In this study, the static method was employed to investigate the solubility of potassium benzoate in ten pure solvents, including methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, formamide, N,N-dimethylformamide, and N,N-dimethylacetamide, within the temperature range from 282.95 to 317.95 K at atmospheric pressure. The influence of temperature and solvent type on the solubility of potassium benzoate was analyzed. The experimental results revealed that the solubility of potassium benzoate increased with the rising of temperature in all the solvents studied. In addition, the experimental solubility data of potassium benzoate was fitted using the modified Apelblat equation and the λh equation. The calculated data showed that the modified Apelblat equation gave the better results compared to the λh equation. Furthermore, the Hansen solubility parameters and dipole moments were used to elucidate the solubilization behavior of potassium benzoate in various solvents. Finally, the dissolution thermodynamic properties of potassium benzoate including the Gibbs free energy, enthalpy and entropy were calculated based on the experimental solubility data and the van't Hoff equation.
{"title":"Solubility and dissolution thermodynamic properties of potassium benzoate in pure solvents","authors":"Zhengda Zhou , Yuchen Yue , Siyu Wang , Tianxia Guo , Zihang Xu , Chunsong Liu , Yun Gao , Yanan Zhou","doi":"10.1016/j.jct.2025.107569","DOIUrl":"10.1016/j.jct.2025.107569","url":null,"abstract":"<div><div>In this study, the static method was employed to investigate the solubility of potassium benzoate in ten pure solvents, including methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, formamide, <em>N</em>,<em>N</em>-dimethylformamide, and <em>N</em>,<em>N</em>-dimethylacetamide, within the temperature range from 282.95 to 317.95 K at atmospheric pressure. The influence of temperature and solvent type on the solubility of potassium benzoate was analyzed. The experimental results revealed that the solubility of potassium benzoate increased with the rising of temperature in all the solvents studied. In addition, the experimental solubility data of potassium benzoate was fitted using the modified Apelblat equation and the λh equation. The calculated data showed that the modified Apelblat equation gave the better results compared to the λh equation. Furthermore, the Hansen solubility parameters and dipole moments were used to elucidate the solubilization behavior of potassium benzoate in various solvents. Finally, the dissolution thermodynamic properties of potassium benzoate including the Gibbs free energy, enthalpy and entropy were calculated based on the experimental solubility data and the van't Hoff equation.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107569"},"PeriodicalIF":2.2,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144933454","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 : 2025-08-21DOI: 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":"2025-08-21","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}
In this work, the density (ρ) and viscosity (η) values were measured experimentally for the n-propanol (NPA) /isopropanol (IPA) (1) + 3-diethylaminopropylamine (DEAPA) Abd et al. (2020) (2) binary mixed system at T = 298.15–318.15 K and P = 100.5 kPa. To further study the physical and chemical properties of the binary mixed system, their excess molar volume (VmE), viscosity deviation (Δη), and excess Gibbs free energy (ΔG⁎E) were calculated, through which there is an interaction between 3-diethylaminopropylamine and n-propanol/isopropanol molecules. To validate the reliability of the basic data, several semi-empirical models were used to predict the experimental densities and viscosities, among which the Jouyban - Acree model (J-A) and the nonlinear least squares method for fitting the density data of the binary mixed system to the composition and temperature, the McAllister four-body viscosity model was used to fit the viscosity data to the composition of binary mixed systems, and the calculated results of ΔG⁎E, Δη and VmE were fitted using the Redlich-Kister (R - K) equations. In addition, the presence of intermolecular hydrogen bond (IHB) structure of the form as -OH···NH2- in the system was demonstrated by spectroscopic characterizations including Raman, ultraviolet (UV) and nuclear magnetic resonance hydrogen spectroscopy (1H NMR), and the existence of IHBs among the binary mixed system was further verified based on computational chemical theory. Finally, the CO2 uptake studies were conducted to compare with the monoamine and alcohol-amine mixed solutions to provide a new way for CO2 capture.
{"title":"Excess properties, intermolecular structure, and CO2 absorption performance of n-propanol/isopropanol and 3-diethylaminopropylamine binary mixed system","authors":"Yuchang Wang, Jiaqi Zang, Rui Cao, Wenjie Zhai, Mengchao Feng, Rongrong Li, Kai Ma, Jianbin Zhang","doi":"10.1016/j.jct.2025.107567","DOIUrl":"10.1016/j.jct.2025.107567","url":null,"abstract":"<div><div>In this work, the density (<em>ρ</em>) and viscosity (<em>η</em>) values were measured experimentally for the n-propanol (NPA) /isopropanol (IPA) (1) + 3-diethylaminopropylamine (DEAPA) Abd et al. (2020) (2) binary mixed system at <em>T</em> = 298.15–318.15 K and <em>P</em> = 100.5 kPa. To further study the physical and chemical properties of the binary mixed system, their excess molar volume (<em>V</em><sub><em>m</em></sub><sup><em>E</em></sup>), viscosity deviation (<em>Δη</em>), and excess Gibbs free energy (<em>ΔG</em><sup><em>⁎E</em></sup>) were calculated, through which there is an interaction between 3-diethylaminopropylamine and n-propanol/isopropanol molecules. To validate the reliability of the basic data, several semi-empirical models were used to predict the experimental densities and viscosities, among which the Jouyban - Acree model (<em>J</em>-A) and the nonlinear least squares method for fitting the density data of the binary mixed system to the composition and temperature, the McAllister four-body viscosity model was used to fit the viscosity data to the composition of binary mixed systems, and the calculated results of <em>ΔG</em><sup><em>⁎E</em></sup>, <em>Δη</em> and <em>V</em><sub><em>m</em></sub><sup><em>E</em></sup> were fitted using the Redlich-Kister (R - K) equations. In addition, the presence of intermolecular hydrogen bond (IHB) structure of the form as -OH···NH<sub>2</sub>- in the system was demonstrated by spectroscopic characterizations including Raman, ultraviolet (UV) and nuclear magnetic resonance hydrogen spectroscopy (<sup>1</sup>H NMR), and the existence of IHBs among the binary mixed system was further verified based on computational chemical theory. Finally, the CO<sub>2</sub> uptake studies were conducted to compare with the monoamine and alcohol-amine mixed solutions to provide a new way for CO<sub>2</sub> capture.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107567"},"PeriodicalIF":2.2,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144912931","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 : 2025-08-20DOI: 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":"2025-08-20","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 : 2025-08-12DOI: 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":"2025-08-12","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":"2025-08-09","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 : 2025-08-08DOI: 10.1016/j.jct.2025.107561
Christian Bouchot , Raquel I. Rodríguez-Cisneros , José Domenzaín-González , Ricardo García-Morales , Francisco J. Verónico-Sánchez , Abel Zúñiga-Moreno , Octavio Elizalde-Solis
Thermophysical properties under high pressure and high temperature of biodiesel are mainly available for samples with methyl ester base constituents produced from vegetable oils. Besides, the behavior of these biofuels blended with additives such as alkanes is of great importance in order to understand their molecular interactions. Therefore, this research is aimed at two main contributions: (I) the experimental determination of densities for two dodecane + biodiesel systems and (II) the modelling of the experimental density sets by an approach based on the Tammann-Tait equation with global parameters dependent on pressure, temperature and composition. Two biodiesel samples were produced from transesterification of waste cooking oil with methanol, and waste beef tallow with ethanol. Density was measured in a vibrating tube densimeter (VTD). The dodecane + waste cooking oil methyl ester biodiesel system was explored at = 0, 0.1000, 0.1511, 0.2014, 0.2502, 0.3004 and 1.000; while the dodecane + waste beef tallow ethyl ester biodiesel system was evaluated at = 0, 0.1000, 0.3000, 0.5012, 0.7001, 0.9002 and 1.000. The proposed model yielded 0.4 kg·m−3 of standard deviation; these deviations were lower compared with those from other semiempirical models proposed in the literature. Moreover, the model was capable to estimate the isothermal compressibility and the thermal expansion coefficients.
{"title":"High pressure density for dodecane + biodiesel produced from residuals from cooking oil and beef tallow: Experiments and correlation with a proposed global (p, T, x) Tammann-Tait base model","authors":"Christian Bouchot , Raquel I. Rodríguez-Cisneros , José Domenzaín-González , Ricardo García-Morales , Francisco J. Verónico-Sánchez , Abel Zúñiga-Moreno , Octavio Elizalde-Solis","doi":"10.1016/j.jct.2025.107561","DOIUrl":"10.1016/j.jct.2025.107561","url":null,"abstract":"<div><div>Thermophysical properties under high pressure and high temperature of biodiesel are mainly available for samples with methyl ester base constituents produced from vegetable oils. Besides, the behavior of these biofuels blended with additives such as alkanes is of great importance in order to understand their molecular interactions. Therefore, this research is aimed at two main contributions: (I) the experimental determination of densities for two dodecane + biodiesel systems and (II) the modelling of the experimental density sets by an approach based on the Tammann-Tait equation with global parameters dependent on pressure, temperature and composition. Two biodiesel samples were produced from transesterification of waste cooking oil with methanol, and waste beef tallow with ethanol. Density was measured in a vibrating tube densimeter (VTD). The dodecane + waste cooking oil methyl ester biodiesel system was explored at <span><math><mrow><msub><mi>x</mi><mrow><mi>C</mi><mn>12</mn></mrow></msub></mrow></math></span> = 0, 0.1000, 0.1511, 0.2014, 0.2502, 0.3004 and 1.000; while the dodecane + waste beef tallow ethyl ester biodiesel system was evaluated at <span><math><mrow><msub><mi>x</mi><mrow><mi>C</mi><mn>12</mn></mrow></msub></mrow></math></span> = 0, 0.1000, 0.3000, 0.5012, 0.7001, 0.9002 and 1.000. The proposed model yielded 0.4 kg·m<sup>−3</sup> of standard deviation; these deviations were lower compared with those from other semiempirical models proposed in the literature. Moreover, the model was capable to estimate the isothermal compressibility and the thermal expansion coefficients.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107561"},"PeriodicalIF":2.2,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145332518","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 : 2025-08-07DOI: 10.1016/j.jct.2025.107562
Xiaoxi Guo , Yinglu Liu , Yuxuan Zhang , Yingqian Wang , Peng Liu , Qiuliang Liu , Hongyang Wu
The thermodynamic parameters on corresponding solid-liquid equilibrium of 2,3,4-Trimethoxybenzoic acid (TMBA) in different solvents are essential for a preliminary study of pharmaceutical engineering and industrial applications. A mass method was used to correct the solid-liquid equilibrium of TMBA in 12 pure solvents (Water, Ethylene glycol, Isopropanol, n-Propanol, n-propyl acetate, Isopropyl acetate, n-Butyl acetate, Ethanol, Ethyl acetate, 2-Butoxy ethanol, 2-Methoxyethanol, Ethylene glycol ethyl ether) in the temperatures (from 278.15 to 318.15 K) under 0.1 MPa. For the temperature range investigation, the solubility of TMBA in the solvents increased with increasing temperature. The solubility of TMBA in Ethylene glycol ethyl ether is superior to other selected pure solvents. The Van't Hoff model, modified Apelblat model, Buchowski-Ksiazaczak λh model and Polynomial empirical model were adopted to describe and predict the change tendency of solubility. Computational results showed that the Van't Hoff model stood out to be more suitable with the higher applicability. And, the solvent effects on TMBA solubility were studied by the KAT-LSER model, which confirms that hydrogen bond donation (α) and temperature (1/T) dominate TMBA's solubility, while hydrogen bond acceptance (β) exhibits inhibition. In addition, the calculated thermodynamic parameters include ΔsolG° (3.0994–17.8991 kJ mol−1), ΔsolH° (15.6814–28.5220 kJ mol−1), and ΔsolS° (35.6965–101.0757 J mol−1 K−1), which indicated that in each studied solvents the dissolution of TMBA is endothermic, entropy increasing and entropy-drive process.
{"title":"Solubility measurement and thermodynamic modeling of 2,3,4-trimethoxybenzoic acid in 12 solvents across a temperature range of 278.15 K–318.15 K","authors":"Xiaoxi Guo , Yinglu Liu , Yuxuan Zhang , Yingqian Wang , Peng Liu , Qiuliang Liu , Hongyang Wu","doi":"10.1016/j.jct.2025.107562","DOIUrl":"10.1016/j.jct.2025.107562","url":null,"abstract":"<div><div>The thermodynamic parameters on corresponding solid-liquid equilibrium of 2,3,4-Trimethoxybenzoic acid (TMBA) in different solvents are essential for a preliminary study of pharmaceutical engineering and industrial applications. A mass method was used to correct the solid-liquid equilibrium of TMBA in 12 pure solvents (Water, Ethylene glycol, Isopropanol, n-Propanol, n-propyl acetate, Isopropyl acetate, n-Butyl acetate, Ethanol, Ethyl acetate, 2-Butoxy ethanol, 2-Methoxyethanol, Ethylene glycol ethyl ether) in the temperatures (from 278.15 to 318.15 K) under 0.1 MPa. For the temperature range investigation, the solubility of TMBA in the solvents increased with increasing temperature. The solubility of TMBA in Ethylene glycol ethyl ether is superior to other selected pure solvents. The Van't Hoff model, modified Apelblat model, Buchowski-Ksiazaczak λh model and Polynomial empirical model were adopted to describe and predict the change tendency of solubility. Computational results showed that the Van't Hoff model stood out to be more suitable with the higher applicability. And, the solvent effects on TMBA solubility were studied by the KAT-LSER model, which confirms that hydrogen bond donation (<em>α</em>) and temperature (1/<em>T</em>) dominate TMBA's solubility, while hydrogen bond acceptance (<em>β</em>) exhibits inhibition. In addition, the calculated thermodynamic parameters include Δ<sub>sol</sub><em>G</em>° (3.0994–17.8991 kJ mol<sup>−1</sup>), Δ<sub>sol</sub><em>H</em>° (15.6814–28.5220 kJ mol<sup>−1</sup>), and Δ<sub>sol</sub><em>S</em>° (35.6965–101.0757 J mol<sup>−1</sup> K<sup>−1</sup>), which indicated that in each studied solvents the dissolution of TMBA is endothermic, entropy increasing and entropy-drive process.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"212 ","pages":"Article 107562"},"PeriodicalIF":2.2,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145004605","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 : 2025-08-06DOI: 10.1016/j.jct.2025.107560
Evis Muzhaqi, Aycan Altun Kavaklı, Osman Nuri Şara, M. Ferdi Fellah
In this study, the density and viscosity of binary mixtures of triethanolamine (TEA) and ethanol were measured over the entire composition range at temperatures of 293.15 and 323.15 K under a pressure of 101.3 kPa. Correlations were obtained expressing density and viscosity values as a function of temperature. Excess molar volume (VE) and viscosity deviation (Δη) were calculated from the measured values. These properties were further fitted to the Redlich–Kister polynomial equation. Thermodynamic parameters such as partial molar volumes, apparent molar volumes, coefficients of thermal expansion, and excess Gibbs free energy of activation for viscous flow were also determined. Moreover, activation enthalpy and entropy values for viscous flow were evaluated. The experimental results and the Density Functional Theory (DFT) calculations were used to discuss the molecular interactions for binary mixtures of TEA and ethanol. Negative values of VE and Δη were observed across all studied temperatures and compositions, indicating strong specific interactions between TEA and ethanol molecules. There is a distinct difference in the temperature dependence of VE and Δη. As the temperature increases, the VE values become increasingly negative, while the Δη values decrease. Both experimental results and Density Functional Theory (DFT) calculations confirm the presence of intermolecular hydrogen bonding in the binary mixtures. Furthermore, FTIR spectroscopy suggests the possible presence of intermolecular interactions between the components.
{"title":"Experimental and computational (DFT) study of a binary system of triethanolamine and ethanol at temperatures from 293.15 to 323.15 K under 101.3 kPa","authors":"Evis Muzhaqi, Aycan Altun Kavaklı, Osman Nuri Şara, M. Ferdi Fellah","doi":"10.1016/j.jct.2025.107560","DOIUrl":"10.1016/j.jct.2025.107560","url":null,"abstract":"<div><div>In this study, the density and viscosity of binary mixtures of triethanolamine (TEA) and ethanol were measured over the entire composition range at temperatures of 293.15 and 323.15 K under a pressure of 101.3 kPa. Correlations were obtained expressing density and viscosity values as a function of temperature. Excess molar volume (V<sup>E</sup>) and viscosity deviation (Δη) were calculated from the measured values. These properties were further fitted to the Redlich–Kister polynomial equation. Thermodynamic parameters such as partial molar volumes, apparent molar volumes, coefficients of thermal expansion, and excess Gibbs free energy of activation for viscous flow were also determined. Moreover, activation enthalpy and entropy values for viscous flow were evaluated. The experimental results and the Density Functional Theory (DFT) calculations were used to discuss the molecular interactions for binary mixtures of TEA and ethanol. Negative values of V<sup>E</sup> and Δη were observed across all studied temperatures and compositions, indicating strong specific interactions between TEA and ethanol molecules. There is a distinct difference in the temperature dependence of V<sup>E</sup> and Δη. As the temperature increases, the V<sup>E</sup> values become increasingly negative, while the Δη values decrease. Both experimental results and Density Functional Theory (DFT) calculations confirm the presence of intermolecular hydrogen bonding in the binary mixtures. Furthermore, FTIR spectroscopy suggests the possible presence of intermolecular interactions between the components.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"211 ","pages":"Article 107560"},"PeriodicalIF":2.2,"publicationDate":"2025-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144809684","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 : 2025-08-05DOI: 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":"2025-08-05","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}
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