Pub 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":"2025-02-28","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 : 2025-02-27DOI: 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":"2025-02-27","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}
The characterization of gaseous mixtures is an increasingly important issue in the fields of fuel analysis and aerosol research. Analyses by refractometry combined with refractive mixing rules are also powerful tools in this area. In this work a setup comprised by a six-laser interferometer and a vacuum system was projected and constructed in order to measure the refractivity of pure inert gases like N2, CO2, Ar and O2 and to study the validity of the refractive mixing rules with binary mixtures of N2 and Ar for different wavelengths. The light sources used in the experiments were a Hene laser (632.8 nm), a frequency-doubled diode-pumped Nd:YAG laser (532 nm) and four diode lasers emitting at 406.4 nm, 453 nm, 655.3 nm and 825 nm. The experimental refractivity data of the binary mixtures were compared with the theoretical ones obtained from a modified, temperature invariant, Gladstone-dale based refractive mixing rule, by introducing the parameter thermal refractivity (TR). The results obtained by the modified refractive mixing rule proposed by us for dry air were also compared with the refractive measurements of atmospheric air for the six wavelengths. In general the experimental results have shown good agreement with the theoretical predictions, and the dispersive character of the thermal refractivities point out to promising applications in evaluating gas mixtures.
{"title":"Gas mixture analysis by temperature-independent, multi-wavelength refractive mixing rules","authors":"J.B.S. Santos , H.A. Helfstein , M.T. Saita , F.T. Degasperi , R.B. Torres , E.A. Barbosa","doi":"10.1016/j.jct.2025.107473","DOIUrl":"10.1016/j.jct.2025.107473","url":null,"abstract":"<div><div>The characterization of gaseous mixtures is an increasingly important issue in the fields of fuel analysis and aerosol research. Analyses by refractometry combined with refractive mixing rules are also powerful tools in this area. In this work a setup comprised by a six-laser interferometer and a vacuum system was projected and constructed in order to measure the refractivity of pure inert gases like N<sub>2</sub>, CO<sub>2</sub>, Ar and O<sub>2</sub> and to study the validity of the refractive mixing rules with binary mixtures of N<sub>2</sub> and Ar for different wavelengths. The light sources used in the experiments were a He<img>ne laser (632.8 nm), a frequency-doubled diode-pumped Nd:YAG laser (532 nm) and four diode lasers emitting at 406.4 nm, 453 nm, 655.3 nm and 825 nm. The experimental refractivity data of the binary mixtures were compared with the theoretical ones obtained from a modified, temperature invariant, Gladstone-dale based refractive mixing rule, by introducing the parameter thermal refractivity (TR). The results obtained by the modified refractive mixing rule proposed by us for dry air were also compared with the refractive measurements of atmospheric air for the six wavelengths. In general the experimental results have shown good agreement with the theoretical predictions, and the dispersive character of the thermal refractivities point out to promising applications in evaluating gas mixtures.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107473"},"PeriodicalIF":2.2,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512352","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 : 2025-02-21DOI: 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":"2025-02-21","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}
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":"2025-02-20","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 : 2025-02-20DOI: 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":"2025-02-20","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 : 2025-02-20DOI: 10.1016/j.jct.2025.107471
Ruyi Lin , Shuaiqi Sun , Qingfen Meng , Dan Li , Yong Ma , Lingzong Meng , Yafei Guo , Tianlong Deng
The solubilities and physicochemical properties in the system Na2B4O5(OH)4–NaB5O6(OH)4–H2O at 323.15 K were studied with the isothermal dissolution method. The phase diagram in the system is composed of one co-saturation point, two solubility curves and two single-salt crystallization regions for Na2B4O5(OH)4·8H2O and NaB5O6(OH)4·3H2O. The water activities and osmotic coefficients were determined based on the sodium chloride standard reference solution with the isopiestic method. With the assumption of only two boron species B4O5(OH)42− and B5O6(OH)4− in the solution, the single salt parameters of NaB5O6(OH)4 and mixing ion interaction parameters in the system were fitted with the solubilities and water activities based on Pitzer model. The dissolution equilibrium constants of NaB5O6(OH)4·3H2O were obtained with the activity product constant method. The agreement for the calculated solubilities and water activities with the experimental results in the system shows that the Pitzer model with the above assumption can be used to describe the experimental values.
{"title":"Thermodynamic properties and thermodynamic modelling for aqueous mixed system containing sodium tetraborate and sodium pentaborate","authors":"Ruyi Lin , Shuaiqi Sun , Qingfen Meng , Dan Li , Yong Ma , Lingzong Meng , Yafei Guo , Tianlong Deng","doi":"10.1016/j.jct.2025.107471","DOIUrl":"10.1016/j.jct.2025.107471","url":null,"abstract":"<div><div>The solubilities and physicochemical properties in the system Na<sub>2</sub>B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub>–NaB<sub>5</sub>O<sub>6</sub>(OH)<sub>4</sub>–H<sub>2</sub>O at 323.15 K were studied with the isothermal dissolution method. The phase diagram in the system is composed of one co-saturation point, two solubility curves and two single-salt crystallization regions for Na<sub>2</sub>B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub>·8H<sub>2</sub>O and NaB<sub>5</sub>O<sub>6</sub>(OH)<sub>4</sub>·3H<sub>2</sub>O. The water activities and osmotic coefficients were determined based on the sodium chloride standard reference solution with the isopiestic method. With the assumption of only two boron species B<sub>4</sub>O<sub>5</sub>(OH)<sub>4</sub><sup>2−</sup> and B<sub>5</sub>O<sub>6</sub>(OH)<sub>4</sub><sup>−</sup> in the solution, the single salt parameters of NaB<sub>5</sub>O<sub>6</sub>(OH)<sub>4</sub> and mixing ion interaction parameters in the system were fitted with the solubilities and water activities based on Pitzer model. The dissolution equilibrium constants of NaB<sub>5</sub>O<sub>6</sub>(OH)<sub>4</sub>·3H<sub>2</sub>O were obtained with the activity product constant method. The agreement for the calculated solubilities and water activities with the experimental results in the system shows that the Pitzer model with the above assumption can be used to describe the experimental values.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107471"},"PeriodicalIF":2.2,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143488906","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 : 2025-02-14DOI: 10.1016/j.jct.2025.107468
Kejia Wang , Wei Zhang , Yuanmo Ren , Ting Li , Shiyu Lin , Funeng Xu , Haohuan Li , Xianxiang Wang , Huaqiao Tang , Gang Shu , Juchun Lin , Xiaoyang Ai , Hualin Fu
Tolnaftate (TNF) is a local antifungal agent. The determination of its solubility can serve as a valuable reference for its crystallization and formulation design, an area that has not yet been comprehensively investigated. In this study, the static method was carried out to determine the solubility of TNF in 10 mono-solvents (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-octanol, 1,2-propanediol, ethylene glycol, acetic acid) and the binary mixed solvents (acetic acid + ethylene glycol) at T = (283.15 to 328.15) K and P = 0.1 MPa. The experiment results showed that TNF dissolves best in acetic acid and worst in ethylene glycol among investigated mono-solvents. And the solubility in mixed solvents was observed to increase as the mole ratio of acetic acid augments. In all solvents, there is obviously increase in the solubility of TNF as temperature elevates. The Apelblat model, van't Hoff model, Jouyban model, GCM model, Sun model and Apelblat-Jouyban-Acree model were used to fit the solubility values. And the root mean square deviation (RMSD) between the calculated values and experimental values are less than 0.025 %, showing that the experimental values are accurate and the models have good fitting effects. At the same time, X-ray powder diffraction (PXRD) tests confirmed that the absence of crystal transformation during the process of TNF dissolution. In addition, according to the KAT-LSER model, the influence of solute-solvent interactions on the solubility of TNF exceeds that of solvent-solvent interactions. The thermodynamic properties including entropy (ΔH0sol), enthalpy (ΔS0sol), Gibbs free energy (ΔG0sol), enthalpy contribution (%ξH) and entropy contribution (%ξS) were calculated, which proved that dissolution process of TNF is endothermic and entropy-driven, and enthalpy mainly affects Gibbs free energy.
{"title":"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":"Kejia Wang , Wei Zhang , Yuanmo Ren , Ting Li , Shiyu Lin , Funeng Xu , Haohuan Li , Xianxiang Wang , Huaqiao Tang , Gang Shu , Juchun Lin , Xiaoyang Ai , Hualin Fu","doi":"10.1016/j.jct.2025.107468","DOIUrl":"10.1016/j.jct.2025.107468","url":null,"abstract":"<div><div>Tolnaftate (TNF) is a local antifungal agent. The determination of its solubility can serve as a valuable reference for its crystallization and formulation design, an area that has not yet been comprehensively investigated. In this study, the static method was carried out to determine the solubility of TNF in 10 mono-solvents (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-octanol, 1,2-propanediol, ethylene glycol, acetic acid) and the binary mixed solvents (acetic acid + ethylene glycol) at T = (283.15 to 328.15) K and <em>P</em> = 0.1 MPa. The experiment results showed that TNF dissolves best in acetic acid and worst in ethylene glycol among investigated mono-solvents. And the solubility in mixed solvents was observed to increase as the mole ratio of acetic acid augments. In all solvents, there is obviously increase in the solubility of TNF as temperature elevates. The Apelblat model, van't Hoff model, Jouyban model, GCM model, Sun model and Apelblat-Jouyban-Acree model were used to fit the solubility values. And the root mean square deviation (RMSD) between the calculated values and experimental values are less than 0.025 %, showing that the experimental values are accurate and the models have good fitting effects. At the same time, X-ray powder diffraction (PXRD) tests confirmed that the absence of crystal transformation during the process of TNF dissolution. In addition, according to the KAT-LSER model, the influence of solute-solvent interactions on the solubility of TNF exceeds that of solvent-solvent interactions. The thermodynamic properties including entropy (Δ<em>H</em><sup>0</sup><sub>sol</sub>), enthalpy (Δ<em>S</em><sup>0</sup><sub>sol</sub>), Gibbs free energy (Δ<em>G</em><sup>0</sup><sub>sol</sub>), enthalpy contribution (%ξ<sub>H</sub>) and entropy contribution (%ξ<sub>S</sub>) were calculated, which proved that dissolution process of TNF is endothermic and entropy-driven, and enthalpy mainly affects Gibbs free energy.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"205 ","pages":"Article 107468"},"PeriodicalIF":2.2,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427992","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 : 2025-02-10DOI: 10.1016/j.jct.2025.107460
Yixin Ma , Zeyu Hu , Lin Yang , Lianzheng Zhang , Shanshan Liu , Zhishan Zhang , Dongmei Xu , Jun Gao , Yinglong Wang
In industrial production, isopropanol (IPA) and isopropyl acetate (IPAC) serve as raw materials and products for each other. Due to the inability to achieve a 100 % conversion rate of the products, they usually exist as a mixture. However, IPA and IPAC can form a binary azeotropic mixture, making it difficult to separate them through conventional separation methods. In the current work, extractive distillation is being considered for the separation of IPA and IPAC using entrainers such as 4-methyl-2-pentanone (MIBK), chlorobenzene and butyl acetate. The vapor-liquid equilibrium (VLE) data of the binary systems (IPAC + MIBK / chlorobenzene / butyl acetate) at 101.3 kPa were determined, and the results passed the thermodynamic consistency tests (van Ness and pure component). Using three commonly used activity coefficient models (NRTL, UNIQUAC and Wilson) to correlate and regress the data, the results indicate that the vapor phase and temperature deviations are respectively less than 0.0037 and 0.1847 K. Afterwards, suitable entrainer was screened using the binary interaction parameters of regression, and an extractive distillation (ED) process was designed. The products purity reached 99.6 wt%, and the parameters were optimized with the goal of minimizing the bottom heat duty.
{"title":"Extractive distillation separation of isopropanol - isopropyl acetate azeotrope: Vapor-liquid equilibrium measurement and process optimization","authors":"Yixin Ma , Zeyu Hu , Lin Yang , Lianzheng Zhang , Shanshan Liu , Zhishan Zhang , Dongmei Xu , Jun Gao , Yinglong Wang","doi":"10.1016/j.jct.2025.107460","DOIUrl":"10.1016/j.jct.2025.107460","url":null,"abstract":"<div><div>In industrial production, isopropanol (IPA) and isopropyl acetate (IPAC) serve as raw materials and products for each other. Due to the inability to achieve a 100 % conversion rate of the products, they usually exist as a mixture. However, IPA and IPAC can form a binary azeotropic mixture, making it difficult to separate them through conventional separation methods. In the current work, extractive distillation is being considered for the separation of IPA and IPAC using entrainers such as 4-methyl-2-pentanone (MIBK), chlorobenzene and butyl acetate. The vapor-liquid equilibrium (VLE) data of the binary systems (IPAC + MIBK / chlorobenzene / butyl acetate) at 101.3 kPa were determined, and the results passed the thermodynamic consistency tests (van Ness and pure component). Using three commonly used activity coefficient models (NRTL, UNIQUAC and Wilson) to correlate and regress the data, the results indicate that the vapor phase and temperature deviations are respectively less than 0.0037 and 0.1847 K. Afterwards, suitable entrainer was screened using the binary interaction parameters of regression, and an extractive distillation (ED) process was designed. The products purity reached 99.6 <em>wt</em>%, and the parameters were optimized with the goal of minimizing the bottom heat duty.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"205 ","pages":"Article 107460"},"PeriodicalIF":2.2,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143445846","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 : 2025-01-29DOI: 10.1016/j.jct.2025.107454
Xiayao Peng, Ying Tan, Zhen Yang, Yuanyuan Duan
{"title":"Corrigendum to “Experimental speed of sound in two emerging mixture working fluids of [R1234ze(Z) + R1233zd(E)] and [R1234ze(Z) + isobutane]” [J. Chem. Thermodyn. 198 (2024) 107340]","authors":"Xiayao Peng, Ying Tan, Zhen Yang, Yuanyuan Duan","doi":"10.1016/j.jct.2025.107454","DOIUrl":"10.1016/j.jct.2025.107454","url":null,"abstract":"","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"204 ","pages":"Article 107454"},"PeriodicalIF":2.2,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379065","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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