Pub Date : 2024-10-10DOI: 10.1021/acs.jced.4c0047910.1021/acs.jced.4c00479
Luisa Alexandre Ferreira, Oscar Rodriguez, Catinca Secuianu and Marcelo S. Zabaloy,
{"title":"Preface to the Maria Eugénia Macedo Special Issue","authors":"Luisa Alexandre Ferreira, Oscar Rodriguez, Catinca Secuianu and Marcelo S. Zabaloy, ","doi":"10.1021/acs.jced.4c0047910.1021/acs.jced.4c00479","DOIUrl":"https://doi.org/10.1021/acs.jced.4c00479https://doi.org/10.1021/acs.jced.4c00479","url":null,"abstract":"","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142407634","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 : 2024-09-27DOI: 10.1021/acs.jced.4c0042210.1021/acs.jced.4c00422
Sergiu Sima, Catinca Secuianu* and Dan Vladimir Nichita*,
The phase behavior of the carbon dioxide and n-hexane binary mixture was examined. The entire available literature was reviewed and analyzed. Despite the apparent abundance of experimental data, both vapor–liquid equilibrium (VLE) and critical data, there is a high degree of discrepancy between them. Therefore, the liquid–vapor critical line was determined up to 117.0 bar and 383.15 K, as well as VLE data at different constant temperatures (313.15 to 383.15 K) using a 60 cm3 stainless-steel cell with sapphire windows connected to a gas chromatograph via rapid online sample injectors─ROLSI valves for accurate composition detection. The new and literature data were successfully calculated with several models (General Equation of state─GEOS, Peng–Robinson─PR, and Soave–Redlich–Kwong─SRK), in association with classical van der Waals mixing rules, i.e., one- (1PCMR) and two-parameter conventional (2PCMR) combining rules, as well as the PPR78 model. We also studied the influence of the structure of organic compounds (n-alkane, cycloalkane, and branched alkane-position isomers) with the same number of carbon atoms on the phase behavior of their corresponding binary systems at high pressures.
{"title":"Fluid-Phase Equilibrium Experiments and Modeling for CO2 + C6 Binary Systems","authors":"Sergiu Sima, Catinca Secuianu* and Dan Vladimir Nichita*, ","doi":"10.1021/acs.jced.4c0042210.1021/acs.jced.4c00422","DOIUrl":"https://doi.org/10.1021/acs.jced.4c00422https://doi.org/10.1021/acs.jced.4c00422","url":null,"abstract":"<p >The phase behavior of the carbon dioxide and <i>n</i>-hexane binary mixture was examined. The entire available literature was reviewed and analyzed. Despite the apparent abundance of experimental data, both vapor–liquid equilibrium (VLE) and critical data, there is a high degree of discrepancy between them. Therefore, the liquid–vapor critical line was determined up to 117.0 bar and 383.15 K, as well as VLE data at different constant temperatures (313.15 to 383.15 K) using a 60 cm<sup>3</sup> stainless-steel cell with sapphire windows connected to a gas chromatograph via rapid online sample injectors─ROLSI valves for accurate composition detection. The new and literature data were successfully calculated with several models (General Equation of state─GEOS, Peng–Robinson─PR, and Soave–Redlich–Kwong─SRK), in association with classical van der Waals mixing rules, i.e., one- (1PCMR) and two-parameter conventional (2PCMR) combining rules, as well as the PPR78 model. We also studied the influence of the structure of organic compounds (<i>n</i>-alkane, cycloalkane, and branched alkane-position isomers) with the same number of carbon atoms on the phase behavior of their corresponding binary systems at high pressures.</p>","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142408340","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 : 2024-09-18DOI: 10.1021/acs.jced.4c00328
Yang-Dian-Dian Wang, Shi-Hua Sang, Han-Zhong Zhang, Ling-Xuan Wang
The solid–liquid phase equilibria of the ternary system LiBr–Li2SO4–H2O at 273.15, 288.15, and 308.15 K were investigated by the isothermal dissolution equilibrium method. The equilibrium solid phases were identified by X-ray powder crystal diffraction. The isothermal phase diagrams of the ternary system at different temperatures were drawn in detail. The equilibrium phase diagrams of the ternary system at 273.15, 288.15, and 308.15 K have one invariant point, two univariate curves, and two crystallization fields (corresponding to LiBr·2H2O and Li2SO4·H2O), respectively. The results show that LiBr has a strong salting-out effect on Li2SO4, and the solubilities of LiBr will be greatly improved with an increase in temperature. Furthermore, multiple linear regression and programming analysis are used to fit the single salt parameters (β(0), β(1), and Cφ) and the mixed ion interaction parameters (ψLi+,Br–,SO42–) of lithium salt at 288.15 and 308.15 K. The Pitzer model and particle swarm optimization (PSO) were used to predict the solubilities in the ternary system at multitemperatures, and the phase diagrams of calculation and experiment are drawn accordingly. The experimental results and model predictions are in good agreement, indicating that fitted ion interaction parameters in this work of the Pitzer model have good applicability.
采用等温溶解平衡法研究了三元体系 LiBr-Li2SO4-H2O 在 273.15、288.15 和 308.15 K 下的固液相平衡。通过 X 射线粉末晶体衍射鉴定了平衡固相。详细绘制了三元体系在不同温度下的等温相图。三元体系在 273.15、288.15 和 308.15 K 下的平衡相图分别有一个不变点、两条单变量曲线和两个结晶场（分别对应于 LiBr-2H2O 和 Li2SO4-H2O）。结果表明，LiBr 对 Li2SO4 有很强的脱盐作用，随着温度的升高，LiBr 的溶解度会大大提高。此外，利用多元线性回归和编程分析拟合了锂盐在 288.15 和 308.15 K 下的单盐参数（β(0)、β(1)和 Cφ）和混合离子相互作用参数（ψLi+,Br-,SO42-），并利用 Pitzer 模型和粒子群优化（PSO）预测了三元体系在多温度下的溶解度，并绘制了相应的计算相图和实验相图。实验结果与模型预测结果吻合良好，表明本研究中的皮策模型拟合的离子相互作用参数具有良好的适用性。
{"title":"Measurements and Thermodynamic Model on the Solid–Liquid Phase Equilibria of the Ternary System LiBr–Li2SO4–H2O at Multitemperatures","authors":"Yang-Dian-Dian Wang, Shi-Hua Sang, Han-Zhong Zhang, Ling-Xuan Wang","doi":"10.1021/acs.jced.4c00328","DOIUrl":"https://doi.org/10.1021/acs.jced.4c00328","url":null,"abstract":"The solid–liquid phase equilibria of the ternary system LiBr–Li<sub>2</sub>SO<sub>4</sub>–H<sub>2</sub>O at 273.15, 288.15, and 308.15 K were investigated by the isothermal dissolution equilibrium method. The equilibrium solid phases were identified by X-ray powder crystal diffraction. The isothermal phase diagrams of the ternary system at different temperatures were drawn in detail. The equilibrium phase diagrams of the ternary system at 273.15, 288.15, and 308.15 K have one invariant point, two univariate curves, and two crystallization fields (corresponding to LiBr·2H<sub>2</sub>O and Li<sub>2</sub>SO<sub>4</sub>·H<sub>2</sub>O), respectively. The results show that LiBr has a strong salting-out effect on Li<sub>2</sub>SO<sub>4</sub>, and the solubilities of LiBr will be greatly improved with an increase in temperature. Furthermore, multiple linear regression and programming analysis are used to fit the single salt parameters (β<sup>(0)</sup>, β<sup>(1)</sup>, and <i>C</i><sup>φ</sup>) and the mixed ion interaction parameters (ψ<sub>Li<sup>+</sup>,Br<sup>–</sup>,SO<sub>4</sub><sup>2–</sup></sub>) of lithium salt at 288.15 and 308.15 K. The Pitzer model and particle swarm optimization (PSO) were used to predict the solubilities in the ternary system at multitemperatures, and the phase diagrams of calculation and experiment are drawn accordingly. The experimental results and model predictions are in good agreement, indicating that fitted ion interaction parameters in this work of the Pitzer model have good applicability.","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.694,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142266816","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 : 2024-09-16DOI: 10.1021/acs.jced.4c00325
Hiroaki Matsukawa, Katsuto Otake
The saturated vapor pressures of tetraethyl orthosilicate (TEOS, (CH3CH2O)4Si), tetrapropyl orthosilicate (TPOS, (CH3CH2CH2O)4Si), and tetrabutyl orthosilicate (TBOS, (CH3CH2CH2CH2O)4Si) were measured at temperatures up to 473 K using an apparatus based on the general static method. The standard uncertainties (us) were us (T) = 0.029 K and us (p) = 0.015 kPa, and the maximum combined expanded uncertainties U (0.95 level of confidence) were U(T) = (0.52, 8.60, and 1.64 K) and U(psat) = (2.81, 3.09, and 0.82 kPa) for TEOS, TPOS, and TBOS, respectively. Furthermore, the saturated vapor pressure was correlated using the Antoine equation to determine its parameters. The measured saturated vapor pressures were correlated with previously reported pressure–volume-temperature data using the PC-SAFT equation of state (EoS), followed by optimizing the pure component parameters of the PC-SAFT EoS. A relationship between the molecular structure and component parameters was identified, and the occupied volumes were determined according to the Sanchez–Lacombe and PC-SAFT EoS, revealing significant differences. Our findings highlight the potential of using the molecular structure to predict pure component parameters. In addition to providing accurate vapor pressure data for these orthosilicates, this study offers insights into correlation methods, emphasizing the importance of parameter determination in equation of state modeling.
使用基于一般静态法的仪器测量了正硅酸四乙酯（TEOS，(CH3CH2O)4Si）、正硅酸四丙酯（TPOS，(CH3CH2CH2O)4Si）和正硅酸四丁酯（TBOS，(CH3CH2CH2CH2O)4Si）在最高 473 K 温度下的饱和蒸汽压。TEOS、TPOS 和 TBOS 的标准不确定度 (us) 分别为 us (T) = 0.029 K 和 us (p) = 0.015 kPa，最大综合扩展不确定度 U（0.95 置信度）分别为 U(T) = (0.52, 8.60, and 1.64 K) 和 U(psat) = (2.81, 3.09, and 0.82 kPa)。此外，还利用安托万方程对饱和蒸气压进行了相关分析，以确定其参数。使用 PC-SAFT 状态方程（EoS）将测得的饱和蒸气压与之前报告的压力-体积-温度数据进行关联，然后优化 PC-SAFT EoS 的纯组分参数。我们确定了分子结构与组分参数之间的关系，并根据 Sanchez-Lacombe 和 PC-SAFT EoS 确定了所占体积，发现两者之间存在显著差异。我们的研究结果凸显了利用分子结构预测纯组分参数的潜力。除了为这些正硅酸盐提供准确的蒸汽压数据外，这项研究还为相关方法提供了见解，强调了参数确定在状态方程建模中的重要性。
{"title":"Saturated Vapor Pressure Measurements for Tetraethyl, Tetrapropyl, and Tetrabutyl Orthosilicates up to 473 K","authors":"Hiroaki Matsukawa, Katsuto Otake","doi":"10.1021/acs.jced.4c00325","DOIUrl":"https://doi.org/10.1021/acs.jced.4c00325","url":null,"abstract":"The saturated vapor pressures of tetraethyl orthosilicate (TEOS, (CH<sub>3</sub>CH<sub>2</sub>O)<sub>4</sub>Si), tetrapropyl orthosilicate (TPOS, (CH<sub>3</sub>CH<sub>2</sub>CH<sub>2</sub>O)<sub>4</sub>Si), and tetrabutyl orthosilicate (TBOS, (CH<sub>3</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>O)<sub>4</sub>Si) were measured at temperatures up to 473 K using an apparatus based on the general static method. The standard uncertainties (<i>u</i><sub><i>s</i></sub>) were <i>u</i><sub><i>s</i></sub> (<i>T</i>) = 0.029 K and <i>u</i><sub><i>s</i></sub> (<i>p</i>) = 0.015 kPa, and the maximum combined expanded uncertainties <i>U</i> (0.95 level of confidence) were <i>U</i>(<i>T</i>) = (0.52, 8.60, and 1.64 K) and <i>U</i>(<i>p</i><sup>sat</sup>) = (2.81, 3.09, and 0.82 kPa) for TEOS, TPOS, and TBOS, respectively. Furthermore, the saturated vapor pressure was correlated using the Antoine equation to determine its parameters. The measured saturated vapor pressures were correlated with previously reported pressure–volume-temperature data using the PC-SAFT equation of state (EoS), followed by optimizing the pure component parameters of the PC-SAFT EoS. A relationship between the molecular structure and component parameters was identified, and the occupied volumes were determined according to the Sanchez–Lacombe and PC-SAFT EoS, revealing significant differences. Our findings highlight the potential of using the molecular structure to predict pure component parameters. In addition to providing accurate vapor pressure data for these orthosilicates, this study offers insights into correlation methods, emphasizing the importance of parameter determination in equation of state modeling.","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.694,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142266844","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 : 2024-09-13DOI: 10.1021/acs.jced.4c00259
Anuj Sharma, Deepika, Siddharth Pandey
Renewable solvents derived from biomass have been regarded as promising alternatives to conventional organic solvents. A knowledge of the physical properties is crucial to accelerate the potential applications of a solvent, especially in industrial setups. Herein, we report water miscibility, surface tension (γ), density (ρ), dynamic viscosity (η), and refractive index (nD) of five structurally different renewable solvents: cyrene, dimethylisosorbide (DMI), γ-valerolactone (GVL), cyclopentylmethyl ether (CPME), and 2-methyltetrahydrofuran (2-MeTHF). Density and dynamic viscosity are measured in the temperature range of 283.15–363.15 K and surface tension is measured in the range of 298.15–363.15 K. Water miscibility and refractive index are estimated under ambient conditions. Comparatively higher water miscibility of cyrene, DMI, and GVL hints toward the availability of a greater number of H-bonding sites. At 298.15 K, all physical properties frame similar trends, with cyrene being at the top followed by DMI and GVL with CPME and 2-MeTHF at the bottom. Entropy of surface formation (Sγ) and enthalpy of surface formation (Hγ) were estimated using temperature dependence of surface tension. Dynamic viscosity follows Arrhenius-like expression with the temperature. The role of structural organization and the strength of intermolecular forces of interactions in controlling physical properties of renewable solvents is established.
从生物质中提取的可再生溶剂一直被视为传统有机溶剂的理想替代品。对物理特性的了解对于加快溶剂的潜在应用至关重要，尤其是在工业装置中。在此，我们报告了五种结构不同的可再生溶剂：芘、二甲基异山梨醇醚（DMI）、γ-戊内酯（GVL）、环戊基甲基醚（CPME）和 2-甲基四氢呋喃（2-MeTHF）的水混溶性、表面张力（γ）、密度（ρ）、动态粘度（η）和折射率（nD）。在 283.15-363.15 K 的温度范围内测量了密度和动态粘度，在 298.15-363.15 K 的温度范围内测量了表面张力。芘、DMI 和 GVL 的水混溶性相对较高，这表明存在更多的 H 键位点。在 298.15 K 时，所有物理性质都呈现出类似的趋势，芘的物理性质最高，其次是 DMI 和 GVL，CPME 和 2-MeTHF 的物理性质最低。利用表面张力的温度依赖性估算了表面形成熵（Sγ）和表面形成焓（Hγ）。动态粘度随温度的变化呈类似阿伦尼乌斯的表达式。确定了结构组织和分子间相互作用力的强度在控制可再生溶剂物理性质方面的作用。
{"title":"Physical Properties of Renewable Solvents Cyrene, Dimethylisosorbide, γ-Valerolactone, Cyclopentylmethyl Ether, and 2-Methyltetrahydrofuran","authors":"Anuj Sharma, Deepika, Siddharth Pandey","doi":"10.1021/acs.jced.4c00259","DOIUrl":"https://doi.org/10.1021/acs.jced.4c00259","url":null,"abstract":"Renewable solvents derived from biomass have been regarded as promising alternatives to conventional organic solvents. A knowledge of the physical properties is crucial to accelerate the potential applications of a solvent, especially in industrial setups. Herein, we report water miscibility, surface tension (γ), density (ρ), dynamic viscosity (η), and refractive index (<i>n</i><sup>D</sup>) of five structurally different renewable solvents: cyrene, dimethylisosorbide (DMI), γ-valerolactone (GVL), cyclopentylmethyl ether (CPME), and 2-methyltetrahydrofuran (2-MeTHF). Density and dynamic viscosity are measured in the temperature range of 283.15–363.15 K and surface tension is measured in the range of 298.15–363.15 K. Water miscibility and refractive index are estimated under ambient conditions. Comparatively higher water miscibility of cyrene, DMI, and GVL hints toward the availability of a greater number of H-bonding sites. At 298.15 K, all physical properties frame similar trends, with cyrene being at the top followed by DMI and GVL with CPME and 2-MeTHF at the bottom. Entropy of surface formation (S<sup>γ</sup>) and enthalpy of surface formation (H<sup>γ</sup>) were estimated using temperature dependence of surface tension. Dynamic viscosity follows Arrhenius-like expression with the temperature. The role of structural organization and the strength of intermolecular forces of interactions in controlling physical properties of renewable solvents is established.","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.694,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142266845","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}
Ionic liquids (ILs) show great potential for the treatment of dichloromethane (DCM)-containing waste gases, but currently there are limited data on the vapor–liquid equilibrium (VLE) of DCM + IL systems. This work uses headspace gas chromatography (HS-GC) to determine the isothermal VLE data of the DCM + [Epy][EtSO4] and DCM + [Emim][EtSO4] systems at 308.15 K, 313.15 K, 318.15 K, 323.15 K, and 328.15 K. The nonrandom two-liquid (NRTL) and universal quasi-chemical correlation activity coefficient (UNIQUAC) models are used to regress the VLE data. The results show that the fitting average relative deviations (ARDs) of the DCM + [Epy][EtSO4] and DCM + [Emim][EtSO4] systems to the NRTL model were 6.97% and 7.95% and the fitting ARDs to the UNIQUAC model were 6.10% and 6.28%, respectively. The fitting effects of the UNIQUAC models for both systems were better than those of the NRTL model. With the models, the calculated activity coefficients of DCM were all less than 1, indicating that the solutions exhibited negative deviations from Raoult’s law, and the nonideality of the solutions increased with increasing IL concentration.
{"title":"Measurement of Vapor–Liquid Equilibrium for Dichloromethane + Alkyl Sulfate-Based Ionic Liquid Systems","authors":"Yutong Zhang, Yinge Bai, Mengjun Wang, Shaojuan Zeng, Wei Han, Xiangping Zhang","doi":"10.1021/acs.jced.4c00240","DOIUrl":"https://doi.org/10.1021/acs.jced.4c00240","url":null,"abstract":"Ionic liquids (ILs) show great potential for the treatment of dichloromethane (DCM)-containing waste gases, but currently there are limited data on the vapor–liquid equilibrium (VLE) of DCM + IL systems. This work uses headspace gas chromatography (HS-GC) to determine the isothermal VLE data of the DCM + [Epy][EtSO<sub>4</sub>] and DCM + [Emim][EtSO<sub>4</sub>] systems at 308.15 K, 313.15 K, 318.15 K, 323.15 K, and 328.15 K. The nonrandom two-liquid (NRTL) and universal quasi-chemical correlation activity coefficient (UNIQUAC) models are used to regress the VLE data. The results show that the fitting average relative deviations (ARDs) of the DCM + [Epy][EtSO<sub>4</sub>] and DCM + [Emim][EtSO<sub>4</sub>] systems to the NRTL model were 6.97% and 7.95% and the fitting ARDs to the UNIQUAC model were 6.10% and 6.28%, respectively. The fitting effects of the UNIQUAC models for both systems were better than those of the NRTL model. With the models, the calculated activity coefficients of DCM were all less than 1, indicating that the solutions exhibited negative deviations from Raoult’s law, and the nonideality of the solutions increased with increasing IL concentration.","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.694,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142266846","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 : 2024-09-11DOI: 10.1021/acs.jced.4c00182
Anjali, Siddharth Pandey
In surfactant-free microemulsions (SFMEs), a hydrotrope assists in microemulsion formation. Use of natural hydrophobic deep eutectic solvents (HDESs) as the oil phase imparts environmental benefits. Density and dynamic viscosity are reported for hydrotrope ethanolamine (ETA)-assisted HDES-based SFME solutions formed using n-decanoic acid (DA) as one constituent of the HDES and one of the five structurally different closed or open ring terpenoids [thymol, l(−)-menthol, linalool, β-citronellol, and geraniol] as the other constituent in equimolar ratio with water as the polar medium. The amount of water was varied at a fixed concentration of hydrotrope where the formation of the microemulsion was optimum. Density decreased linearly with an increase in temperature for all systems. At higher water fractions, the SFMEs exhibit higher density than that expected, ideally providing evidence for the presence of water pools. Because of the inherent complexity associated, the temperature dependence of the dynamic viscosity adheres better to the Vogel–Fulcher–Tammann (VFT) formulation instead of the Arrhenius equation. As water is added to a high-viscosity (HDES/ETA) system, viscosity initially decreases but increases at higher water contents. It is attributed to the increasing size of the microemulsions formed as they create a hindrance to the overall fluidity. The density and dynamic viscosities of the SFME systems reveal important structural information about these organized assemblies.
{"title":"Density and Dynamic Viscosity of Hydrotrope-Assisted Surfactant Free Microemulsions Formed with Hydrophobic Deep Eutectic Solvents","authors":"Anjali, Siddharth Pandey","doi":"10.1021/acs.jced.4c00182","DOIUrl":"https://doi.org/10.1021/acs.jced.4c00182","url":null,"abstract":"In surfactant-free microemulsions (SFMEs), a hydrotrope assists in microemulsion formation. Use of natural hydrophobic deep eutectic solvents (HDESs) as the oil phase imparts environmental benefits. Density and dynamic viscosity are reported for hydrotrope ethanolamine (ETA)-assisted HDES-based SFME solutions formed using <i>n</i>-decanoic acid (DA) as one constituent of the HDES and one of the five structurally different closed or open ring terpenoids [thymol, <span>l</span>(−)-menthol, linalool, β-citronellol, and geraniol] as the other constituent in equimolar ratio with water as the polar medium. The amount of water was varied at a fixed concentration of hydrotrope where the formation of the microemulsion was optimum. Density decreased linearly with an increase in temperature for all systems. At higher water fractions, the SFMEs exhibit higher density than that expected, ideally providing evidence for the presence of water pools. Because of the inherent complexity associated, the temperature dependence of the dynamic viscosity adheres better to the Vogel–Fulcher–Tammann (VFT) formulation instead of the Arrhenius equation. As water is added to a high-viscosity (HDES/ETA) system, viscosity initially decreases but increases at higher water contents. It is attributed to the increasing size of the microemulsions formed as they create a hindrance to the overall fluidity. The density and dynamic viscosities of the SFME systems reveal important structural information about these organized assemblies.","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.694,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142188008","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}
Weak acid–salt solutions have become an alternative to antifreeze in frost-free air-source heat pumps (FFASHPs) owing to their low corrosiveness and cost. Although mixed weak acid–salts are effective for further reducing the freezing points and vapor pressures of the solutions, corresponding data are currently lacking, especially for temperatures ≤273 K. In this study, the vapor pressures of mixed potassium acetate (CH3COOK)–sodium formate (HCOONa)–water (H2O) and sodium acetate (CH3COONa)–potassium formate (HCOOK)–H2O were measured and correlated. Considering the circulation of antifreeze solutions in FFASHPs, 1:1 and 1:5 mass ratios of CH3COOK to HCOONa and CH3COONa to HCOOK were selected, respectively. The tested solute concentrations ranged from 0 to 50 wt %, and the tested temperatures ranged from 258 to 333 K. In total, 145 vapor pressure data points, ranging from 0.1121 to 12.9726 kPa, were obtained and fitted with modified Antoine equations. The average absolute deviations between the measured and calculated values were within 2.26%. The vapor pressures of the 44 wt % CH3COOK–HCOONa (CH3COOK:HCOONa = 1:1) and 42 wt % CH3COONa–HCOOK (CH3COONa:HCOOK = 1:5) solutions were approximate to those of the 30 wt % CaCl2 solution below 278 K, and the mixed weak acid–salt solutions could be regenerated at lower temperature conditions.
{"title":"Experimental Study on the Equilibrium Vapor Pressures of Mixed Weak Acid–Salt Solutions for Frost-Free Air-Source Heat Pumps","authors":"Hongshuo Qu, Libo Wang, Xiao Zhang, Xiaosong Zhang, Shifang Huang","doi":"10.1021/acs.jced.4c00309","DOIUrl":"https://doi.org/10.1021/acs.jced.4c00309","url":null,"abstract":"Weak acid–salt solutions have become an alternative to antifreeze in frost-free air-source heat pumps (FFASHPs) owing to their low corrosiveness and cost. Although mixed weak acid–salts are effective for further reducing the freezing points and vapor pressures of the solutions, corresponding data are currently lacking, especially for temperatures ≤273 K. In this study, the vapor pressures of mixed potassium acetate (CH<sub>3</sub>COOK)–sodium formate (HCOONa)–water (H<sub>2</sub>O) and sodium acetate (CH<sub>3</sub>COONa)–potassium formate (HCOOK)–H<sub>2</sub>O were measured and correlated. Considering the circulation of antifreeze solutions in FFASHPs, 1:1 and 1:5 mass ratios of CH<sub>3</sub>COOK to HCOONa and CH<sub>3</sub>COONa to HCOOK were selected, respectively. The tested solute concentrations ranged from 0 to 50 wt %, and the tested temperatures ranged from 258 to 333 K. In total, 145 vapor pressure data points, ranging from 0.1121 to 12.9726 kPa, were obtained and fitted with modified Antoine equations. The average absolute deviations between the measured and calculated values were within 2.26%. The vapor pressures of the 44 wt % CH<sub>3</sub>COOK–HCOONa (CH<sub>3</sub>COOK:HCOONa = 1:1) and 42 wt % CH<sub>3</sub>COONa–HCOOK (CH<sub>3</sub>COONa:HCOOK = 1:5) solutions were approximate to those of the 30 wt % CaCl<sub>2</sub> solution below 278 K, and the mixed weak acid–salt solutions could be regenerated at lower temperature conditions.","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.694,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142224649","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 : 2024-09-11DOI: 10.1021/acs.jced.4c00035
Gyan Prakash Dubey, Aarzoo Ahuja, Rachana Singh
Densities, speeds of sound, and viscosity values have been experimentally measured at temperature ranges from (298.15 to 308.15 K) and a pressure of 0.1 MPa for the whole compositions for the binary mixtures of tetrahydrofuran with methyl acetate, propyl acetate, and pentyl acetate. Excess molar volume (VmE), excess molar isentropic compressibility (ΔKS,mE), viscosity deviation (Δη), excess Gibb’s free energy of activation for viscous flow (ΔG*E), and partial molar volume (V̅m,i) have been derived with the help of experimental results and fitted to an extended Redlich–Kister equation by the least-squares approach that simultaneously considers the dependency on composition and temperature. For the calculated and experimental data, the standard deviations are estimated. The magnitude and sign of these excess properties have been utilized to explain the results in terms of structural and intermolecular interactions. Various semiempirical viscosity relations were tested using the data of viscosity of binary mixtures.
{"title":"Temperature and Composition Dependence of the Densities, Speed of Sound, and Viscosities of Binary Liquid Mixtures of Tetrahydrofuran with Methyl Acetate, Propyl Acetate, and Pentyl Acetate","authors":"Gyan Prakash Dubey, Aarzoo Ahuja, Rachana Singh","doi":"10.1021/acs.jced.4c00035","DOIUrl":"https://doi.org/10.1021/acs.jced.4c00035","url":null,"abstract":"Densities, speeds of sound, and viscosity values have been experimentally measured at temperature ranges from (298.15 to 308.15 K) and a pressure of 0.1 MPa for the whole compositions for the binary mixtures of tetrahydrofuran with methyl acetate, propyl acetate, and pentyl acetate. Excess molar volume (<i>V</i><sub><i>m</i></sub><sup><i>E</i></sup>), excess molar isentropic compressibility (Δ<i>K</i><sub><i>S,m</i></sub><sup><i>E</i></sup>), viscosity deviation (Δη), excess Gibb’s free energy of activation for viscous flow (Δ<i>G</i><sup>*<i>E</i></sup>), and partial molar volume (<i>V̅</i><sub><i>m</i>,<i>i</i></sub>) have been derived with the help of experimental results and fitted to an extended Redlich–Kister equation by the least-squares approach that simultaneously considers the dependency on composition and temperature. For the calculated and experimental data, the standard deviations are estimated. The magnitude and sign of these excess properties have been utilized to explain the results in terms of structural and intermolecular interactions. Various semiempirical viscosity relations were tested using the data of viscosity of binary mixtures.","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.694,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142188009","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 : 2024-09-10DOI: 10.1021/acs.jced.4c00419
Junjie Li, Long Zhao, Xin Xing, Yusheng Xiao, Min Ding, Peng Wang, Bingbing Li
The mole fraction solubility of Fmoc-l-valine in 14 pure solvents (methanol, ethanol n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, n-pentanol, isopentanol, butyl acetate, acetone, acetonitrile, 2-butanone, dimethyl carbonate) was determined by the static gravimetric method at a temperature range of 283.15 to 323.15 K under a pressure of 101.2 kPa. Among the 14 monosolvents, solubility increased with the increase of absolute temperature. The order of solubility is as follows: acetone (0.06274 mol/mol) > 2-butanone (0.05704 mol/mol) > methanol (0.03966 mol/mol) > ethanol (0.03124 mol/mol) > sec-butanol (0.02749 mol/mol) > n-propanol (0.02535 mol/mol) > n-butanol (0.02445 mol/mol) > n-pentanol (0.02335 mol/mol) > butyl acetate (0.02088 mol/mol) > isopropanol (0.02038 mol/mol) > isopentanol (0.01916 mol/mol) > isobutanol (0.01525 mol/mol) > dimethyl carbonate (0.01078 mol/mol) > acetonitrile (0.004770 mol/mol). The equilibrium solid phase of Fmoc-l-valine in the solvent systems was characterized by powder X-ray diffraction analysis. The solubility data were fitted using the modified Apelblat model, NRTL model, UNIQUAC model, and Margules model; at the same time, the model parameters and data deviation values were calculated. The results showed that the modified Apelblat model had better correlation results. Interaction energy, interaction region indicator (IRI), and molecular electrostatic potential surface (MEPS) were used to determine the internal interactions within Fmoc-l-valine solutions. The Hansen solubility parameters (HSPs) was utilized to assess the solvents’ capability and to elucidate its ability to dissolve Fmoc-l-valine. Furthermore, the mixing thermodynamic characteristics of Fmoc-l-valine in selected solvents were calculated using the NRTL model, which revealed that the mixing process was spontaneous and entropy-driven. The solubility data can be used for the preparation and optimization of the Fmoc-l-valine crystallization processes.
{"title":"Solubility of Fmoc-l-valine in Fourteen Monosolvents: Characterization, Determination, Analysis, and Model Correlation","authors":"Junjie Li, Long Zhao, Xin Xing, Yusheng Xiao, Min Ding, Peng Wang, Bingbing Li","doi":"10.1021/acs.jced.4c00419","DOIUrl":"https://doi.org/10.1021/acs.jced.4c00419","url":null,"abstract":"The mole fraction solubility of Fmoc-<span>l</span>-valine in 14 pure solvents (methanol, ethanol <i>n</i>-propanol, isopropanol, <i>n</i>-butanol, isobutanol, <i>sec</i>-butanol, <i>n</i>-pentanol, isopentanol, butyl acetate, acetone, acetonitrile, 2-butanone, dimethyl carbonate) was determined by the static gravimetric method at a temperature range of 283.15 to 323.15 K under a pressure of 101.2 kPa. Among the 14 monosolvents, solubility increased with the increase of absolute temperature. The order of solubility is as follows: acetone (0.06274 mol/mol) > 2-butanone (0.05704 mol/mol) > methanol (0.03966 mol/mol) > ethanol (0.03124 mol/mol) > <i>sec</i>-butanol (0.02749 mol/mol) > <i>n</i>-propanol (0.02535 mol/mol) > <i>n</i>-butanol (0.02445 mol/mol) > <i>n</i>-pentanol (0.02335 mol/mol) > butyl acetate (0.02088 mol/mol) > isopropanol (0.02038 mol/mol) > isopentanol (0.01916 mol/mol) > isobutanol (0.01525 mol/mol) > dimethyl carbonate (0.01078 mol/mol) > acetonitrile (0.004770 mol/mol). The equilibrium solid phase of Fmoc-<span>l</span>-valine in the solvent systems was characterized by powder X-ray diffraction analysis. The solubility data were fitted using the modified Apelblat model, NRTL model, UNIQUAC model, and Margules model; at the same time, the model parameters and data deviation values were calculated. The results showed that the modified Apelblat model had better correlation results. Interaction energy, interaction region indicator (IRI), and molecular electrostatic potential surface (MEPS) were used to determine the internal interactions within Fmoc-<span>l</span>-valine solutions. The Hansen solubility parameters (HSPs) was utilized to assess the solvents’ capability and to elucidate its ability to dissolve Fmoc-<span>l</span>-valine. Furthermore, the mixing thermodynamic characteristics of Fmoc-<span>l</span>-valine in selected solvents were calculated using the NRTL model, which revealed that the mixing process was spontaneous and entropy-driven. The solubility data can be used for the preparation and optimization of the Fmoc-<span>l</span>-valine crystallization processes.","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":null,"pages":null},"PeriodicalIF":2.694,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142224647","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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