Pub Date : 2025-08-01Epub Date: 2025-04-17DOI: 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":"2025-08-01","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}
Pub Date : 2025-08-01Epub Date: 2025-03-26DOI: 10.1016/j.jct.2025.107487
Hai-Fang Wang
7-Amino-6-nitrobenzodifuroxan (ANBDF) solubility was determined using a laser dynamic technique from 288.15 K to 333.15 K under 0.1 MPa in fifteen pure solvents, including methanol, ethanol, acetone, cyclohexanone, ethyl acetate, acetonitrile, dichloromethane, 1,2-dichloroethane, ethanoic acid, propanoic acid, toluene, o-xylene, N-Methylpyrrolidone (NMP), N,N-Dimethylformamide (DMF), Dimethyl sulfoxide (DMSO). ANBDF might become more soluble in fifteen pure solvents as the temperature rose. At 298.15 K, the following substances dissolve ANBDF in the following order: DMSO > NMP > DMF > cyclohexanone > acetone > acetonitrile > ethyl acetate > ethanoic acid >1,2-dichloroethane > o-xylene > propanoic acid > methanol > dichloromethane > toluene > ethanol. The KAT-LSER model was used to study the influence of the solvent, and it revealed that the acidity of the solvents' hydrogen bonds has a stronger impact on the solubility of ANBDF. The solubility of ANBDF was correlated using van't Hoff equation, modified Apelblat equation, Yaws equation and polynomial empirical equation. In addition, thermodynamic parameters such as the standard dissolution enthalpy, standard dissolution entropy, and standard Gibbs free energy were calculated based on the experimental solubility values. The dissolution process of ANBDF could be an enthalpy-driven, non-spontaneous and endothermic process in fifteen pure solvents. The measurement and fitting solubility of ANBDF have important guiding significance for the purification and crystallization of its preparation process.
采用激光动力学技术测定了7-氨基-6-硝基苯并二硝基呋喃（ANBDF）在0.1 MPa、288.15 K ~ 333.15 K范围内，在甲醇、乙醇、丙酮、环己酮、乙酸乙酯、乙腈、二氯甲烷、1,2-二氯乙烷、乙醇酸、丙酸、甲苯、邻二甲苯、N-甲基吡罗烷酮（NMP）、N，N-二甲基甲酰胺（DMF）、二甲基亚砜（DMSO）等15种纯溶剂中的溶解度。随着温度的升高，ANBDF可能在15种纯溶剂中更容易溶解。在298.15 K时，下列物质按顺序溶解ANBDF: DMSO >；NMP祝辞DMF祝辞环己酮在丙酮比;乙腈比;乙酸乙酯>；乙酸>；1,2-二氯乙烷>；邻二甲苯的在丙酸>；甲醇比;二氯甲烷比;甲苯比;乙醇。利用KAT-LSER模型研究了溶剂的影响，发现溶剂氢键的酸度对ANBDF的溶解度有较大的影响。利用van't Hoff方程、修正Apelblat方程、Yaws方程和多项式经验方程对ANBDF的溶解度进行了相关性分析。根据实验溶解度值计算了标准溶解焓、标准溶解熵和标准吉布斯自由能等热力学参数。ANBDF在15种纯溶剂中的溶解过程为焓驱动、非自发和吸热过程。ANBDF溶解度的测定和拟合对其制备过程的纯化和结晶具有重要的指导意义。
{"title":"Measurement and correlation solubility of 7-amino-6-nitrobenzodifuroxan in fifteen pure solvents from 288.15 to 333.15 K","authors":"Hai-Fang Wang","doi":"10.1016/j.jct.2025.107487","DOIUrl":"10.1016/j.jct.2025.107487","url":null,"abstract":"<div><div>7-Amino-6-nitrobenzodifuroxan (ANBDF) solubility was determined using a laser dynamic technique from 288.15 K to 333.15 K under 0.1 MPa in fifteen pure solvents, including methanol, ethanol, acetone, cyclohexanone, ethyl acetate, acetonitrile, dichloromethane, 1,2-dichloroethane, ethanoic acid, propanoic acid, toluene, o-xylene, N-Methylpyrrolidone (NMP), <em>N</em>,<em>N</em>-Dimethylformamide (DMF), Dimethyl sulfoxide (DMSO). ANBDF might become more soluble in fifteen pure solvents as the temperature rose. At 298.15 K, the following substances dissolve ANBDF in the following order: DMSO > NMP > DMF > cyclohexanone > acetone > acetonitrile > ethyl acetate > ethanoic acid >1,2-dichloroethane > o-xylene > propanoic acid > methanol > dichloromethane > toluene > ethanol. The KAT-LSER model was used to study the influence of the solvent, and it revealed that the acidity of the solvents' hydrogen bonds has a stronger impact on the solubility of ANBDF. The solubility of ANBDF was correlated using van't Hoff equation, modified Apelblat equation, Yaws equation and polynomial empirical equation. In addition, thermodynamic parameters such as the standard dissolution enthalpy, standard dissolution entropy, and standard Gibbs free energy were calculated based on the experimental solubility values. The dissolution process of ANBDF could be an enthalpy-driven, non-spontaneous and endothermic process in fifteen pure solvents. The measurement and fitting solubility of ANBDF have important guiding significance for the purification and crystallization of its preparation process.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107487"},"PeriodicalIF":2.2,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143747199","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 : 2025-08-01Epub Date: 2025-03-22DOI: 10.1016/j.jct.2025.107484
Allison Kabin, Dhishithaa Kumarandurai, Bradley Lin, William E. Acree
A polemic is given regarding the solution models used by Wang and coworkers to correlate the solubility behavior of tolnaftate in ten organic mono-solvents and in binary acetic acid + ethylene glycol solvent mixtures. For several of the mixtures studied authors' calculated curve-fit parameters yielded mole fraction solubilities that exceeded unity.
{"title":"Comments on “solubility determination, correlation, solvent effect and thermodynamic properties of tolnaftate in ten mono-solvents and binary solvent systems from 283.15 K to 328.15 K\"","authors":"Allison Kabin, Dhishithaa Kumarandurai, Bradley Lin, William E. Acree","doi":"10.1016/j.jct.2025.107484","DOIUrl":"10.1016/j.jct.2025.107484","url":null,"abstract":"<div><div>A polemic is given regarding the solution models used by Wang and coworkers to correlate the solubility behavior of tolnaftate in ten organic mono-solvents and in binary acetic acid + ethylene glycol solvent mixtures. For several of the mixtures studied authors' calculated curve-fit parameters yielded mole fraction solubilities that exceeded unity.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107484"},"PeriodicalIF":2.2,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143704238","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 : 2025-08-01Epub Date: 2025-04-15DOI: 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.
尽管CO2处理和在超临界流体萃取中使用脂肪族醇作为助溶剂的重要性日益增加，但在文献中明显缺乏近临界CO2中稀醇的密度或体积数据。为此，在T = 298-313 K和p = 8-13 MPa的条件下，使用改进的高压测量流量密度计，通过测量密度差（δΔρ = 0.01-1.60 kg m - 3），计算出甲醇、乙醇和2-丙醇在CO2中的二元溶液的表观摩尔体积。选择这个温度和压力范围是为了接近纯二氧化碳的临界点，在那里，体积变化非常敏感，可以更好地校准二进制参数。采用纯组分亥姆霍兹状态方程和涨落解理论，利用混合物的表观摩尔体积来优化混合系数。与波动解理论相比，这些醇溶质的表观摩尔体积导致二元混合系数的拟合较差，参比质量降低了亥姆霍兹状态方程；然而，未来的研究人员可能会开发出具有更多参数的过剩函数。利用波动解理论方程，确定了CO2中每种醇的克里切夫斯基参数。这些数值与之前对CO2中H2O的研究相似；然而，不同外推方法的文献值存在差异。
{"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":"2025-08-01","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}
The thermodynamic quantities (ΔG, ΔH, and ΔS) for the formation of U(VI) complexes with three amino acids, L-serine, L-phenylalanine, and L-cysteine were determined, where the stability constants were obtained by potentiometric titration and the reaction enthalpies were directly measured by calorimetric titration. Prior to the U(VI) complexation study, the ΔG, ΔH, and ΔS of the protonation of the three amino acids were determined using the same techniques. The obtained thermodynamic quantities are compared to discuss the complex formation's driving forces and mechanism. The obtained thermodynamic data indicates that U(VI)-L-serine and U(VI)-L-phenylalanine complexes are entropy-driven reactions, whereas a significant enthalpy benefit drives L-cysteine complexation. From the comparison between the obtained thermodynamic data in this study and the spectroscopic and theoretical analyses in previous research, it was suggested that the complex formation of the amino acid with U(VI) proceed without significant involvement of the amino group while the thiol group in L-cysteine significantly contributes to the complexation with U(VI).
测定了l -丝氨酸、l -苯丙氨酸和l -半胱氨酸三种氨基酸形成U（VI）配合物的热力学量（ΔG、ΔH和ΔS），其中稳定性常数由电位滴定法获得，反应焓由量热滴定法直接测定。在U（VI）络合研究之前，使用相同的技术测定了三种氨基酸的质子化的ΔG， ΔH和ΔS。通过对所得热力学量的比较，探讨了复杂地层的驱动力和机理。得到的热力学数据表明，U(VI)- l -丝氨酸和U(VI)- l -苯丙氨酸配合物是熵驱动的反应，而l -半胱氨酸配合物有显著的焓效益驱动。从本研究获得的热力学数据与前人研究的光谱和理论分析的对比可以看出，氨基酸与U（VI）的络合反应在没有氨基参与的情况下进行，而l -半胱氨酸中的巯基对与U（VI）的络合反应起着重要作用。
{"title":"Determination of the thermodynamic quantities for complex formation of U(VI) with amino acids in aqueous solution","authors":"Akira Kirishima , Masahide Takei , Akihiro Uehara , Daisuke Akiyama","doi":"10.1016/j.jct.2025.107469","DOIUrl":"10.1016/j.jct.2025.107469","url":null,"abstract":"<div><div>The thermodynamic quantities (Δ<em>G</em>, Δ<em>H</em>, and Δ<em>S</em>) for the formation of U(VI) complexes with three amino acids, L-serine, L-phenylalanine, and L-cysteine were determined, where the stability constants were obtained by potentiometric titration and the reaction enthalpies were directly measured by calorimetric titration. Prior to the U(VI) complexation study, the Δ<em>G</em>, Δ<em>H</em>, and Δ<em>S</em> of the protonation of the three amino acids were determined using the same techniques. The obtained thermodynamic quantities are compared to discuss the complex formation's driving forces and mechanism. The obtained thermodynamic data indicates that U(VI)-L-serine and U(VI)-L-phenylalanine complexes are entropy-driven reactions, whereas a significant enthalpy benefit drives L-cysteine complexation. From the comparison between the obtained thermodynamic data in this study and the spectroscopic and theoretical analyses in previous research, it was suggested that the complex formation of the amino acid with U(VI) proceed without significant involvement of the amino group while the thiol group in L-cysteine significantly contributes to the complexation with U(VI).</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107469"},"PeriodicalIF":2.2,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143534154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-01Epub Date: 2025-02-28DOI: 10.1016/j.jct.2025.107475
Haifang Mao , Jiangmei Chen , Qiyu Wang , Mengjie Luo , Zhiqing Li , Changtao Zhou , Bing Wei , Jibo Liu , Miaomiao Jin
The molar fraction solubility of sulfentrazone (Form I) in ethanol, n-propanol, i-propanol, n-butanol, and binary solvents (ethanol + water) was measured by a laser dynamic method at temperatures from 278.15 K to 313.15 K under 101.6 kPa (standard uncertainty is = 1.2 kPa). The solid-liquid phase equilibrium data were verified using five thermodynamic models: van't Hoff equation, modified Apelblat equation, λh equation, Wilson model, and modified Jouyban-Acree model. The modified Apelblat equation showed the best fitting results for the solubility correlation of sulfentrazone (Form I). In addition, the molecular interaction was analyzed using the Hirshfeld surface analysis, molecular electrostatic potential surface analysis, and Hansen solubility parameters to understand the dissolution mechanism of sulfentrazone (Form I). Molecular dynamics simulation was used to analyze the radial distribution function to explore intermolecular interactions of sulfentrazone (Form I) in ethanol + water binary solvents. Finally, the thermodynamic properties of sulfentrazone (Form I) in the studied solvents were also discussed using the van't Hoff equation, and the results implied that the dissolution of sulfentrazone (Form I) was an endothermic and entropy-driven process. The solubility data and the relevant thermodynamic analysis of sulfentrazone (Form I) provide fundamental guidance for the crystallization and purification of sulfentrazone (Form I).
{"title":"Solubility determination, model evaluation, molecular simulation and thermodynamic analysis of sulfentrazone (Form I) in single and binary solvents","authors":"Haifang Mao , Jiangmei Chen , Qiyu Wang , Mengjie Luo , Zhiqing Li , Changtao Zhou , Bing Wei , Jibo Liu , Miaomiao Jin","doi":"10.1016/j.jct.2025.107475","DOIUrl":"10.1016/j.jct.2025.107475","url":null,"abstract":"<div><div>The molar fraction solubility of sulfentrazone (Form I) in ethanol, n-propanol, i-propanol, n-butanol, and binary solvents (ethanol + water) was measured by a laser dynamic method at temperatures from 278.15 <em>K</em> to 313.15 <em>K</em> under 101.6 <em>kPa</em> (standard uncertainty is <span><math><mi>u</mi><mfenced><mi>p</mi></mfenced></math></span> = 1.2 <em>kPa</em>). The solid-liquid phase equilibrium data were verified using five thermodynamic models: van't Hoff equation, modified Apelblat equation, <em>λh</em> equation, Wilson model, and modified Jouyban-Acree model. The modified Apelblat equation showed the best fitting results for the solubility correlation of sulfentrazone (Form I). In addition, the molecular interaction was analyzed using the Hirshfeld surface analysis, molecular electrostatic potential surface analysis, and Hansen solubility parameters to understand the dissolution mechanism of sulfentrazone (Form I). Molecular dynamics simulation was used to analyze the radial distribution function to explore intermolecular interactions of sulfentrazone (Form I) in ethanol + water binary solvents. Finally, the thermodynamic properties of sulfentrazone (Form I) in the studied solvents were also discussed using the van't Hoff equation, and the results implied that the dissolution of sulfentrazone (Form I) was an endothermic and entropy-driven process. The solubility data and the relevant thermodynamic analysis of sulfentrazone (Form I) provide fundamental guidance for the crystallization and purification of sulfentrazone (Form I).</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107475"},"PeriodicalIF":2.2,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143548559","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 : 2025-07-01Epub Date: 2025-02-20DOI: 10.1016/j.jct.2025.107470
Airat A. Notfullin, Dmitrii N. Bolmatenkov, Andrey A. Sokolov, Ilya S. Balakhontsev, Alexander D. Kachmarzhik, Boris N. Solomonov, Mikhail I. Yagofarov
In this paper, we report a comprehensive analysis of the thermodynamic properties of organic semiconductors, namely, N,N,N′,N′-tetraphenyl-p-phenylenediamine (DDP), N,N′-diphenyl-N,N′-di-p-tolylbenzene-1,4-diamine (p-TTP), and 4,4′-bis(m-tolylphenylamino) biphenyl (TPD). Vapor pressures above crystalline and liquid (including supercooled liquid) phases over a wide temperature range were measured using thermogravimetry-fast scanning calorimetry method (TG- FSC). Based on the vapor pressures, the vaporization and sublimation enthalpies of the studied compounds were derived. Heat capacities of condensed phases, melting points and fusion enthalpies of DDP, p-TTP, and TPD were measured by differential scanning calorimetry. Using the measured heat capacities of the liquid and crystalline phases and the computed heat capacities of the ideal gas phase, the experimental data obtained in the present work were adjusted to 298.15 K and compared with the available literature values. For additional verification of the obtained results, the solution calorimetry method was applied, providing an independent way to determine fusion enthalpies at 298.15 K. The obtained data can be used for optimization of the vacuum deposition processes and determination of thermodynamic properties of glasses.
{"title":"Phase transition thermodynamics of organic semiconductors N,N,N′,N′-tetraphenyl-p-phenylenediamine, N,N′-diphenyl-N,N′-di-p-tolylbenzene-1,4-diamine, and 4,4′-bis(m-tolylphenylamino)biphenyl","authors":"Airat A. Notfullin, Dmitrii N. Bolmatenkov, Andrey A. Sokolov, Ilya S. Balakhontsev, Alexander D. Kachmarzhik, Boris N. Solomonov, Mikhail I. Yagofarov","doi":"10.1016/j.jct.2025.107470","DOIUrl":"10.1016/j.jct.2025.107470","url":null,"abstract":"<div><div>In this paper, we report a comprehensive analysis of the thermodynamic properties of organic semiconductors, namely, <em>N,N,N′,N′</em>-tetraphenyl-<em>p</em>-phenylenediamine (DDP), <em>N,N′</em>-diphenyl-<em>N,N′</em>-di-<em>p</em>-tolylbenzene-1,4-diamine (<em>p-</em>TTP), and 4,4′-bis(<em>m</em>-tolylphenylamino) biphenyl (TPD). Vapor pressures above crystalline and liquid (including supercooled liquid) phases over a wide temperature range were measured using thermogravimetry-fast scanning calorimetry method (TG- FSC). Based on the vapor pressures, the vaporization and sublimation enthalpies of the studied compounds were derived. Heat capacities of condensed phases, melting points and fusion enthalpies of DDP, <em>p-</em>TTP, and TPD were measured by differential scanning calorimetry. Using the measured heat capacities of the liquid and crystalline phases and the computed heat capacities of the ideal gas phase, the experimental data obtained in the present work were adjusted to 298.15 K and compared with the available literature values. For additional verification of the obtained results, the solution calorimetry method was applied, providing an independent way to determine fusion enthalpies at 298.15 K. The obtained data can be used for optimization of the vacuum deposition processes and determination of thermodynamic properties of glasses.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107470"},"PeriodicalIF":2.2,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143480425","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 : 2025-07-01Epub Date: 2025-02-27DOI: 10.1016/j.jct.2025.107474
Yang Yu, Yue Wang, Cunbin Du
The knowledge of solubility is indispensable in the pharmaceuticals development, crystal forms design, manufacturing and application. The high-quality solubility facilitates the selection of appropriate solvents for the formulation and purification of pharmaceutical products. In this study, the phase equilibrium of Lisinopril was established in ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, acetonitrile, ethyl acetate, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), as well as mixtures of DMSO + ethanol and DMSO +2-propanol. The solubility, solvent effect discussion, molecular dynamics (MD) simulations, molecular interaction analysis, model correlation and thermodynamics evaluation were all conducted. The outcomes of Lisinopril solubility in molarity show a direct correlation with temperature, and the rank was as listed: DMSO (1.013 × 10−3, 318.15 K) > ethanol (3.887 × 10−4, 318.15 K) > 1-propanol (3.277 × 10−4, 318.15 K) > NMP (2.292 × 10−4, 318.15 K) > 1-butanol (1.642 × 10−4, 318.15 K) > DMF (1.217 × 10−4, 318.15 K) > 2-propanol (8.504 × 10−5, 318.15 K) > acetone (5.212 × 10−5, 318.15 K) > acetonitrile (3.201 × 10−5, 318.15 K) > ethyl acetate (1.851 × 10−5, 318.15 K). The solubility of Lisinopril in DMSO +2-propanol increased with the increasing content of DMSO, however, co-solvency phenomenon exhibited at w = 0.80 in mixture of DMSO + ethanol, and the maximum solubility is 1.271 × 10−3 (3.21-fold increase). The molecular interaction was discussed by preferential solvation in depth. Solvent effect was evaluated by KAT-LSER model which concluded that solute-solvent interactions significantly affect solubility more than solvent-solvent interactions. The contributions of solute-solvent interactions and solvent-solvent interactions 71.01 % and 28.99 %. Furthermore, MD simulation at the molecular level showed that hydrogen bonds can form more readily between molecules and play a crucial role in enhancing dissolution of Lisinopril. Additionally, the Apelblat, Wilson, Jouyban-Acree and Apelblat-Jouyban-Acree models were applied to correlate the Lisinopril solubility data. The greatest values of relative average deviation (RAD) and root-mean-square deviation (RMSD) values were 1.75 % and 1.68 × 10−5, respectively. Finally, the values of thermodynamic properties were all positive which indicated that the dissolution of Lisinopril was an endothermic and entropy increment process.
{"title":"Research on solubility, solvent effect and thermodynamics analysis of Lisinopril dissolution and molecular dynamics simulation","authors":"Yang Yu, Yue Wang, Cunbin Du","doi":"10.1016/j.jct.2025.107474","DOIUrl":"10.1016/j.jct.2025.107474","url":null,"abstract":"<div><div>The knowledge of solubility is indispensable in the pharmaceuticals development, crystal forms design, manufacturing and application. The high-quality solubility facilitates the selection of appropriate solvents for the formulation and purification of pharmaceutical products. In this study, the phase equilibrium of Lisinopril was established in ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, acetonitrile, ethyl acetate, dimethyl sulfoxide (DMSO), <em>N,N</em>-dimethylformamide (DMF), <em>N</em>-methylpyrrolidone (NMP), as well as mixtures of DMSO + ethanol and DMSO +2-propanol. The solubility, solvent effect discussion, molecular dynamics (MD) simulations, molecular interaction analysis, model correlation and thermodynamics evaluation were all conducted. The outcomes of Lisinopril solubility in molarity show a direct correlation with temperature, and the rank was as listed: DMSO (1.013 × 10<sup>−3</sup>, 318.15 K) > ethanol (3.887 × 10<sup>−4</sup>, 318.15 K) > 1-propanol (3.277 × 10<sup>−4</sup>, 318.15 K) > NMP (2.292 × 10<sup>−4</sup>, 318.15 K) > 1-butanol (1.642 × 10<sup>−4</sup>, 318.15 K) > DMF (1.217 × 10<sup>−4</sup>, 318.15 K) > 2-propanol (8.504 × 10<sup>−5</sup>, 318.15 K) > acetone (5.212 × 10<sup>−5</sup>, 318.15 K) > acetonitrile (3.201 × 10<sup>−5</sup>, 318.15 K) > ethyl acetate (1.851 × 10<sup>−5</sup>, 318.15 K). The solubility of Lisinopril in DMSO +2-propanol increased with the increasing content of DMSO, however, co-solvency phenomenon exhibited at <em>w</em> = 0.80 in mixture of DMSO + ethanol, and the maximum solubility is 1.271 × 10<sup>−3</sup> (3.21-fold increase). The molecular interaction was discussed by preferential solvation in depth. Solvent effect was evaluated by KAT-LSER model which concluded that solute-solvent interactions significantly affect solubility more than solvent-solvent interactions. The contributions of solute-solvent interactions and solvent-solvent interactions 71.01 % and 28.99 %. Furthermore, MD simulation at the molecular level showed that hydrogen bonds can form more readily between molecules and play a crucial role in enhancing dissolution of Lisinopril. Additionally, the Apelblat, Wilson, Jouyban-Acree and Apelblat-Jouyban-Acree models were applied to correlate the Lisinopril solubility data. The greatest values of relative average deviation (<em>RAD</em>) and root-mean-square deviation (<em>RMSD</em>) values were 1.75 % and 1.68 × 10<sup>−5</sup>, respectively. Finally, the values of thermodynamic properties were all positive which indicated that the dissolution of Lisinopril was an endothermic and entropy increment process.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107474"},"PeriodicalIF":2.2,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143592414","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 : 2025-07-01Epub Date: 2025-02-28DOI: 10.1016/j.jct.2025.107476
Mohamed Lifi , Jean-Patrick Bazile , Jean-Luc Daridon , Eduardo A. Montero , Fernando Aguilar , Natalia Muñoz-Rujas
High-temperature and high-pressure density data for the binary mixtures x 2-(2-ethoxyethoxy)ethanol + (1-x) 2-propanol are presented in this work, covering temperatures from 293.15 to 353.15 K and at pressures from 0.1 to 70 MPa. The experimental density data were generated using a vibrating tube densimeter with an uncertainty of 0.5 kg/m3. Experimental density data was fitted by using the Tait-like equation, yielding low standard deviations. Derivative properties such as excess molar volumes, isothermal compressibilities, excess isothermal compressibilities, and isobaric thermal expansions were calculated from the obtained density data. Additionally, the experimental measurements were modeled using PC-SAFT equation of state. The intermolecular interactions, as reflected in the derivative properties for each binary mixture, are thoroughly discussed.
{"title":"Density, isothermal compressibility, isobaric thermal expansion, and related excess properties of mixtures of 2-(2-ethoxyethoxy)ethanol + 2-propanol at temperatures from 293.15 K to 353.15 K and pressures up to 70 MPa: Measurements, correlation, and PC-SAFT modeling","authors":"Mohamed Lifi , Jean-Patrick Bazile , Jean-Luc Daridon , Eduardo A. Montero , Fernando Aguilar , Natalia Muñoz-Rujas","doi":"10.1016/j.jct.2025.107476","DOIUrl":"10.1016/j.jct.2025.107476","url":null,"abstract":"<div><div>High-temperature and high-pressure density data for the binary mixtures <em>x</em> 2-(2-ethoxyethoxy)ethanol + (1-<em>x</em>) 2-propanol are presented in this work, covering temperatures from 293.15 to 353.15 K and at pressures from 0.1 to 70 MPa. The experimental density data were generated using a vibrating tube densimeter with an uncertainty of 0.5 kg/m<sup>3</sup>. Experimental density data was fitted by using the Tait-like equation, yielding low standard deviations. Derivative properties such as excess molar volumes, isothermal compressibilities, excess isothermal compressibilities, and isobaric thermal expansions were calculated from the obtained density data. Additionally, the experimental measurements were modeled using PC-SAFT equation of state. The intermolecular interactions, as reflected in the derivative properties for each binary mixture, are thoroughly discussed.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107476"},"PeriodicalIF":2.2,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143548558","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 : 2025-07-01Epub Date: 2025-02-21DOI: 10.1016/j.jct.2025.107472
Ting Qin , Jiawei Zhao , Xiongtao Ji , Jinyue Yang , Na Wang , Baohong Hou , Ting Wang , Hongxun Hao
Abscisic acid (ABA) is one of the five natural growth regulators for plants and crystallization technology is used in the manufacturing of it. The thermodynamic behavior of it plays an important role in the development and design of crystallization processes. In this study, the solubility of ABA in twelve pure solvents was gravimetrically investigated over the temperature range of 278.15 K to 313.15 K. It was found that the solubility of ABA increased steadily with the rise of temperature. Four thermodynamic models (the modified Apelblat equation, van't Hoff equation, λh model and NRTL model) were applied to correlate the experimental solubility data, and the modified Apelblat equation model showed better fitting performance. The mixed thermodynamic properties of ABA in various pure solvents were also calculated, indicating that the mixed process is spontaneous and entropy-driven. Furthermore, to further explore the solid–liquid equilibrium behavior, Hirshfeld surface of ABA crystal was calculated and molecular dynamics simulations of different systems were performed. Based on equilibrium configurations of different systems, solute–solvent interaction energy was calculated, providing a reasonable explanation for the solubility of ABA. Meanwhile, the radial distribution function (RDF) plots were also employed to analyze the hydrogen bonding interactions between ABA molecules and solvent molecules.
{"title":"Solid-liquid equilibrium of abscisic acid in twelve pure solvents: Experiments, modeling, and molecular simulation","authors":"Ting Qin , Jiawei Zhao , Xiongtao Ji , Jinyue Yang , Na Wang , Baohong Hou , Ting Wang , Hongxun Hao","doi":"10.1016/j.jct.2025.107472","DOIUrl":"10.1016/j.jct.2025.107472","url":null,"abstract":"<div><div>Abscisic acid (ABA) is one of the five natural growth regulators for plants and crystallization technology is used in the manufacturing of it. The thermodynamic behavior of it plays an important role in the development and design of crystallization processes. In this study, the solubility of ABA in twelve pure solvents was gravimetrically investigated over the temperature range of 278.15 K to 313.15 K. It was found that the solubility of ABA increased steadily with the rise of temperature. Four thermodynamic models (the modified Apelblat equation, <em>van't Hoff</em> equation, <em>λh</em> model and NRTL model) were applied to correlate the experimental solubility data, and the modified Apelblat equation model showed better fitting performance. The mixed thermodynamic properties of ABA in various pure solvents were also calculated, indicating that the mixed process is spontaneous and entropy-driven. Furthermore, to further explore the solid–liquid equilibrium behavior, Hirshfeld surface of ABA crystal was calculated and molecular dynamics simulations of different systems were performed. Based on equilibrium configurations of different systems, solute–solvent interaction energy was calculated, providing a reasonable explanation for the solubility of ABA. Meanwhile, the radial distribution function (RDF) plots were also employed to analyze the hydrogen bonding interactions between ABA molecules and solvent molecules.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107472"},"PeriodicalIF":2.2,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509486","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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