Artificial sweeteners also known as non-caloric sweeteners, have surged in popularity owing to their sweet taste and lack of metabolic impact. Sugar alcohols have applications in various food products, thereby holding a significant position in both the food and pharmaceutical sectors. Erythritol is a type of sugar alcohol, it plays a significant role in the present study as a key component of a ternary mixture. Other important components of this study are DEGMME (diethylene glycol monomethyl ether) and DEGMEE (diethylene glycol monoethyl ether). These are basically glycol ethers that are used in many industries for different purposes. Using values of density, and speed of sound, , for a ternary mixture at various concentrations (0.10, 0.20, and 0.30) , this study calculates volumetric and acoustic properties at different four temperatures (288.15––318.15 K). Additionally, other useful parameters such as limiting apparent molar expansibilities () and its first-order derivatives were also calculated. Unlike previous research, which primarily focused on binary mixtures, this study delves into a more complex system, and providing valuable insights into solvation behaviour and molecular interactions. These results, derived from precise measurements using a Density and Sound Analyzer (DSA), that provide a comprehensive understanding of the interaction behaviour and structural changes within the studied systems.
{"title":"Study of thermodynamic and acoustic properties of DEGMME/ DEGMEE in aqueous erythritol solutions at different temperatures","authors":"Harsimaran Kaur , Nabaparna Chakraborty , K.C. Juglan , Arun Upmanyu","doi":"10.1016/j.jct.2024.107446","DOIUrl":"10.1016/j.jct.2024.107446","url":null,"abstract":"<div><div>Artificial sweeteners also known as non-caloric sweeteners, have surged in popularity owing to their sweet taste and lack of metabolic impact. Sugar alcohols have applications in various food products, thereby holding a significant position in both the food and pharmaceutical sectors. Erythritol is a type of sugar alcohol, it plays a significant role in the present study as a key component of a ternary mixture. Other important components of this study are DEGMME (diethylene glycol monomethyl ether) and DEGMEE (diethylene glycol monoethyl ether). These are basically glycol ethers that are used in many industries for different purposes. Using values of density, <span><math><mrow><mfenced><mrow><mi>ρ</mi></mrow></mfenced><mo>,</mo></mrow></math></span> and speed of sound, <span><math><mfenced><mrow><mi>c</mi></mrow></mfenced></math></span>, for a ternary mixture at various concentrations (0.10, 0.20, and 0.30) <span><math><msup><mrow><mi>mol</mi><mo>∙</mo><mi>k</mi><mi>g</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msup></math></span>, this study calculates volumetric and acoustic properties at different four temperatures (288.15––318.15 K). Additionally, other useful parameters such as limiting apparent molar expansibilities (<span><math><msubsup><mi>E</mi><mrow><mi>ϕ</mi></mrow><mn>0</mn></msubsup></math></span>) and its first-order derivatives <span><math><msub><mfenced><mrow><mrow><mi>∂</mi><msubsup><mi>E</mi><mi>ϕ</mi><mn>0</mn></msubsup><mo>/</mo><mi>∂</mi><mi>T</mi></mrow></mrow></mfenced><mi>p</mi></msub></math></span> were also calculated. Unlike previous research, which primarily focused on binary mixtures, this study delves into a more complex system, and providing valuable insights into solvation behaviour and molecular interactions. These results, derived from precise measurements using a Density and Sound Analyzer (DSA), that provide a comprehensive understanding of the interaction behaviour and structural changes within the studied systems.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"204 ","pages":"Article 107446"},"PeriodicalIF":2.2,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143182574","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}
Densities and viscosities of caffeine in various aqueous molal solution [m = (0.005–0.020) mol kg−1] of D-sorbitol were measured at T = (298.15–318.15) K and ambient pressure P = 101 kPa. A number of volumetric, viscometric and thermodynamic properties like apparent molar volumes, standard partial molar volumes, apparent specific volumes, standard isobaric partial molar expansibilities and their temperature dependence, viscosity B-coefficients, solvation number, etc., have been determined from the measured data. Further, the standard volume of transfer and viscosity B-coefficient of transfer for caffeine from water to aqueous D-sorbitol solutions were derived in order to have insights into the variety of interactions in the ternary solutions. In terms of solute–solvent and solute–solute interactions, the effects of molality, solute structure, temperature and taste behavior were examined. These findings showed that caffeine acts as a structure maker and that the solute–solvent interactions dominate in the ternary solutions. UV–visible and 1H NMR spectroscopic studies were performed to substantiate these findings. Further, bond length changes due to interaction between D-sorbitol and caffeine, molecular electrostatic potential maps, Mülliken charge distribution, etc., were also studied theoretically and correlated to various interactions in the studied solutions.
{"title":"Volumetric and viscometric study of caffeine in aqueous D-sorbitol solutions","authors":"Dhurba Jyoti Roy , Sachindra Kumar Singh , Tanmoy Dutta , Sudarshan Pradhan , Biswajit Sinha","doi":"10.1016/j.jct.2024.107445","DOIUrl":"10.1016/j.jct.2024.107445","url":null,"abstract":"<div><div>Densities and viscosities of caffeine in various aqueous molal solution [m = (0.005–0.020) mol <span><math><mo>∙</mo></math></span> kg<sup>−1</sup>] of D-sorbitol were measured at T = (298.15–318.15) K and ambient pressure <em>P</em> = 101 kPa. A number of volumetric, viscometric and thermodynamic properties like apparent molar volumes, standard partial molar volumes, apparent specific volumes, standard isobaric partial molar expansibilities and their temperature dependence, viscosity <em>B</em>-coefficients, solvation number, <em>etc</em>., have been determined from the measured data. Further, the standard volume of transfer and viscosity <em>B</em>-coefficient of transfer for caffeine from water to aqueous D-sorbitol solutions were derived in order to have insights into the variety of interactions in the ternary solutions. In terms of solute–solvent and solute–solute interactions, the effects of molality, solute structure, temperature and taste behavior were examined. These findings showed that caffeine acts as a structure maker and that the solute–solvent interactions dominate in the ternary solutions. UV–visible and <sup>1</sup>H NMR spectroscopic studies were performed to substantiate these findings. Further, bond length changes due to interaction between D-sorbitol and caffeine, molecular electrostatic potential maps, Mülliken charge distribution, etc., were also studied theoretically and correlated to various interactions in the studied solutions.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"204 ","pages":"Article 107445"},"PeriodicalIF":2.2,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143182572","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 : 2024-12-20DOI: 10.1016/j.jct.2024.107435
Zhuozhuo Li, Guangyong Liu
The transport properties of cyclohexane, p-xylene and cyclohexanone in Ethylene Propylene Diene Monomer (EPDM) were determined by equilibrium swelling method, and the effects of temperature on the diffusion (D), adsorption (S) and permeation (P) behaviors were investigated. The results showed that the diffusion behaviors of cyclohexane, p-xylene and cyclohexanone in EPDM crosslinking network were not only related to the compatibility but also more significantly affected by temperature, and the swelling mechanism of EPDM crosslinking network was inferred. Fick diffusion contribution index (Kf) was obtained by Peppas-Sahlin model, and the D and P values of the three EPDM swelling systems could be correlated by the same D ∼ Kf relationship and P ∼ Kf relationship, respectively. The temperature dependance of the D and P values of EPDM/cyclohexane and EPDM/p-xylene system was less at low-temperature and higher above 35 ℃. The diffusion (ED) and permeation activation energies (EP) determined for the EPDM/p-xylene swelling system showed the lowest values, corresponding to the highest D and P values, that is, the diffusion and permeation of p-xylene in EPDM was very fast. This work can provide an important guiding significance for evaluating the liquid resistance of EPDM-based industrial and automotive rubber products.
{"title":"Investigation on the thermodynamic and kinetic parameters in the process of solvents transporting into EPDM crosslinking network at incremental temperatures","authors":"Zhuozhuo Li, Guangyong Liu","doi":"10.1016/j.jct.2024.107435","DOIUrl":"10.1016/j.jct.2024.107435","url":null,"abstract":"<div><div>The transport properties of cyclohexane, p-xylene and cyclohexanone in Ethylene Propylene Diene Monomer (EPDM) were determined by equilibrium swelling method, and the effects of temperature on the diffusion (D), adsorption (S) and permeation (P) behaviors were investigated. The results showed that the diffusion behaviors of cyclohexane, p-xylene and cyclohexanone in EPDM crosslinking network were not only related to the compatibility but also more significantly affected by temperature, and the swelling mechanism of EPDM crosslinking network was inferred. Fick diffusion contribution index (K<sub>f</sub>) was obtained by Peppas-Sahlin model, and the D and P values of the three EPDM swelling systems could be correlated by the same D ∼ K<sub>f</sub> relationship and P ∼ K<sub>f</sub> relationship, respectively. The temperature dependance of the D and P values of EPDM/cyclohexane and EPDM/p-xylene system was less at low-temperature and higher above 35 ℃. The diffusion (E<sub>D</sub>) and permeation activation energies (E<sub>P</sub>) determined for the EPDM/p-xylene swelling system showed the lowest values, corresponding to the highest D and P values, that is, the diffusion and permeation of p-xylene in EPDM was very fast. This work can provide an important guiding significance for evaluating the liquid resistance of EPDM-based industrial and automotive rubber products.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"203 ","pages":"Article 107435"},"PeriodicalIF":2.2,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143156061","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 experimental solubility of β-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in binary solvent mixtures of sulfolane + (H2O, acetonitrile, and ethanol) was measured at temperature ranging from (298.15 K to 343.15 K) by dynamic method under atmospheric pressure. The results showed that the solubility of β-HMX monotonously increases with increasing mole fraction of sulfolane at a given temperature in the studied binary solvent mixtures. Furthermore, the experimental solubility data in binary solvents were fitted using the modified Apelblat equation, the GCM model and the Jouyban-Acree model successfully. Hirshfeld surface analysis and molecular electrostatic potential (ESP) were employed to visualize close contacts and charge distribution of β-HMX and solvents. In addition, the molar dissolution thermodynamic properties of the solution of different binary solvent mixtures, such as Gibbs free energy, enthalpy and entropy, were calculated and analyzed based on the van’t Hoff equation and the experimental solubility data. Solid-liquid surface tension and surface entropy factor of β-HMX were estimated by the experimental solubility data. The solubility of β-HMX in sulfolane based binary solvent systems will provide essential support for the further study of crystallization and spheroidization of β-HMX in industry.
{"title":"Solubility and thermodynamic properties of β-HMX in sulfolane based binary solvent systems","authors":"Haoyang Xie , Yuan Gao , Zichao Guo , Wanghua Chen","doi":"10.1016/j.jct.2024.107426","DOIUrl":"10.1016/j.jct.2024.107426","url":null,"abstract":"<div><div>The experimental solubility of <em>β</em>-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) in binary solvent mixtures of sulfolane + (H<sub>2</sub>O, acetonitrile, and ethanol) was measured at temperature ranging from (298.15 K to 343.15 K) by dynamic method under atmospheric pressure. The results showed that the solubility of <em>β</em>-HMX monotonously increases with increasing mole fraction of sulfolane at a given temperature in the studied binary solvent mixtures. Furthermore, the experimental solubility data in binary solvents were fitted using the modified Apelblat equation, the GCM model and the Jouyban-Acree model successfully. Hirshfeld surface analysis and molecular electrostatic potential (ESP) were employed to visualize close contacts and charge distribution of <em>β</em>-HMX and solvents. In addition, the molar dissolution thermodynamic properties of the solution of different binary solvent mixtures, such as Gibbs free energy, enthalpy and entropy, were calculated and analyzed based on the van’t Hoff equation and the experimental solubility data. Solid-liquid surface tension and surface entropy factor of <em>β</em>-HMX were estimated by the experimental solubility data. The solubility of <em>β</em>-HMX in sulfolane based binary solvent systems will provide essential support for the further study of crystallization and spheroidization of <em>β</em>-HMX in industry.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"203 ","pages":"Article 107426"},"PeriodicalIF":2.2,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100477","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}
Knowledge of physicochemical properties of new developed absorbents is important for understanding the hydrodynamics and mass transfer behaviors during CO2 absorption. In this work, density and viscosity of partially carbonated nonaqueous systems containing amine and 2-(hexyloxy)ethanol (EGHE) were measured at temperatures of (293.15–353.15) K and 101.3 kPa. Three secondary alkanolamines (i.e., 2-(methylamino)ethanol, 2-(ethylamino)ethanol and 2-(butylamino)ethanol) were investigated in the concentration range of 10–60 mass%. It was found that viscosities of the carbonated solutions presented an exponential change with the temperature, CO2 loading and amine concentration. However, an approximately linear increase in density with the decreasing temperature and the increasing CO2 loading was observed for all the studied blends. Property data of the CO2-loaded solutions can be represented by two proposed models with simple parameters based on CO2-free property data. These models can provide good prediction of thermophysical properties in a CO2 capture process.
{"title":"Measurement and modeling of density and viscosity of nonaqueous systems (secondary alkanolamines + 2-hexyloxyethanol + CO2) at temperatures of (293.15–353.15) K","authors":"Qinghai Long, Guangyi Cui, Shuo Wang, Shufeng Shen","doi":"10.1016/j.jct.2024.107431","DOIUrl":"10.1016/j.jct.2024.107431","url":null,"abstract":"<div><div>Knowledge of physicochemical properties of new developed absorbents is important for understanding the hydrodynamics and mass transfer behaviors during CO<sub>2</sub> absorption. In this work, density and viscosity of partially carbonated nonaqueous systems containing amine and 2-(hexyloxy)ethanol (EGHE) were measured at temperatures of (293.15–353.15) K and 101.3 kPa. Three secondary alkanolamines (i.e., 2-(methylamino)ethanol, 2-(ethylamino)ethanol and 2-(butylamino)ethanol) were investigated in the concentration range of 10–60 mass%. It was found that viscosities of the carbonated solutions presented an exponential change with the temperature, CO<sub>2</sub> loading and amine concentration. However, an approximately linear increase in density with the decreasing temperature and the increasing CO<sub>2</sub> loading was observed for all the studied blends. Property data of the CO<sub>2</sub>-loaded solutions can be represented by two proposed models with simple parameters based on CO<sub>2</sub>-free property data. These models can provide good prediction of thermophysical properties in a CO<sub>2</sub> capture process.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"203 ","pages":"Article 107431"},"PeriodicalIF":2.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100478","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 : 2024-12-17DOI: 10.1016/j.jct.2024.107434
Iván Montenegro, Begoña González, Ángeles Domínguez, Elena Gómez
In recent years, there has been great interest in exploring the recovery of polyphenols from natural resources. However, in studies that address this topic, results present high recovery yield but low selectivity in the extraction of these compounds. This work seeks to improve the selectivity of these processes by an appropriate selection of the solvents. To achieve this objective, the solubility of five polyphenolic compounds: trans-piceid, myricetin, quercetin, kaempferol and trans-resveratrol in pure methanol, ethyl acetate, n-propyl acetate, and butyl acetate were determined at T = 298.15 K at 0.1 MPa, as well as the solubility of quercetin and trans-piceid in three binary solvent mixtures (methanol + ethyl acetate, methanol + n-propyl acetate and methanol + butyl acetate). Experimental results for ternary systems were correlated with the combined nearly ideal binary solvent/Redlich-Kister (CNIBS/R-K) equation.
{"title":"Solubility study of several polyphenolic compounds in pure and binary solvents","authors":"Iván Montenegro, Begoña González, Ángeles Domínguez, Elena Gómez","doi":"10.1016/j.jct.2024.107434","DOIUrl":"10.1016/j.jct.2024.107434","url":null,"abstract":"<div><div>In recent years, there has been great interest in exploring the recovery of polyphenols from natural resources. However, in studies that address this topic, results present high recovery yield but low selectivity in the extraction of these compounds. This work seeks to improve the selectivity of these processes by an appropriate selection of the solvents. To achieve this objective, the solubility of five polyphenolic compounds: <em>trans</em>-piceid, myricetin, quercetin, kaempferol and <em>trans</em>-resveratrol in pure methanol, ethyl acetate, <em>n</em>-propyl acetate, and butyl acetate were determined at <em>T</em> = 298.15 K at 0.1 MPa, as well as the solubility of quercetin and <em>trans</em>-piceid in three binary solvent mixtures (methanol + ethyl acetate, methanol + <em>n</em>-propyl acetate and methanol + butyl acetate). Experimental results for ternary systems were correlated with the combined nearly ideal binary solvent/Redlich-Kister (CNIBS/R-K) equation.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"203 ","pages":"Article 107434"},"PeriodicalIF":2.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100480","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 : 2024-12-17DOI: 10.1016/j.jct.2024.107432
Alexis Gibson , Shuhao Yang , Richard E. Riman , Alexandra Navrotsky , Brian F. Woodfield
This study investigates the heat capacity and thermodynamic properties of rare earth oxyfluorides (REOF), focusing on NdOF, YOF, and YbOF-monoclinic. To increase our understanding of their physical properties and stability, we measured the heat capacities of these REOF materials over a temperature range of 1.8 to 300 K. Our results reveal several Schottky anomalies at low temperatures due to interactions involving rare earth nuclei with nonzero magnetic moments and electronic contributions. We fitted the experimental data using theoretical models to derive standard entropy, enthalpy, and Gibbs energy. These values were combined with literature values to calculate Gibbs energies of formation from the elements and the fluorides and oxides at selected temperatures. At 298.15 K, the Gibbs energy of formation relative to oxides and fluorides was calculated to be −26.717 kJ·mol−1, −12.394 kJ·mol−1, and −11.011 kJ·mol−1for NdOF, YOF, and YbOF-mon, respectively. The Gibbs energy of formation of REOF relative to the elements at 298.15 K was calculated to be −1143.889 kJ·mol−1, −1191.304 kJ·mol−1, and −1115.430 kJ·mol−1 for NdOF, YOF, and YbOF-mon, respectively. The results confirm the stability of these three REOF compounds, underlining their potential for diverse technological applications.
{"title":"Heat capacity and thermodynamic functions of rare earth Oxyfluorides, REOF","authors":"Alexis Gibson , Shuhao Yang , Richard E. Riman , Alexandra Navrotsky , Brian F. Woodfield","doi":"10.1016/j.jct.2024.107432","DOIUrl":"10.1016/j.jct.2024.107432","url":null,"abstract":"<div><div>This study investigates the heat capacity and thermodynamic properties of rare earth oxyfluorides (REOF), focusing on NdOF, YOF, and YbOF-monoclinic. To increase our understanding of their physical properties and stability, we measured the heat capacities of these REOF materials over a temperature range of 1.8 to 300 K. Our results reveal several Schottky anomalies at low temperatures due to interactions involving rare earth nuclei with nonzero magnetic moments and electronic contributions. We fitted the experimental data using theoretical models to derive standard entropy, enthalpy, and Gibbs energy. These values were combined with literature values to calculate Gibbs energies of formation from the elements and the fluorides and oxides at selected temperatures. At 298.15 K, the Gibbs energy of formation relative to oxides and fluorides was calculated to be −26.717 kJ·mol<sup>−1</sup>, −12.394 kJ·mol<sup>−1</sup>, and −11.011 kJ·mol<sup>−1</sup>for NdOF, YOF, and YbOF-mon, respectively. The Gibbs energy of formation of REOF relative to the elements at 298.15 K was calculated to be −1143.889 kJ·mol<sup>−1</sup>, −1191.304 kJ·mol<sup>−1</sup>, and −1115.430 kJ·mol<sup>−1</sup> for NdOF, YOF, and YbOF-mon, respectively. The results confirm the stability of these three REOF compounds, underlining their potential for diverse technological applications.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"204 ","pages":"Article 107432"},"PeriodicalIF":2.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143182571","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 : 2024-12-17DOI: 10.1016/j.jct.2024.107433
Shikuo Li , Shidong Li , Yixin Liu , Huimin Li , Haowei Yuan , Zidan Cao , Weihua Zou , Yu Li , Tao Li , Baozeng Ren
The solubility of 2-naphthoxyacetic acid in methanol + water, ethanol + water, and n-propanol + water was determined by static method over the temperature range of 278.15–323.15 K and atmospheric pressure. The experimental results demonstrated that the solubility of 2-Naphthoxyacetic Acid (BNOA) in three binary mixed solvents increased with the rise in the mass fraction of the alcoholic solvents at constant temperature. Additionally, the solubility of BNOA in the identified binary solvents demonstrated a positive correlation with temperature throughout the temperature range studied. Three mathematical models: including the modified Apelblat equation, NRTL model, the Ma model, were employed to fit the experimental solubility data. The results suggest that the modified Apelblat model exhibited the most favorable correlation. The solubility of BNOA in the studied solvents was discussed using the Hansen Solubility Parameters (HSPs), providing a reasonable explanation for the solubility of BNOA in three binary solvents. Using molecular dynamic (MD) simulation to obtain the radial distribution function (RDF) and analyzing the intermolecular interactions between solutes and binary mixed solvents, the findings indicated that the interactions between the solute and solvent, as well as between the solvent and solvent, exerted a considerable influence on the dissolution behavior of BNOA in the binary mixture. Based on the van’t Hoff equation, the apparent thermodynamic parameters (, , , and ) of the dissolution process were calculated, and the results showed that the dissolution process of BNOA in the studied mixed solvent was an endothermic and entropy increasing process, with enthalpy contribution greater than entropy contribution during the dissolution process.
{"title":"Solubility, correlation, Hansen solubility parameter and thermodynamic properties of 2-naphthoxyacetic acid in three binary mixed solvents","authors":"Shikuo Li , Shidong Li , Yixin Liu , Huimin Li , Haowei Yuan , Zidan Cao , Weihua Zou , Yu Li , Tao Li , Baozeng Ren","doi":"10.1016/j.jct.2024.107433","DOIUrl":"10.1016/j.jct.2024.107433","url":null,"abstract":"<div><div>The solubility of 2-naphthoxyacetic acid in methanol + water, ethanol + water, and n-propanol + water was determined by static method over the temperature range of 278.15–323.15 K and atmospheric pressure. The experimental results demonstrated that the solubility of 2-Naphthoxyacetic Acid (BNOA) in three binary mixed solvents increased with the rise in the mass fraction of the alcoholic solvents at constant temperature. Additionally, the solubility of BNOA in the identified binary solvents demonstrated a positive correlation with temperature throughout the temperature range studied. Three mathematical models: including the modified Apelblat equation, NRTL model, the Ma model, were employed to fit the experimental solubility data. The results suggest that the modified Apelblat model exhibited the most favorable correlation. The solubility of BNOA in the studied solvents was discussed using the Hansen Solubility Parameters (HSPs), providing a reasonable explanation for the solubility of BNOA in three binary solvents. Using molecular dynamic (MD) simulation to obtain the radial distribution function (RDF) and analyzing the intermolecular interactions between solutes and binary mixed solvents, the findings indicated that the interactions between the solute and solvent, as well as between the solvent and solvent, exerted a considerable influence on the dissolution behavior of BNOA in the binary mixture. Based on the van’t Hoff equation, the apparent thermodynamic parameters (<span><math><mrow><msub><mi>Δ</mi><mrow><mi>sol</mi></mrow></msub><msup><mrow><mi>G</mi></mrow><mi>o</mi></msup></mrow></math></span>, <span><math><mrow><msub><mi>Δ</mi><mrow><mi>sol</mi></mrow></msub><msup><mrow><mi>H</mi></mrow><mi>o</mi></msup></mrow></math></span>, <span><math><mrow><msub><mi>Δ</mi><mrow><mi>sol</mi></mrow></msub><msup><mrow><mi>S</mi></mrow><mi>o</mi></msup></mrow></math></span>, <span><math><msub><mi>ζ</mi><mi>H</mi></msub></math></span> and <span><math><msub><mi>ζ</mi><mrow><mi>TS</mi></mrow></msub></math></span>) of the dissolution process were calculated, and the results showed that the dissolution process of BNOA in the studied mixed solvent was an endothermic and entropy increasing process, with enthalpy contribution greater than entropy contribution during the dissolution process.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"204 ","pages":"Article 107433"},"PeriodicalIF":2.2,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143182573","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}
Solubility and thermodynamic properties of metronidazole (MET) in different solvents are important for the separation and optimization of particle shape in crystallization processes. In this study, the solubility of MET in 7 mono-solvents (methanol, ethanol, i-propanol, n-butanol, ethyl acetate, chloroform, water) and 2 binary solvent systems (methanol + water, and ethanol + water) was determined by using gravimetric method within the temperature range from 293.15 to 327.35 K under atmospheric pressure. The sequence of mole fraction solubility of MET in the studied mono-solvent is methanol > n-butanol > ethanol > i-propanol > ethyl acetate > chloroform > water, and the solubility increases monotonically with increasing temperature. For 2 binary solvent systems, the solubilities increased with increasing temperature for fixed solvent compositions, but for situation of fixed temperature, and the solubilities would reach a maximum value for mole fraction of methanol in methanol + water is 0.6999 and for mole fraction of ethanol is 0.5994. The model calibration of the solubility data in 7 mono-solvents were investigated using the modified Apelblat equation, λh equation, non-random two-liquid (NRTL) model and Wilson model, and the solubility data of MET in methanol + water and ethanol + water were also modeled using van’t Hoff-Jouyban Acree model, modified Apelblat-Jouyban-Acree equation except for these five thermodynamic models used for 7 mono-solvents. The relative average deviations for the experimental solubility data and corresponding prediction values were calculated to report the accuracy of each model. The thermodynamics of mixing for the dissolution of MET were studied using the Wilson model, and the dissolution process was endothermic and entropy driven in 7 mono-solvents and 2 binary solvent systems studied. The difference in solubility of MET between mono-solvents was investigated using the Hansen Solubility Parameters (HSPs) method, it was found that MET is insoluble in water and soluble in alcohols based on the calculated Δδt values of solutes and solvents. The cohesive energy of the solvent was analyzed as the greatest influence on the solubility of MET using the calibrated model parameters of KAT-LSER model.
{"title":"Solubility measurement, correlation, thermodynamic properties, and solvent effect of metronidazole in seven pure solvents and two binary solvent systems","authors":"Guobang Yu , Cuihong Chen , Yuze Xie, Wenyu Yuan, Yang Zhang, Jiajun Chen","doi":"10.1016/j.jct.2024.107430","DOIUrl":"10.1016/j.jct.2024.107430","url":null,"abstract":"<div><div>Solubility and thermodynamic properties of metronidazole (MET) in different solvents are important for the separation and optimization of particle shape in crystallization processes. In this study, the solubility of MET in 7 mono-solvents (methanol, ethanol, i-propanol, n-butanol, ethyl acetate, chloroform, water) and 2 binary solvent systems (methanol + water, and ethanol + water) was determined by using gravimetric method within the temperature range from 293.15 to 327.35 K under atmospheric pressure. The sequence of mole fraction solubility of MET in the studied mono-solvent is methanol > n-butanol > ethanol > i-propanol > ethyl acetate > chloroform > water, and the solubility increases monotonically with increasing temperature. For 2 binary solvent systems, the solubilities increased with increasing temperature for fixed solvent compositions, but for situation of fixed temperature, and the solubilities would reach a maximum value for mole fraction of methanol in methanol + water is 0.6999 and for mole fraction of ethanol is 0.5994. The model calibration of the solubility data in 7 mono-solvents were investigated using the modified Apelblat equation, λh equation, non-random two-liquid (NRTL) model and Wilson model, and the solubility data of MET in methanol + water and ethanol + water were also modeled using van’t Hoff-Jouyban Acree model, modified Apelblat-Jouyban-Acree equation except for these five thermodynamic models used for 7 mono-solvents. The relative average deviations for the experimental solubility data and corresponding prediction values were calculated to report the accuracy of each model. The thermodynamics of mixing for the dissolution of MET were studied using the Wilson model, and the dissolution process was endothermic and entropy driven in 7 mono-solvents and 2 binary solvent systems studied. The difference in solubility of MET between mono-solvents was investigated using the Hansen Solubility Parameters (HSPs) method, it was found that MET is insoluble in water and soluble in alcohols based on the calculated Δ<em>δ</em><sub>t</sub> values of solutes and solvents. The cohesive energy of the solvent was analyzed as the greatest influence on the solubility of MET using the calibrated model parameters of KAT-LSER model.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"203 ","pages":"Article 107430"},"PeriodicalIF":2.2,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100479","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 : 2024-12-12DOI: 10.1016/j.jct.2024.107429
Francisco M.T. Pereira Filho , Lucas H.G. de Medeiros , Lorena M. Alexandre e Silva , Kirley M. Canuto , Filipe X. Feitosa , Hosiberto B. de Sant’Ana
In this work, the effects of cations and anions on the density of pure compounds N-methyl-2-hydroxyethylammonium acetate [m-2-HEAA], 2-hydroxyethylammonium acetate [2-HEAA], and 2-hydroxyethylammonium pentanoate [HEAPe], as well as their mixtures following mixtures [m-2-HEAA] + [2-HEAA] and [HEAPe] + [2-HEAA], were determined. These measurements were conducted at pressures up to 100.0 MPa and within a temperature range of T = (298.15 to 373.15) K using the vibrating tube method. A Tammann-Tait equation correlated the experimental density data with an average absolute relative deviation () less than 0.065 %. From this Tammann-Tait equation, the following derivative properties were determined for pure compounds: isothermal compressibility (), isobaric expansivity (), thermal pressure coefficient (), and internal pressure (). For the binary mixtures, excess molar volume (VE) was determined. These data showed that N-methyl-2-hydroxyethylammonium anion impacts more than pentanoate cation when compared to their effect on the ILs packing efficiency. Furthermore, density data was estimated using Paduszynski and Domanska, Lazzus, and Evangelista et al. group contributing methods.
{"title":"Density for M−2−HEAA + 2-HEAA and HEAPe + 2-HEAA binary mixtures and pure compounds at high pressure","authors":"Francisco M.T. Pereira Filho , Lucas H.G. de Medeiros , Lorena M. Alexandre e Silva , Kirley M. Canuto , Filipe X. Feitosa , Hosiberto B. de Sant’Ana","doi":"10.1016/j.jct.2024.107429","DOIUrl":"10.1016/j.jct.2024.107429","url":null,"abstract":"<div><div>In this work, the effects of cations and anions on the density of pure compounds N-methyl-2-hydroxyethylammonium acetate [m-2-HEAA], 2-hydroxyethylammonium acetate [2-HEAA], and 2-hydroxyethylammonium pentanoate [HEAPe], as well as their mixtures following mixtures [m-2-HEAA] + [2-HEAA] and [HEAPe] + [2-HEAA], were determined. These measurements were conducted at pressures up to 100.0 MPa and within a temperature range of T = (298.15 to 373.15) K using the vibrating tube method. A Tammann-Tait equation correlated the experimental density data with an average absolute relative deviation (<span><math><mrow><mo>%</mo><mi>A</mi><mi>A</mi><mi>R</mi><mi>D</mi></mrow></math></span>) less than 0.065 %. From this Tammann-Tait equation, the following derivative properties were determined for pure compounds: isothermal compressibility (<span><math><mrow><msub><mi>κ</mi><mi>T</mi></msub></mrow></math></span>), isobaric expansivity (<span><math><mrow><msub><mi>α</mi><mi>p</mi></msub></mrow></math></span>), thermal pressure coefficient (<span><math><mrow><msub><mi>γ</mi><mi>V</mi></msub></mrow></math></span>)<sub>,</sub> and internal pressure (<span><math><mrow><msub><mi>P</mi><mi>i</mi></msub></mrow></math></span>). For the binary mixtures, excess molar volume (<em>V<sup>E</sup></em>) was determined. These data showed that N-methyl-2-hydroxyethylammonium anion impacts more than pentanoate cation when compared to their effect on the ILs packing efficiency. Furthermore, density data was estimated using Paduszynski and Domanska, Lazzus, and Evangelista et al. group contributing methods.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"203 ","pages":"Article 107429"},"PeriodicalIF":2.2,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100795","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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