-tube apparatus and is reported at temperatures T = (288.15, 298.15, 308.15 and 318.15) K. The mixture exhibits positive excess molar volumes. Isobaric vapor-liquid equilibrium (VLE) of the system were obtained at three pressures P = (30, 60 and 101.3) kPa. Pure components vapor pressures were also acquired over a range of P = (20 to 160) kPa. Equilibrium data were measured using a recirculation ebulliometer (Gillespie-type VLE cell).

The 2,2,4-trimethylpentane – ethyl ethanoate presents a Bancroft point within the investigated pressure range and, consequently, an azeotropic behavior at each studied pressure. The azeotropic coordinates, derived from the measured VLE data, are reported. A notable dependence of the azeotropic composition on pressure was observed.

The NRTL and Wilson activity coefficient models were used to correlate the VLE data. Temperature-dependent interaction parameters were determined, enabling precise correlation of the reported VLE data. The predictive UNIFAC (Dortmund) model was also tested. While it produced accurate results at 30 kPa, significant deviations were noted at higher pressures.

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