Pub Date : 2025-12-01Epub Date: 2025-08-21DOI: 10.1016/j.jct.2025.107565
Zhouxuan Zang, Jianhua Zhou, Ningke Pang, Xin Fang, Yong Xiang, Wencai Bai, Yi Yu, Li Xu, Guoji Liu
In our work, the solubility of cyclododecanone (CDON) in four binary solvent systems (ethanol + ethyl acetate, ethanol + acetone, ethanol + toluene and ethanol +1,2-dichloroethane) was experimentally investigated using the isothermal saturation method under 101.3 kPa over a temperature range of 278.15–313.15 K. The results demonstrate that the solubility of (CDON) increases with rising temperature. The dissolution behavior of CDON was elucidated using the Hansen solubility parameters. The experimental data were correlated and analyzed using the λh equation, modified Apelblat equation, van't Hoff equation, Yaws model, Jouyban-Acree model, Sun model. The values of RD and RMSD indicate that the selected model exhibits well fitted with the solubility data in the binary solvent systems. The thermodynamic properties (ΔsolH0, ΔsolS0, ΔsolG0, %ξH and %ξTS) of the system were discussed using the van't Hoff equation. The experimental results indicate that the dissolution process of CDON was entropy-driven and endothermic. The solvation free energy changes of CDON in a binary solution system were investigated through molecular dynamics methods. Furthermore, the relationship was elucidated between the mixed solvents and the solubility. In summary, this research will provide strong guidance for the improvement of CDON production processes.
{"title":"Measurement and molecular simulation of the solubility properties of cyclododecanone in binary solvents","authors":"Zhouxuan Zang, Jianhua Zhou, Ningke Pang, Xin Fang, Yong Xiang, Wencai Bai, Yi Yu, Li Xu, Guoji Liu","doi":"10.1016/j.jct.2025.107565","DOIUrl":"10.1016/j.jct.2025.107565","url":null,"abstract":"<div><div>In our work, the solubility of cyclododecanone (CDON) in four binary solvent systems (ethanol + ethyl acetate, ethanol + acetone, ethanol + toluene and ethanol +1,2-dichloroethane) was experimentally investigated using the isothermal saturation method under 101.3 kPa over a temperature range of 278.15–313.15 K. The results demonstrate that the solubility of (CDON) increases with rising temperature. The dissolution behavior of CDON was elucidated using the Hansen solubility parameters. The experimental data were correlated and analyzed using the λh equation, modified Apelblat equation, van't Hoff equation, Yaws model, Jouyban-Acree model, Sun model. The values of RD and RMSD indicate that the selected model exhibits well fitted with the solubility data in the binary solvent systems. The thermodynamic properties (Δ<sub>sol</sub>H<sup>0</sup>, Δ<sub>sol</sub>S<sup>0</sup>, Δ<sub>sol</sub>G<sup>0</sup>, %ξ<sub>H</sub> and %ξ<sub>TS</sub>) of the system were discussed using the van't Hoff equation. The experimental results indicate that the dissolution process of CDON was entropy-driven and endothermic. The solvation free energy changes of CDON in a binary solution system were investigated through molecular dynamics methods. Furthermore, the relationship was elucidated between the mixed solvents and the solubility. In summary, this research will provide strong guidance for the improvement of CDON production processes.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107565"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144893122","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 : 2025-12-01Epub Date: 2025-07-17DOI: 10.1016/j.jct.2025.107546
Maxwell Risseli Laurentino da Silva, Alanderson Arthu Araújo Alves, Lucas Henrique Gomes de Medeiros, Hugo Andersson Dantas Medeiros, Hosiberto Batista de Sant'Ana, Filipe Xavier Feitosa
The phase equilibria of two hexadecane + butylcyclohexane mixtures were investigated by adding carbon dioxide, for which no data are available in the literature, using a variable-volume high-pressure view cell. Five isopleths ranging from 13 to 85 mol% carbon dioxide were studied at five different temperature conditions. In addition, high-pressure density data were obtained for three different hexadecane + butylcyclohexane mixtures at five temperatures and pressures up to 100 MPa. The classical Peng-Robinson equation of state (PR EoS) was applied with a fully predictive mixing rule incorporating a temperature-dependent binary interaction parameter () to model the experimentally measured phase equilibria. The two ternary mixtures exhibited classical behavior across all global compositions investigated, presenting only simple liquid-vapor equilibrium. The PR EoS approach qualitatively captured the experimental phase behavior of both systems. Moreover, the experimental density data were correlated using the Tammann–Tait equation, and the following thermodynamic derivative properties were calculated: isothermal compressibility (), isobaric thermal expansivity (, thermal pressure coefficient (), and internal pressure ().
{"title":"High-pressure phase equilibria and volumetric properties of the CO2 + hexadecane + butylcyclohexane system: Experimental and modeling study","authors":"Maxwell Risseli Laurentino da Silva, Alanderson Arthu Araújo Alves, Lucas Henrique Gomes de Medeiros, Hugo Andersson Dantas Medeiros, Hosiberto Batista de Sant'Ana, Filipe Xavier Feitosa","doi":"10.1016/j.jct.2025.107546","DOIUrl":"10.1016/j.jct.2025.107546","url":null,"abstract":"<div><div>The phase equilibria of two hexadecane + butylcyclohexane mixtures were investigated by adding carbon dioxide, for which no data are available in the literature, using a variable-volume high-pressure view cell. Five isopleths ranging from 13 to 85 mol% carbon dioxide were studied at five different temperature conditions. In addition, high-pressure density data were obtained for three different hexadecane + butylcyclohexane mixtures at five temperatures and pressures up to 100 MPa. The classical Peng-Robinson equation of state (PR EoS) was applied with a fully predictive mixing rule incorporating a temperature-dependent binary interaction parameter (<span><math><mrow><msub><mi>k</mi><mi>ij</mi></msub></mrow></math></span>) to model the experimentally measured phase equilibria. The two ternary mixtures exhibited classical behavior across all global compositions investigated, presenting only simple liquid-vapor equilibrium. The PR EoS approach qualitatively captured the experimental phase behavior of both systems. Moreover, the experimental density data were correlated using the Tammann–Tait equation, and the following thermodynamic derivative properties were calculated: isothermal compressibility (<span><math><mrow><msub><mi>κ</mi><mi>T</mi></msub></mrow></math></span><em>)</em>, isobaric thermal expansivity (<span><math><mrow><msub><mi>α</mi><mi>P</mi></msub><mo>)</mo></mrow></math></span>, thermal pressure coefficient (<span><math><mrow><msub><mi>γ</mi><mi>v</mi></msub></mrow></math></span>), and internal pressure (<span><math><mrow><msub><mi>P</mi><mi>i</mi></msub></mrow></math></span>).</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107546"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144672174","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 : 2025-12-01Epub Date: 2025-07-29DOI: 10.1016/j.jct.2025.107549
Alexis Gibson , Shuhao Yang , Richard E. Riman , Alexandra Navrotsky , Brian F. Woodfield
This work investigates the heat capacity and thermodynamic properties of three rare earth oxychlorides (REOCl), TmOCl, NdOCl, and YOCl. To understand their thermodynamic landscapes, we measured their heat capacities from 1.8 to 300 K. Our results indicate the presence of several Schottky anomalies at low temperatures (below 7 K), and TmOCl had an additional Schottky anomaly centered around 25 K, which we attribute to a contribution from f-block electrons. We fitted the data to theoretical functions and used these models to derive the standard entropy, enthalpy, and Gibbs energy. Using previously published enthalpy of formation data, we determined the Gibbs energies of formation from the elements and the oxides and chlorides at selected temperatures. At 298.15 K, the Gibbs energy of formation relative to oxides and chlorides was calculated to be −59.4 kJ·mol−1, −41.0 kJ·mol−1, and − 11.1 kJ·mol−1 for NdOCl, YOCl, and TmOCl, respectively. The Gibbs energy of formation of REOCl relative to the elements at 298.15 K was calculated to be −952.3 kJ·mol−1, −967.4 kJ·mol−1, and − 938.9 kJ·mol−1 for NdOCl, YOCl, and TmOCl, respectively. These results confirm the stability of REOCl relative to the elements and the binary chlorides and oxides.
{"title":"Heat capacity and thermodynamic functions of stoichiometric rare earth oxychlorides (REOCl)","authors":"Alexis Gibson , Shuhao Yang , Richard E. Riman , Alexandra Navrotsky , Brian F. Woodfield","doi":"10.1016/j.jct.2025.107549","DOIUrl":"10.1016/j.jct.2025.107549","url":null,"abstract":"<div><div>This work investigates the heat capacity and thermodynamic properties of three rare earth oxychlorides (REOCl), TmOCl, NdOCl, and YOCl. To understand their thermodynamic landscapes, we measured their heat capacities from 1.8 to 300 K. Our results indicate the presence of several Schottky anomalies at low temperatures (below 7 K), and TmOCl had an additional Schottky anomaly centered around 25 K, which we attribute to a contribution from f-block electrons. We fitted the data to theoretical functions and used these models to derive the standard entropy, enthalpy, and Gibbs energy. Using previously published enthalpy of formation data, we determined the Gibbs energies of formation from the elements and the oxides and chlorides at selected temperatures. At 298.15 K, the Gibbs energy of formation relative to oxides and chlorides was calculated to be −59.4 kJ·mol<sup>−1</sup>, −41.0 kJ·mol<sup>−1</sup>, and − 11.1 kJ·mol<sup>−1</sup> for NdOCl, YOCl, and TmOCl, respectively. The Gibbs energy of formation of REOCl relative to the elements at 298.15 K was calculated to be −952.3 kJ·mol<sup>−1</sup>, −967.4 kJ·mol<sup>−1</sup>, and − 938.9 kJ·mol<sup>−1</sup> for NdOCl, YOCl, and TmOCl, respectively. These results confirm the stability of REOCl relative to the elements and the binary chlorides and oxides.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107549"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144749987","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 : 2025-12-01Epub Date: 2025-07-23DOI: 10.1016/j.jct.2025.107550
Houchun Yan, He Ma, Xuqiang Li, Shaolong Dong, Qingsong Li
To separate higher-rank phenols from the coal tar, the model oil was constructed, and the separation efficiency of various solvents was analyzed using solvent power, selectivity, and performance index. The liquid-liquid equilibrium data of cumene + {4-ethylphenol, 4-propylphenol, 2-allylphenol, and 2-isopropylphenol} + ethanolamine was measured at 298.2 K and 101.3 kPa, and the distribution coefficient and separation factor were calculated. Furthermore, the NRTL and UNIQUAC models were correlated with the LLE data, and the model parameters were tested by the GMcal_TieLinesLL tool, which shows that the results meet the Gibbs stability criteria. The separation mechanism was explored by analyzing σ-profile, deformation charge density, interaction energy, and RDG analysis.
{"title":"Separation of higher-rank phenols from coal tar models: a combination of experiment and mechanism analysis","authors":"Houchun Yan, He Ma, Xuqiang Li, Shaolong Dong, Qingsong Li","doi":"10.1016/j.jct.2025.107550","DOIUrl":"10.1016/j.jct.2025.107550","url":null,"abstract":"<div><div>To separate higher-rank phenols from the coal tar, the model oil was constructed, and the separation efficiency of various solvents was analyzed using solvent power, selectivity, and performance index. The liquid-liquid equilibrium data of cumene + {4-ethylphenol, 4-propylphenol, 2-allylphenol, and 2-isopropylphenol} + ethanolamine was measured at 298.2 K and 101.3 kPa, and the distribution coefficient and separation factor were calculated. Furthermore, the NRTL and UNIQUAC models were correlated with the LLE data, and the model parameters were tested by the GMcal_TieLinesLL tool, which shows that the results meet the Gibbs stability criteria. The separation mechanism was explored by analyzing σ-profile, deformation charge density, interaction energy, and RDG analysis.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107550"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144713685","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 : 2025-12-01Epub Date: 2025-08-20DOI: 10.1016/j.jct.2025.107566
Alessandro A.L. Araújo , Hugo A. Dantas Medeiros , Dival de Brito Guerra-Neto , Anderson A. Jesus , Eduardo L. Barros Neto , Osvaldo Chiavone-Filho
Nonionic surfactant aqueous solutions exhibit phase separation into two distinct liquid micellar phases: a dilute phase with a low surfactant concentration and a surfactant-rich phase, known as coacervate. The application of these surfactants in solute extraction processes from aqueous media has been increasing, highlighting the importance of understanding their solubility behavior. This work reports cloud point data of a systematic series of binary aqueous mixtures of polyethylene glycol monododecyl ethers, ranging the degree of ethoxylation (6, 7, 8, 9, and 10). The cloud points were detected in a high-pressure apparatus by monitoring the turbidity appearance and disappearance of the mixtures as the temperature changed at a constant rate of 0.1 K/min, under constant pressures up to 30 MPa (4 isobarics). The miscibility behavior of the studied systems was positively affected by both the degree of ethoxylation and the applied pressure. The Flory-Huggins (FH) equation was applied to correlate the solubility curves, allowing the generation of pseudo-experimental tie lines across the observed temperature range. These tie lines were further correlated using the nonrandom two-liquid (NRTL) model with a linear temperature dependence for the interaction parameters. The Flory-Huggins and NRTL models showed agreement within the bounds of experimental uncertainty, with root-mean-square deviations (RMSD) of 0.5 K for temperature and 0.1 % for composition, respectively. Feasible process applications of these models, including enhanced oil recovery through chemical flooding, are indicated.
{"title":"Solubility behavior for aqueous polyethylene glycol monododecyl ether systems up to 30 MPa: measurement and correlation","authors":"Alessandro A.L. Araújo , Hugo A. Dantas Medeiros , Dival de Brito Guerra-Neto , Anderson A. Jesus , Eduardo L. Barros Neto , Osvaldo Chiavone-Filho","doi":"10.1016/j.jct.2025.107566","DOIUrl":"10.1016/j.jct.2025.107566","url":null,"abstract":"<div><div>Nonionic surfactant aqueous solutions exhibit phase separation into two distinct liquid micellar phases: a dilute phase with a low surfactant concentration and a surfactant-rich phase, known as coacervate. The application of these surfactants in solute extraction processes from aqueous media has been increasing, highlighting the importance of understanding their solubility behavior. This work reports cloud point data of a systematic series of binary aqueous mixtures of polyethylene glycol monododecyl ethers, ranging the degree of ethoxylation (6, 7, 8, 9, and 10). The cloud points were detected in a high-pressure apparatus by monitoring the turbidity appearance and disappearance of the mixtures as the temperature changed at a constant rate of 0.1 K/min, under constant pressures up to 30 MPa (4 isobarics). The miscibility behavior of the studied systems was positively affected by both the degree of ethoxylation and the applied pressure. The Flory-Huggins (FH) equation was applied to correlate the solubility curves, allowing the generation of pseudo-experimental tie lines across the observed temperature range. These tie lines were further correlated using the nonrandom two-liquid (NRTL) model with a linear temperature dependence for the interaction parameters. The Flory-Huggins and NRTL models showed agreement within the bounds of experimental uncertainty, with root-mean-square deviations (RMSD) of 0.5 K for temperature and 0.1 % for composition, respectively. Feasible process applications of these models, including enhanced oil recovery through chemical flooding, are indicated.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107566"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144889393","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 : 2025-12-01Epub Date: 2025-08-12DOI: 10.1016/j.jct.2025.107564
Zhiruo Li , Yue Xu , Yini Wang , Yinxin Yang , Ruoxi Huang , Linxu Dong , Haikuan Yuan , Lijuan Zhang , Xijian Liu , Yifeng Zhang , Jie Lu
The solubility of (S)- and (R,S)-dropropizine in seven single solvents at 283.15–323.15 K was investigated by the static method, and the relevance of the experimental solubility data was evaluated through three thermodynamic models (λh, Apelblat and Yaws formulas). All thermodynamic models had a good fit and ARD% values were all less than 3 %. The solubility of (S)- and (R,S)-dropropizine in the chosen solvents increased as the temperature rose. Then the solvent effect on solubility was elucidated by the KAT-LSER model. Furthermore, the solvation free energy of solutes in the selected solvents was simulated to investigate the solute-solvent interactions. In addition, the crystal structure of (S)- and (R,S)-dropropizine was predicted using the PXRD patterns. The unit cells of (S)- and (R,S)-dropropizine belonged to the monoclinic and triclinic systems, respectively. The analysis of intermolecular interactions was conducted using Hirshfeld surface analysis. Ultimately, the solubility isotherm ternary phase diagram in ethanol further identified that (R,S)-dropropizine was a racemic compound. This finding of this study will offer theoretical support to the pharmaceutical industry for better understanding the crystallization resolution of this chiral system.
{"title":"Solubility study and molecular simulation of (S)- and (R,S)-dropropizine in seven single solvents","authors":"Zhiruo Li , Yue Xu , Yini Wang , Yinxin Yang , Ruoxi Huang , Linxu Dong , Haikuan Yuan , Lijuan Zhang , Xijian Liu , Yifeng Zhang , Jie Lu","doi":"10.1016/j.jct.2025.107564","DOIUrl":"10.1016/j.jct.2025.107564","url":null,"abstract":"<div><div>The solubility of (<em>S</em>)- and (<em>R</em>,<em>S</em>)-dropropizine in seven single solvents at 283.15–323.15 K was investigated by the static method, and the relevance of the experimental solubility data was evaluated through three thermodynamic models (<em>λh</em>, Apelblat and Yaws formulas). All thermodynamic models had a good fit and <em>ARD</em>% values were all less than 3 %. The solubility of (<em>S</em>)- and (<em>R</em>,<em>S</em>)-dropropizine in the chosen solvents increased as the temperature rose. Then the solvent effect on solubility was elucidated by the KAT-LSER model. Furthermore, the solvation free energy of solutes in the selected solvents was simulated to investigate the solute-solvent interactions. In addition, the crystal structure of (<em>S</em>)- and (<em>R</em>,<em>S</em>)-dropropizine was predicted using the PXRD patterns. The unit cells of (<em>S</em>)- and (<em>R</em>,<em>S</em>)-dropropizine belonged to the monoclinic and triclinic systems, respectively. The analysis of intermolecular interactions was conducted using Hirshfeld surface analysis. Ultimately, the solubility isotherm ternary phase diagram in ethanol further identified that (<em>R</em>,<em>S</em>)-dropropizine was a racemic compound. This finding of this study will offer theoretical support to the pharmaceutical industry for better understanding the crystallization resolution of this chiral system.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107564"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144852754","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}
Four deep eutectic solvents (DESs) based on 1,1,3,3-tetramethylguanidine (TMG) and N-heterocycles (succinimide, 2-pyrrolidinone, 2-oxazolidone, N-methylurea) were prepared and assessed for NO capture. At 313.2 K and 1 bar, the viscosities of TMG/succinimide (TMG-Succ) and TMG/2-pyrrolidinone (TMG-Pyrr) were measured as 49.23 mPa·s and 2.85 mPa·s, respectively, while their corresponding nitric oxide (NO) uptake capacities reached 1.62 Mol·kg−1 and 1.10 Mol·kg−1 under identical conditions. Spectroscopic analysis confirmed chemisorption in TMG-Succ versus physical dissolution in TMG-Pyrr. Thermodynamic fits yielded the absorption enthalpy ΔH = −16.94 kJ·Mol−1 for TMG-Succ and − 70.1 kJ·Mol−1 for TMG-Pyrr DES. In addition, the absorption capacities of both DESs remained almost unchanged during the 10 cycles of absorption-desorption experiments, highlighting their low-viscosity, high-capacity, and energy-efficient reversible NO capture performance
{"title":"Thermodynamic analysis of nitric oxide absorption in deep eutectic solvents comprising 1,1,3,3-tetramethylguanidine","authors":"Wentao Zheng , Jialing Chen , Yujiao Jia , Nengqi Sun , Xiankun Wu","doi":"10.1016/j.jct.2025.107563","DOIUrl":"10.1016/j.jct.2025.107563","url":null,"abstract":"<div><div>Four deep eutectic solvents (DESs) based on 1,1,3,3-tetramethylguanidine (TMG) and N-heterocycles (succinimide, 2-pyrrolidinone, 2-oxazolidone, <em>N</em>-methylurea) were prepared and assessed for NO capture. At 313.2 K and 1 bar, the viscosities of TMG/succinimide (TMG-Succ) and TMG/2-pyrrolidinone (TMG-Pyrr) were measured as 49.23 mPa·s and 2.85 mPa·s, respectively, while their corresponding nitric oxide (NO) uptake capacities reached 1.62 Mol·kg<sup>−1</sup> and 1.10 Mol·kg<sup>−1</sup> under identical conditions. Spectroscopic analysis confirmed chemisorption in TMG-Succ <em>versus</em> physical dissolution in TMG-Pyrr. Thermodynamic fits yielded the absorption enthalpy ΔH = −16.94 kJ·Mol<sup>−1</sup> for TMG-Succ and − 70.1 kJ·Mol<sup>−1</sup> for TMG-Pyrr DES. In addition, the absorption capacities of both DESs remained almost unchanged during the 10 cycles of absorption-desorption experiments, highlighting their low-viscosity, high-capacity, and energy-efficient reversible NO capture performance</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107563"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144830074","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 : 2025-12-01Epub Date: 2025-07-31DOI: 10.1016/j.jct.2025.107551
Bo Wang , Bo Li , Jun Chen , Hong-xia Pan , Chong Li , Li-zhen Chen , Jian-long Wang
The solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven pure solvents (acetone, cyclohexanone, 2-butanone, methyl acetate, ethyl acetate, benzene, chlorobenzene, pyridine, acetonitrile, 1,2-dichloroethane and 1,4-dioxane) was measured by laser dynamic method at the temperature range from 293.15 K to 333.15 K under the pressure of 101.3 kPa. The study found that the solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl is positively correlated with increasing temperature. The experimental data were correlated using four thermodynamic models: the modified Apelblat model, van't Hoff model, NRTL model, and Wilson model. The modified Apelblat model demonstrated superior correlation performance. Hirshfeld surface and molecular electrostatic potential surface analysis were also conducted to investigate the solvent-solute interaction sites and the effects of interactions on the solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven selected pure solvents. Additionally, the thermodynamic properties of the dissolution process were calculated using the van't Hoff model, and the results indicated that the dissolution of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven selected pure solvents is an endothermic and entropy-increasing process.
{"title":"Solubility determination, model evaluation and thermodynamic analysis of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven pure solvents","authors":"Bo Wang , Bo Li , Jun Chen , Hong-xia Pan , Chong Li , Li-zhen Chen , Jian-long Wang","doi":"10.1016/j.jct.2025.107551","DOIUrl":"10.1016/j.jct.2025.107551","url":null,"abstract":"<div><div>The solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven pure solvents (acetone, cyclohexanone, 2-butanone, methyl acetate, ethyl acetate, benzene, chlorobenzene, pyridine, acetonitrile, 1,2-dichloroethane and 1,4-dioxane) was measured by laser dynamic method at the temperature range from 293.15 K to 333.15 K under the pressure of 101.3 kPa. The study found that the solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl is positively correlated with increasing temperature. The experimental data were correlated using four thermodynamic models: the modified Apelblat model, van't Hoff model, NRTL model, and Wilson model. The modified Apelblat model demonstrated superior correlation performance. Hirshfeld surface and molecular electrostatic potential surface analysis were also conducted to investigate the solvent-solute interaction sites and the effects of interactions on the solubility of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven selected pure solvents. Additionally, the thermodynamic properties of the dissolution process were calculated using the van't Hoff model, and the results indicated that the dissolution of 2,2′,4,4′,6,6′-hexanitrobibenzyl in eleven selected pure solvents is an endothermic and entropy-increasing process.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107551"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144767225","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 : 2025-12-01Epub Date: 2025-08-05DOI: 10.1016/j.jct.2025.107552
Yingxi Qi, Tuo Zheng, Wenlin Xu, Xi Chen, Hua Zhang
The gas-phase pρTx properties of the R290/R744/R1234ze(E) ternary mixed refrigerants are measured by the Burnett isothermal expansion method at temperatures ranging from 270 K to 320 K and corresponding pressures from 115 kPa to 1861 kPa. The standard uncertainties of the experimental system are evaluated: temperature uncertainty of 8.1 mK, pressure uncertainty of 1.7 kPa, and mass fraction uncertainty of 0.006. The relative standard uncertainty of density is derived as 0.006. The experimental results are correlated with the Virial equation of state (EOS) and the virial coefficients are fitted. The pressures calculated by the fitted Virial EOS agrees well with the experimental pressures with the relative deviations are within ±1.0 %. This study is useful for development of new environmentally friendly mixed refrigerants.
{"title":"Experimental study of pρTx characteristics of R290/R744/R1234ze(E) ternary mixed refrigerants","authors":"Yingxi Qi, Tuo Zheng, Wenlin Xu, Xi Chen, Hua Zhang","doi":"10.1016/j.jct.2025.107552","DOIUrl":"10.1016/j.jct.2025.107552","url":null,"abstract":"<div><div>The gas-phase <em>pρTx</em> properties of the R290/R744/R1234ze(E) ternary mixed refrigerants are measured by the Burnett isothermal expansion method at temperatures ranging from 270 K to 320 K and corresponding pressures from 115 kPa to 1861 kPa. The standard uncertainties of the experimental system are evaluated: temperature uncertainty of 8.1 mK, pressure uncertainty of 1.7 kPa, and mass fraction uncertainty of 0.006. The relative standard uncertainty of density is derived as 0.006. The experimental results are correlated with the Virial equation of state (EOS) and the virial coefficients are fitted. The pressures calculated by the fitted Virial EOS agrees well with the experimental pressures with the relative deviations are within ±1.0 %. This study is useful for development of new environmentally friendly mixed refrigerants.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107552"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144771340","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 : 2025-12-01Epub Date: 2025-07-28DOI: 10.1016/j.jct.2025.107548
Clara M. Dixon , Mina Aziziha , Amir Mofrad , Jorge Paz Soldan Palma , Ronald E. Booth , Aiswarya Padinhare Manissery , Jack A. Wilson , Hans-Conrad zur Loye , Hunter B. Tisdale , Juliano Schorne-Pinto , Theodore M. Besmann
Gibbs energy models necessary to describe the thermochemical behavior of cesium and iodine in molten FLiNaK (46.5LiF-11.5NaF-42KF mol%), a proposed molten salt reactor coolant and fuel solvent, have been developed as they are of concern due to their high radiotoxicity and volatility. The six constituent pseudo-binary systems LiI-CsI, LiI-KI, LiI-NaI, NaI-KI, KI-CsI and NaI-CsI were evaluated using available phase equilibria and mixing enthalpy measurements. The models for the ternary reciprocal salt systems Li,Cs|F,I, Li,K|F,I, Li,Na|F,I, Na,K|F,I, Na,Cs|F,I and K,Cs|F,I were obtained by interpolation of the optimized pseudo-binary systems and parameters fit as necessary based on observed behavior. The additive (common cation) pseudo-ternary system representations were obtained by interpolation of the optimized pseudo-binary systems, and parameters for those as well modified as necessary to best fit observations. Together, the evaluated systems contain the necessary thermochemical models to generate quaternary and higher order reciprocal salt system descriptions, with the representations of the Li,Na,Cs|F,I, Li,K,Cs|F,I and Na,K,Cs|F,I quaternary reciprocal salt systems largely well-reproducing reported behavior. These salt system representations have subsequently been incorporated in the Molten Salt Thermal Properties Database – Thermochemical (MSTDB-TC).
{"title":"Thermodynamic assessment of the Li, Na, K, Cs | F, I reciprocal salt for MSR applications","authors":"Clara M. Dixon , Mina Aziziha , Amir Mofrad , Jorge Paz Soldan Palma , Ronald E. Booth , Aiswarya Padinhare Manissery , Jack A. Wilson , Hans-Conrad zur Loye , Hunter B. Tisdale , Juliano Schorne-Pinto , Theodore M. Besmann","doi":"10.1016/j.jct.2025.107548","DOIUrl":"10.1016/j.jct.2025.107548","url":null,"abstract":"<div><div>Gibbs energy models necessary to describe the thermochemical behavior of cesium and iodine in molten FLiNaK (46.5LiF-11.5NaF-42KF mol%), a proposed molten salt reactor coolant and fuel solvent, have been developed as they are of concern due to their high radiotoxicity and volatility. The six constituent pseudo-binary systems LiI-CsI, LiI-KI, LiI-NaI, NaI-KI, KI-CsI and NaI-CsI were evaluated using available phase equilibria and mixing enthalpy measurements. The models for the ternary reciprocal salt systems Li,Cs|F,I, Li,K|F,I, Li,Na|F,I, Na,K|F,I, Na,Cs|F,I and K,Cs|F,I were obtained by interpolation of the optimized pseudo-binary systems and parameters fit as necessary based on observed behavior. The additive (common cation) pseudo-ternary system representations were obtained by interpolation of the optimized pseudo-binary systems, and parameters for those as well modified as necessary to best fit observations. Together, the evaluated systems contain the necessary thermochemical models to generate quaternary and higher order reciprocal salt system descriptions, with the representations of the Li,Na,Cs|F,I, Li,K,Cs|F,I and Na,K,Cs|F,I quaternary reciprocal salt systems largely well-reproducing reported behavior. These salt system representations have subsequently been incorporated in the Molten Salt Thermal Properties Database – Thermochemical (<em>MSTDB-TC</em>).</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107548"},"PeriodicalIF":2.2,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144852766","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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