Pub Date : 2024-10-13DOI: 10.1016/j.jct.2024.107402
Densities of mixtures of uracil (Ura) with glycyl-glycine (GlyGly) and glycyl-phenylalanine (GlyPhe) in a buffered saline (pH 7.4) were measured at T=(288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K using the density meter DMA 5000 M (Anton Paar). The apparent molar volumes, limiting apparent molar volumes at infinite dilution and their derivatives with respect to temperature have been evaluated. Interactions of uracil (Ura) with glycylpeptides (GlyGly, GlyPhe, GlyTyr, GlyGlu) were studied with using review volumetric properties obtained early for Ura in GlyTyr and GlyGlu buffered solutions. The effect of concentration, ionic state and hydrophobicity of reagents on the Ura volume properties were discussed. The results indicate the complex formation between Ura and glycylpeptides with 1:1 stoichiometry. It was shown that the complexation of uracil with the glycylpeptides is accompanied by the positive changes of molar volume of Ura. The positive values of Hepler parameter indicate an increase in the ordering of the solvent in the environment of uracil with the addition of peptides. Uracil acts as a structure maker and its structure-making ability increases in series: Ura < GlyPhe < GlyGly < GlyGlu < GlyTyr.
使用密度计 DMA 5000 M（Anton Paar）测量了尿嘧啶（Ura）与甘氨酰-甘氨酸（GlyGly）和甘氨酰-苯丙氨酸（GlyPhe）在缓冲盐水（pH 7.4）中的混合物密度，温度分别为（288.15、293.15、298.15、303.15、308.15 和 313.15）K。评估了表观摩尔体积、无限稀释时的极限表观摩尔体积及其随温度变化的导数。研究了尿嘧啶（Ura）与糖肽（GlyGly、GlyPhe、GlyTyr、GlyGlu）的相互作用，并回顾了早期获得的 Ura 在 GlyTyr 和 GlyGlu 缓冲溶液中的体积特性。讨论了试剂的浓度、离子状态和疏水性对 Ura 体积特性的影响。结果表明，Ura 与糖肽之间形成了 1:1 的复合物。结果表明，尿嘧啶与糖肽的络合伴随着 Ura 摩尔体积的正向变化。赫普勒参数的正值表明，随着肽的加入，尿嘧啶环境中溶剂的有序性增强。尿嘧啶是一种结构制造者，其结构制造能力随系列的增加而增强：Ura < GlyPhe < GlyGly < GlyGlu < GlyTyr。
{"title":"Characterization of complexation of uracil with peptides through its volumetric properties in buffer saline solution at different temperatures","authors":"","doi":"10.1016/j.jct.2024.107402","DOIUrl":"10.1016/j.jct.2024.107402","url":null,"abstract":"<div><div>Densities of mixtures of uracil (Ura) with glycyl-glycine (GlyGly) and glycyl-phenylalanine (GlyPhe) in a buffered saline (pH 7.4) were measured at <em>T</em>=(288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K using the density meter DMA 5000 M (Anton Paar). The apparent molar volumes, limiting apparent molar volumes at infinite dilution and their derivatives with respect to temperature have been evaluated. Interactions of uracil (Ura) with glycylpeptides (GlyGly, GlyPhe, GlyTyr, GlyGlu) were studied with using review volumetric properties obtained early for Ura in GlyTyr and GlyGlu buffered solutions. The effect of concentration, ionic state and hydrophobicity of reagents on the Ura volume properties were discussed. The results indicate the complex formation between Ura and glycylpeptides with 1:1 stoichiometry. It was shown that the complexation of uracil with the glycylpeptides is accompanied by the positive changes of molar volume of Ura. The positive values of Hepler parameter indicate an increase in the ordering of the solvent in the environment of uracil with the addition of peptides. Uracil acts as a structure maker and its structure-making ability increases in series: Ura < GlyPhe < GlyGly < GlyGlu < GlyTyr.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142446634","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 : 2024-10-12DOI: 10.1016/j.jct.2024.107401
The pressure of saturated and unsaturated water vapor over α-CD·nH2O hydrates has been measured by static method with membrane-gauge manometer under conditions of complete loss of water. The temperature dependences of water vapor pressure have been obtained in the wide range of temperatures (287–469 K), pressures (0.04–34.95 kPa) and water content (0.17 ≤ n ≤ 6.0).
The data obtained indicate the presence of water molecules with different volatility in α-CD·nH2O hydrates. Water molecules with lower volatility can be considered “external”, included in the network of intermolecular hydrogen bonds, while water molecules with higher volatility, discovered in our previous study, are considered “internal”, presumably located in the α-CD cavity. For each composition, the amount of “external” and “internal” water has been determined and the equations described the dependence of the content of each type of water on n in α-CD·nH2O have been obtained. The analytical expressions for the lnp – 1/T dependences as well as the values of enthalpy and entropy of processes studied have been calculated. Experimental data were used to obtain the Gibbs energy changes when “external” water molecules bind to the α-CD framework. The values obtained are differed from the values for “internal” water given in our previous study. The phase transition in α-CD·nH2O revealed in our previous study is also observed in this work and its thermodynamic characteristics are in good agreement with the results obtained earlier. The findings have been confirmed by 1H NMR studies.
{"title":"Different States of water in α-Cyclodextrin hydrates","authors":"","doi":"10.1016/j.jct.2024.107401","DOIUrl":"10.1016/j.jct.2024.107401","url":null,"abstract":"<div><div>The pressure of saturated and unsaturated water vapor over <em>α</em>-CD·<em>n</em>H<sub>2</sub>O hydrates has been measured by static method with membrane-gauge manometer under conditions of complete loss of water. The temperature dependences of water vapor pressure have been obtained in the wide range of temperatures (287–469 K), pressures (0.04–34.95 kPa) and water content (0.17 ≤ <em>n</em> ≤ 6.0).</div><div>The data obtained indicate the presence of water molecules with different volatility in <em>α</em>-CD·<em>n</em>H<sub>2</sub>O hydrates. Water molecules with lower volatility can be considered “external”, included in the network of intermolecular hydrogen bonds, while water molecules with higher volatility, discovered in our previous study, are considered “internal”, presumably located in the α-CD cavity. For each composition, the amount of “external” and “internal” water has been determined and the equations described the dependence of the content of each type of water on <em>n</em> in <em>α</em>-CD·<em>n</em>H<sub>2</sub>O have been obtained. The analytical expressions for the ln<em>p</em> – 1<em>/T</em> dependences as well as the values of enthalpy and entropy of processes studied have been calculated. Experimental data were used to obtain the Gibbs energy changes when “external” water molecules bind to the <em>α</em>-CD framework. The values obtained are differed from the values for “internal” water given in our previous study. The phase transition in <em>α</em>-CD·<em>n</em>H<sub>2</sub>O revealed in our previous study is also observed in this work and its thermodynamic characteristics are in good agreement with the results obtained earlier. The findings have been confirmed by <sup>1</sup>H NMR studies.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142441014","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 : 2024-10-04DOI: 10.1016/j.jct.2024.107398
Based on the transient hot-wire apparatus, the thermal conductivity of ethane was measured in the temperature range of 146–247 K and pressure < 14 MPa in the liquid phase. The thermal conductivity of ethane + propane binary mixture was measured in the temperature range of 156–288 K and pressure < 25 MPa in the liquid phase. The mole fractions of ethane in binary systems are 0.198, 0.525, and 0.736. The deviation between experimental results and REFPROP calculation falls within 3 % of ethane and mixture. Subsequently, the previous established thermal conductivity model, derived from dimensional analysis, was employed to predict the thermal conductivity of n-alkanes mixture. The mixture critical parameters were obtained first by the mixing rules, and the thermal conductivity of the mixture were calculated. Comparisons were made between the experimental data of ethane and the previously constructed n-alkane model, resulting in an average absolute relative deviation (AARD) of 4.42 %. Similarly, the experimental data of the ethane + propane mixture was compared with the mixture prediction model proposed in this study, yielding an AARD of 1.92 %. The relative deviation between experimental data and model calculations demonstrates good consistency.
{"title":"Thermal conductivity measurements of liquid ethane and ethane + propane binary mixtures","authors":"","doi":"10.1016/j.jct.2024.107398","DOIUrl":"10.1016/j.jct.2024.107398","url":null,"abstract":"<div><div>Based on the transient hot-wire apparatus, the thermal conductivity of ethane was measured in the temperature range of 146–247 K and pressure < 14 MPa in the liquid phase. The thermal conductivity of ethane + propane binary mixture was measured in the temperature range of 156–288 K and pressure < 25 MPa in the liquid phase. The mole fractions of ethane in binary systems are 0.198, 0.525, and 0.736. The deviation between experimental results and REFPROP calculation falls within 3 % of ethane and mixture. Subsequently, the previous established thermal conductivity model, derived from dimensional analysis, was employed to predict the thermal conductivity of n-alkanes mixture. The mixture critical parameters were obtained first by the mixing rules, and the thermal conductivity of the mixture were calculated. Comparisons were made between the experimental data of ethane and the previously constructed n-alkane model, resulting in an average absolute relative deviation (AARD) of 4.42 %. Similarly, the experimental data of the ethane + propane mixture was compared with the mixture prediction model proposed in this study, yielding an AARD of 1.92 %. The relative deviation between experimental data and model calculations demonstrates good consistency.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142419883","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 : 2024-10-03DOI: 10.1016/j.jct.2024.107397
Levulinic acid (LA) is a crucial bio-based chemical with extensive industrial applications. Due to its significant share in the cost of production, the development of efficient techniques for the separation of LA is essential. Traditional separation using sulphuric acid raises environmental and cost concerns, making liquid–liquid extraction a more sustainable and cost-effective alternative. liquid–liquid equilibrium (LLE) investigation was carried out for two ternary mixtures of water + LA + isopropyl ether / methyl tert-butyl ether (MTBE) at two temperatures and 101.3 kPa. The results indicated that the solvent MTBE, as an extractant, showed a higher partition coefficient and selectivity for LA than isopropyl ether, demonstrating its superior effectiveness in recovering LA. The interaction insights between LA and the extractants were explored using quantum chemistry calculations, which aligned well with the collected results. The ascertained LLE data was modeled using the NRTL equation, achieving the RMSD values below 0.01, demonstrating a good concordance between the collected data and computed values. The fitted NRTL model parameters are conducive to the designing and optimizing the LA separation process.
乙酰丙酸（LA）是一种重要的生物基化学品，具有广泛的工业用途。由于其在生产成本中占很大比重，因此开发高效的 LA 分离技术至关重要。在两种温度和 101.3 kPa 条件下，对水 + LA + 异丙醚/甲基叔丁基醚（MTBE）的两种三元混合物进行了液液平衡（LLE）研究。结果表明，与异丙醚相比，作为萃取剂的 MTBE 对 LA 的分配系数和选择性更高，这表明 MTBE 在回收 LA 方面具有更好的效果。利用量子化学计算探讨了 LA 与萃取剂之间的相互作用，结果与收集到的数据十分吻合。使用 NRTL 方程对已确定的 LLE 数据进行建模，RMSD 值低于 0.01，表明收集的数据与计算值之间具有良好的一致性。拟合的 NRTL 模型参数有利于设计和优化 LA 分离过程。
{"title":"Liquid-Liquid equilibrium Behavior and intermolecular interactions of Levulinic acid and water with isopropyl ether and methyl Tert-Butyl ether","authors":"","doi":"10.1016/j.jct.2024.107397","DOIUrl":"10.1016/j.jct.2024.107397","url":null,"abstract":"<div><div>Levulinic acid (LA) is a crucial bio-based chemical with extensive industrial applications. Due to its significant share in the cost of production, the development of efficient techniques for the separation of LA is essential. Traditional separation using sulphuric acid raises environmental and cost concerns, making liquid–liquid extraction a more sustainable and cost-effective alternative. liquid–liquid equilibrium (LLE) investigation was carried out for two ternary mixtures of water + LA + isopropyl ether / methyl <em>tert</em>-butyl ether (MTBE) at two temperatures and 101.3 kPa. The results indicated that the solvent MTBE, as an extractant, showed a higher partition coefficient and selectivity for LA than isopropyl ether, demonstrating its superior effectiveness in recovering LA. The interaction insights between LA and the extractants were explored using quantum chemistry calculations, which aligned well with the collected results. The ascertained LLE data was modeled using the NRTL equation, achieving the <em>RMSD</em> values below 0.01, demonstrating a good concordance between the collected data and computed values. The fitted NRTL model parameters are conducive to the designing and optimizing the LA separation process.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142419884","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 : 2024-09-28DOI: 10.1016/j.jct.2024.107395
<div><div>The isothermal VLE properties (<em>PTxy</em> relationship) of a binary supercritical (SC) C<sub>3</sub>H<sub>8</sub> + o-toluidine mixture was measured by means of static-analytic method with fluid phase sampling at equilibrium conditions. The measurements were made at three temperatures of (393.15, 433.15, and 473.15) K and pressures up to 10.41 MPa. An experimental VLE apparatus, a high-temperature and high-pressure optical cell, has been used to measure the phase equilibrium properties (<em>PTxy</em>) of the binary SC C<sub>3</sub>H<sub>8</sub> + o-toluidine mixture. The combined expanded absolute and relative uncertainties of the temperature, pressure, and the phase concentration measurements at 0.95 confidence level with a coverage factor of <em>k</em> = 2 is estimated at 0.15 K, 0.5 %, 4.2 % (for <em>x</em>) and 4.8 % (for <em>y</em>), respectively. The critical curve data, <span><math><mrow><msub><mi>T</mi><mtext>C</mtext></msub></mrow></math></span>−<span><math><mrow><mi>x</mi></mrow></math></span>,<span><math><mrow><msub><mi>P</mi><mtext>C</mtext></msub></mrow></math></span>-<span><math><mrow><mi>x</mi></mrow></math></span>, and <span><math><mrow><msub><mi>P</mi><mtext>C</mtext></msub></mrow></math></span>− <span><math><mrow><msub><mi>T</mi><mtext>C</mtext></msub></mrow></math></span> projections, have been derived based on the measured VLE data. The measured VLE and the derived critical curve data were used to estimate the theoretically important and physical meaning of Krichevskii parameter, <span><math><mrow><msubsup><mrow><mfenced><mrow><mfrac><mrow><mi>∂</mi><mi>P</mi></mrow><mrow><mi>∂</mi><mi>x</mi></mrow></mfrac></mrow></mfenced></mrow><mrow><msub><mi>T</mi><mi>C</mi></msub><msub><mi>V</mi><mi>C</mi></msub></mrow><mi>∞</mi></msubsup></mrow></math></span>. Thermodynamic (partial molar properties, <span><math><mrow><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mn>2</mn><mi>∞</mi></msubsup><mo>,</mo><msubsup><mover><mrow><mi>H</mi></mrow><mrow><mo>¯</mo></mrow></mover><mn>2</mn><mi>∞</mi></msubsup><mo>,</mo><msubsup><mover><mrow><mi>C</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>P</mi><mn>2</mn></mrow><mi>∞</mi></msubsup></mrow></math></span>, and distribution equilibrium constant <span><math><mrow><msub><mi>K</mi><mi>D</mi></msub></mrow></math></span>), and microstructural (cluster’s size, <span><math><mrow><msubsup><mi>N</mi><mrow><mi>exc</mi></mrow><mi>∞</mi></msubsup></mrow></math></span>) properties of infinite-dilute C<sub>3</sub>H<sub>8</sub> + o-toluidine mixture near the critical point of pure solvent (C<sub>3</sub>H<sub>8</sub>) were calculated based on the derived Krichevskii parameter and pure solvent (SC C<sub>3</sub>H<sub>8</sub>) properties. CP-PC-SAFT and mg-SAFT equation of state (EoS), with zero interaction parameter, <span><math><mrow><msub><mi>k</mi><mn>12</mn></msub></mrow></math></span> = 0, for both models (pure prediction models, no adjustable parameters) were success
{"title":"Partial molar and microstructural properties of binary propane + o-toluidine system near the critical point of pure solvent based on the VLE measurements and modeling with CP-PC-SAFT and mg-SAFT equation of states","authors":"","doi":"10.1016/j.jct.2024.107395","DOIUrl":"10.1016/j.jct.2024.107395","url":null,"abstract":"<div><div>The isothermal VLE properties (<em>PTxy</em> relationship) of a binary supercritical (SC) C<sub>3</sub>H<sub>8</sub> + o-toluidine mixture was measured by means of static-analytic method with fluid phase sampling at equilibrium conditions. The measurements were made at three temperatures of (393.15, 433.15, and 473.15) K and pressures up to 10.41 MPa. An experimental VLE apparatus, a high-temperature and high-pressure optical cell, has been used to measure the phase equilibrium properties (<em>PTxy</em>) of the binary SC C<sub>3</sub>H<sub>8</sub> + o-toluidine mixture. The combined expanded absolute and relative uncertainties of the temperature, pressure, and the phase concentration measurements at 0.95 confidence level with a coverage factor of <em>k</em> = 2 is estimated at 0.15 K, 0.5 %, 4.2 % (for <em>x</em>) and 4.8 % (for <em>y</em>), respectively. The critical curve data, <span><math><mrow><msub><mi>T</mi><mtext>C</mtext></msub></mrow></math></span>−<span><math><mrow><mi>x</mi></mrow></math></span>,<span><math><mrow><msub><mi>P</mi><mtext>C</mtext></msub></mrow></math></span>-<span><math><mrow><mi>x</mi></mrow></math></span>, and <span><math><mrow><msub><mi>P</mi><mtext>C</mtext></msub></mrow></math></span>− <span><math><mrow><msub><mi>T</mi><mtext>C</mtext></msub></mrow></math></span> projections, have been derived based on the measured VLE data. The measured VLE and the derived critical curve data were used to estimate the theoretically important and physical meaning of Krichevskii parameter, <span><math><mrow><msubsup><mrow><mfenced><mrow><mfrac><mrow><mi>∂</mi><mi>P</mi></mrow><mrow><mi>∂</mi><mi>x</mi></mrow></mfrac></mrow></mfenced></mrow><mrow><msub><mi>T</mi><mi>C</mi></msub><msub><mi>V</mi><mi>C</mi></msub></mrow><mi>∞</mi></msubsup></mrow></math></span>. Thermodynamic (partial molar properties, <span><math><mrow><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mn>2</mn><mi>∞</mi></msubsup><mo>,</mo><msubsup><mover><mrow><mi>H</mi></mrow><mrow><mo>¯</mo></mrow></mover><mn>2</mn><mi>∞</mi></msubsup><mo>,</mo><msubsup><mover><mrow><mi>C</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>P</mi><mn>2</mn></mrow><mi>∞</mi></msubsup></mrow></math></span>, and distribution equilibrium constant <span><math><mrow><msub><mi>K</mi><mi>D</mi></msub></mrow></math></span>), and microstructural (cluster’s size, <span><math><mrow><msubsup><mi>N</mi><mrow><mi>exc</mi></mrow><mi>∞</mi></msubsup></mrow></math></span>) properties of infinite-dilute C<sub>3</sub>H<sub>8</sub> + o-toluidine mixture near the critical point of pure solvent (C<sub>3</sub>H<sub>8</sub>) were calculated based on the derived Krichevskii parameter and pure solvent (SC C<sub>3</sub>H<sub>8</sub>) properties. CP-PC-SAFT and mg-SAFT equation of state (EoS), with zero interaction parameter, <span><math><mrow><msub><mi>k</mi><mn>12</mn></msub></mrow></math></span> = 0, for both models (pure prediction models, no adjustable parameters) were success","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142419882","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 : 2024-09-26DOI: 10.1016/j.jct.2024.107394
A deeper comprehension of the mechanism behind various internal interactions and their influence on system properties encourages the utilization of ionic liquid mixture systems. In this work, the excess molar volume, viscosity deviation, change of electrical conductivity, and ionicity of both binary mixtures for N-methyl-N-methoxyethylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([MOEMPYrr][TFSI]) ether-functionalized ionic liquids (ILs) with 1,4-butyrolactone (GBL) or propylene carbonate (PC) were systematically studied. The specific interactions between ILs and solvent molecules were investigated by using the COSMO-RS model in terms of DFT calculation. The results indicate that [MOEMPYrr]+ tends to act as a hydrogen bond donor and [TFSI]- tends to act as a hydrogen bond acceptor, and GBL (or PC) has a strong hydrogen bond acceptance ability. Furthermore, based on the radial distribution functions (RDFs) from molecular dynamics (MD) simulations, the H1 atom in [MOEMPYrr]+, the O2 atom in [TFSI]-, the O3 atom in GBL, and the O4 atom in PC are selected as reference sites to study the interaction between cations and anions (or solvent molecules). It is found that the interaction between anions and cations in the [MOEMPYrr][TFSI] + PC system is stronger than that in the [MOEMPYrr][TFSI] + GBL system, and the interaction between cations and GBL is stronger than that between cations and PC. This result further explains why the excess molar volumes (VE) of [MOMPYrr][TFSI] + GBL binary mixtures are greater than that of [MOMPYrr][TFSI] + PC binary mixtures from a microscopic perspective.
深入了解各种内部相互作用的机理及其对系统特性的影响，有助于对离子液体混合物系统的利用。本研究系统研究了 N-甲基-N-甲氧基乙基吡咯烷鎓双三氟甲磺酰亚胺（[MOEMPYrr][TFSI]）醚官能化离子液体（ILs）与 1,4-丁内酯（GBL）或碳酸丙烯酯（PC）二元混合物的过剩摩尔体积、粘度偏差、电导率变化和离子性。在 DFT 计算方面，采用 COSMO-RS 模型研究了离子液体与溶剂分子之间的特定相互作用。结果表明，[MOEMPYrr]+倾向于作为氢键供体，而[TFSI]-倾向于作为氢键受体，GBL（或 PC）具有很强的氢键接受能力。此外，根据分子动力学（MD）模拟的径向分布函数（RDF），选择[MOEMPYrr]+ 中的 H1 原子、[TFSI]- 中的 O2 原子、GBL 中的 O3 原子和 PC 中的 O4 原子作为研究阳离子和阴离子（或溶剂分子）相互作用的参考位点。结果发现，[MOEMPYrr][TFSI] + PC 体系中阴离子与阳离子之间的相互作用强于[MOEMPYrr][TFSI] + GBL 体系，而阳离子与 GBL 之间的相互作用强于阳离子与 PC 之间的相互作用。这一结果进一步解释了为什么从微观角度来看，[MOMPYrr][TFSI] + GBL 二元混合物的过量摩尔体积（VE）大于[MOMPYrr][TFSI] + PC 二元混合物的过量摩尔体积（VE）。
{"title":"Insight into behaviors of internal interactions and thermodynamic properties of binary mixtures composed of ether-functionalized ionic liquids and 1,4-butyrolactone or propylene carbonate","authors":"","doi":"10.1016/j.jct.2024.107394","DOIUrl":"10.1016/j.jct.2024.107394","url":null,"abstract":"<div><div>A deeper comprehension of the mechanism behind various internal interactions and their influence on system properties encourages the utilization of ionic liquid mixture systems. In this work, the excess molar volume, viscosity deviation, change of electrical conductivity, and ionicity of both binary mixtures for N-methyl-N-methoxyethylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([MOEMPYrr][TFSI]) ether-functionalized ionic liquids (ILs) with 1,4-butyrolactone (GBL) or propylene carbonate (PC) were systematically studied. The specific interactions between ILs and solvent molecules were investigated by using the COSMO-RS model in terms of DFT calculation. The results indicate that [MOEMPYrr]<sup>+</sup> tends to act as a hydrogen bond donor and [TFSI]<sup>-</sup> tends to act as a hydrogen bond acceptor, and GBL (or PC) has a strong hydrogen bond acceptance ability. Furthermore, based on the radial distribution functions (RDFs) from molecular dynamics (MD) simulations, the H<sub>1</sub> atom in [MOEMPYrr]<sup>+</sup>, the O<sub>2</sub> atom in [TFSI]<sup>-</sup>, the O<sub>3</sub> atom in GBL, and the O<sub>4</sub> atom in PC are selected as reference sites to study the interaction between cations and anions (or solvent molecules). It is found that the interaction between anions and cations in the [MOEMPYrr][TFSI] + PC system is stronger than that in the [MOEMPYrr][TFSI] + GBL system, and the interaction between cations and GBL is stronger than that between cations and PC. This result further explains why the excess molar volumes (<em>V</em><sup>E</sup>) of [MOMPYrr][TFSI] + GBL binary mixtures are greater than that of [MOMPYrr][TFSI] + PC binary mixtures from a microscopic perspective.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142356951","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 : 2024-09-23DOI: 10.1016/j.jct.2024.107396
<div><div>In the present investigation density, speed of sound, and viscosity have been reported for binary liquid mixtures of 1,2-propanediol (1,2-PD) with 2-methoxyethanol (2-ME) and 2-ethoxyethanol (2-EE) over the entire composition range at T= (298.15–323.15) K. From the experimental data, excess molar volume, (<span><math><msubsup><mi>V</mi><mi>m</mi><mi>E</mi></msubsup></math></span>), excess isentropic compressibility, (<span><math><msubsup><mi>κ</mi><mi>s</mi><mi>E</mi></msubsup></math></span>), excess molar isentropic compressibility, (<span><math><msubsup><mi>κ</mi><mrow><mi>s</mi><mo>,</mo><mi>m</mi></mrow><mi>E</mi></msubsup></math></span>), excess speed of sound, (<span><math><msup><mi>u</mi><mi>E</mi></msup></math></span>), excess isobaric thermal expansion,<span><math><msubsup><mi>α</mi><mrow><mi>p</mi></mrow><mi>E</mi></msubsup></math></span>, and deviation in viscosity (<span><math><mrow><mi>Δ</mi><mi>η</mi></mrow></math></span>) of liquid mixtures have been calculated. The excess partial molar volume,<span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>1</mn></mrow><mi>E</mi></msubsup></math></span>, <span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>2</mn></mrow><mi>E</mi></msubsup></math></span> , excess partial molar isentropic compressibility, <span><math><msubsup><mover><mrow><mi>K</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>s</mi><mo>,</mo><mi>m</mi><mo>,</mo><mn>1</mn></mrow><mi>E</mi></msubsup></math></span><span><math><msubsup><mover><mrow><mi>K</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>s</mi><mo>,</mo><mi>m</mi><mo>,</mo><mn>2</mn></mrow><mi>E</mi></msubsup></math></span> over the whole composition range together with partial molar volume,<span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>1</mn></mrow><mn>0</mn></msubsup></math></span>, <span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>2</mn></mrow><mn>0</mn></msubsup></math></span>, partial molar isentropic compressibility <span><math><msubsup><mover><mrow><mi>K</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>s</mi><mo>,</mo><mi>m</mi><mo>,</mo><mn>1</mn></mrow><mn>0</mn></msubsup></math></span>,<span><math><msubsup><mover><mrow><mi>K</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>s</mi><mo>,</mo><mi>m</mi><mo>,</mo><mn>2</mn></mrow><mn>0</mn></msubsup></math></span>, excess partial molar volume,<span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>1</mn></mrow><mrow><mn>0</mn><mi>E</mi></mrow></msubsup></math></span>, <span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>2</mn></mrow><mrow><mn>0</mn><mi>E</mi></mrow></msubsup></math></span> and excess partial molar isentropic compressibil
{"title":"Thermodynamic and transport properties of binary mixtures containing 1,2-propanediol with 2-methoxyethanol and 2-ethoxyethanol at different temperatures","authors":"","doi":"10.1016/j.jct.2024.107396","DOIUrl":"10.1016/j.jct.2024.107396","url":null,"abstract":"<div><div>In the present investigation density, speed of sound, and viscosity have been reported for binary liquid mixtures of 1,2-propanediol (1,2-PD) with 2-methoxyethanol (2-ME) and 2-ethoxyethanol (2-EE) over the entire composition range at T= (298.15–323.15) K. From the experimental data, excess molar volume, (<span><math><msubsup><mi>V</mi><mi>m</mi><mi>E</mi></msubsup></math></span>), excess isentropic compressibility, (<span><math><msubsup><mi>κ</mi><mi>s</mi><mi>E</mi></msubsup></math></span>), excess molar isentropic compressibility, (<span><math><msubsup><mi>κ</mi><mrow><mi>s</mi><mo>,</mo><mi>m</mi></mrow><mi>E</mi></msubsup></math></span>), excess speed of sound, (<span><math><msup><mi>u</mi><mi>E</mi></msup></math></span>), excess isobaric thermal expansion,<span><math><msubsup><mi>α</mi><mrow><mi>p</mi></mrow><mi>E</mi></msubsup></math></span>, and deviation in viscosity (<span><math><mrow><mi>Δ</mi><mi>η</mi></mrow></math></span>) of liquid mixtures have been calculated. The excess partial molar volume,<span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>1</mn></mrow><mi>E</mi></msubsup></math></span>, <span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>2</mn></mrow><mi>E</mi></msubsup></math></span> , excess partial molar isentropic compressibility, <span><math><msubsup><mover><mrow><mi>K</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>s</mi><mo>,</mo><mi>m</mi><mo>,</mo><mn>1</mn></mrow><mi>E</mi></msubsup></math></span><span><math><msubsup><mover><mrow><mi>K</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>s</mi><mo>,</mo><mi>m</mi><mo>,</mo><mn>2</mn></mrow><mi>E</mi></msubsup></math></span> over the whole composition range together with partial molar volume,<span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>1</mn></mrow><mn>0</mn></msubsup></math></span>, <span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>2</mn></mrow><mn>0</mn></msubsup></math></span>, partial molar isentropic compressibility <span><math><msubsup><mover><mrow><mi>K</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>s</mi><mo>,</mo><mi>m</mi><mo>,</mo><mn>1</mn></mrow><mn>0</mn></msubsup></math></span>,<span><math><msubsup><mover><mrow><mi>K</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>s</mi><mo>,</mo><mi>m</mi><mo>,</mo><mn>2</mn></mrow><mn>0</mn></msubsup></math></span>, excess partial molar volume,<span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>1</mn></mrow><mrow><mn>0</mn><mi>E</mi></mrow></msubsup></math></span>, <span><math><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mn>2</mn></mrow><mrow><mn>0</mn><mi>E</mi></mrow></msubsup></math></span> and excess partial molar isentropic compressibil","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142328299","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 : 2024-09-21DOI: 10.1016/j.jct.2024.107393
The excess isentropic compressibility, excess speed of sound, excess molar isentropic compressibility and deviation in viscosity were evaluated from the experimental values of speeds of sound and viscosities of N,N-dimethylformamide + methyl acrylate/ethyl acrylate/n-butyl acrylate binary mixtures over the entire composition range at temperatures (288.15–318.15) K and pressure (101 kPa). Further, the partial molar isentropic compressibility; excess partial molar isentropic compressibility of the components over the entire composition range and also at infinite dilution have been calculated. These evaluated parameters have been interpreted in relations to prevailing interactions in these mixtures. These interactions were found dependent on the size of alkyl group in acrylate molecules and the amide-acrylate interactions decline with increase in size of the alkyl group. Moreover, the speeds of sound for the mixtures were calculated by scaled particle theory and the results compared well with the experimental results. Also, the viscosities of these mixtures were correlated by means of various empirical relations and the results were found in good agreement with the experimental results.
根据 N,N-二甲基甲酰胺 + 丙烯酸甲酯/丙烯酸乙酯/丙烯酸正丁酯二元混合物在温度 (288.15-318.15) K 和压力 (101 kPa) 下整个成分范围内的声速和粘度实验值，评估了过量等熵压缩率、过量声速、过量摩尔等熵压缩率和粘度偏差。此外，还计算了各组分在整个成分范围内以及无限稀释时的部分摩尔等熵压缩率和过量部分摩尔等熵压缩率。这些评估参数与这些混合物中普遍存在的相互作用有关。研究发现，这些相互作用取决于丙烯酸酯分子中烷基的大小，酰胺-丙烯酸酯的相互作用随着烷基的增大而减弱。此外，混合物的声速是通过缩放粒子理论计算得出的，其结果与实验结果比较吻合。此外，还通过各种经验关系对这些混合物的粘度进行了相关分析，结果与实验结果十分吻合。
{"title":"Insight into molecular interactions prevailing in N,N-dimethylformamide + alkyl acrylates mixtures at different temperatures: An experimental and theoretical investigation","authors":"","doi":"10.1016/j.jct.2024.107393","DOIUrl":"10.1016/j.jct.2024.107393","url":null,"abstract":"<div><div>The excess isentropic compressibility, excess speed of sound, excess molar isentropic compressibility and deviation in viscosity were evaluated from the experimental values of speeds of sound and viscosities of N,N-dimethylformamide + methyl acrylate/ethyl acrylate/<em>n</em>-butyl acrylate binary mixtures over the entire composition range at temperatures (288.15–318.15) K and pressure (101 kPa). Further, the partial molar isentropic compressibility; excess partial molar isentropic compressibility of the components over the entire composition range and also at infinite dilution have been calculated. These evaluated parameters have been interpreted in relations to prevailing interactions in these mixtures. These interactions were found dependent on the size of alkyl group in acrylate molecules and the amide-acrylate interactions decline with increase in size of the alkyl group. Moreover, the speeds of sound for the mixtures were calculated by scaled particle theory and the results compared well with the experimental results. Also, the viscosities of these mixtures were correlated by means of various empirical relations and the results were found in good agreement with the experimental results.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142419881","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 : 2024-09-19DOI: 10.1016/j.jct.2024.107392
Thermodynamic properties like excess volume , excess partial volume in isentropic compressibility deviations Δ , and refractive index deviations have been calculated based on experimental density ρ, speed of sound u, and refractive index by an Anton Paar / DSA 5000/ densimeter and Anton Paar Abbemat / 500/ refractometer. The systems of diethylene glycol monoethyl ether (DEGEE) + 2-propanol, or + 2-butanol, or + 2-pentanol, or + 2-hexanol, or + 2-heptanol, were given at T = (298.15–318.15) in 10 K intervals at ambient pressure (81.5 kPa) have been investigated. Data was fitted by Redlich-Kister relation. is negative for + 2-propanol and positive sign for other systems observed. The Δ is negative for all systems, except for + 2-heptanol system is positive. The is negative for + 2-hexanol or + 2-heptanol systems and is positive for all the rest. The The intermolecular interactions and structure factors were discussed for the binary mixtures. In addition the Prigogine–Flory–Patterson theory (PFP) and Extended Real Associated Solutions (ERAS) models were used to correlate data of binary mixtures. The fitting data for all systems reasonable consistency with experimental data for all the systems.
{"title":"The study of thermodynamic properties of diethylene glycol monoethyl ether with 2-alkanols (C3 − C7) with use of PFP and ERAS modeling","authors":"","doi":"10.1016/j.jct.2024.107392","DOIUrl":"10.1016/j.jct.2024.107392","url":null,"abstract":"<div><div>Thermodynamic properties like excess volume <span><math><msubsup><mi>V</mi><mrow><mi>m</mi></mrow><mi>E</mi></msubsup></math></span>, excess partial volume <span><math><mrow><msubsup><mover><mrow><mi>V</mi></mrow><mrow><mo>¯</mo></mrow></mover><mrow><mi>m</mi><mo>,</mo><mi>i</mi></mrow><mi>E</mi></msubsup><mo>,</mo></mrow></math></span> in isentropic compressibility deviations Δ <span><math><msub><mi>K</mi><mi>s</mi></msub></math></span>, and refractive index deviations <span><math><mrow><mi>Δ</mi><msub><mi>n</mi><mi>D</mi></msub><mo>,</mo><mspace></mspace></mrow></math></span> have been calculated based on experimental density <em>ρ</em>, speed of sound <em>u</em>, and refractive index <span><math><msub><mi>n</mi><mrow><mi>D</mi><mo>,</mo><mspace></mspace><mspace></mspace></mrow></msub></math></span> by an Anton Paar / DSA 5000/ densimeter and Anton Paar Abbemat / 500/ refractometer. The systems of diethylene glycol monoethyl ether (DEGEE) + 2-propanol, or + 2-butanol, or + 2-pentanol, or + 2-hexanol, or + 2-heptanol, were given at <em>T</em> = (298.15–318.15) in 10 K intervals at ambient pressure (81.5 kPa) have been investigated. Data was fitted by Redlich-Kister relation.<span><math><msubsup><mrow><mspace></mspace><mi>T</mi><mi>h</mi><mi>e</mi><mi>V</mi></mrow><mrow><mi>m</mi></mrow><mi>E</mi></msubsup></math></span> is negative for + 2-propanol and positive sign for other systems observed. The Δ <span><math><msub><mi>K</mi><mi>s</mi></msub></math></span> is negative for all systems, except for + 2-heptanol system is positive. The <span><math><mrow><mi>Δ</mi><msub><mi>n</mi><mi>D</mi></msub></mrow></math></span> is negative for + 2-hexanol or + 2-heptanol systems and is positive for all the rest. The The intermolecular interactions and structure factors were discussed for the binary mixtures. In addition the Prigogine–Flory–Patterson theory (PFP) and Extended Real Associated Solutions (ERAS) models were used to correlate <span><math><msubsup><mi>V</mi><mrow><mi>m</mi></mrow><mi>E</mi></msubsup></math></span> data of binary mixtures. The fitting data for all systems reasonable consistency with experimental data for all the systems.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314600","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: 10.1016/j.jct.2024.107391
The intermolecular interactions in ethyl acetate + polyethylene glycols (PEG) mixtures were examined by means of the excess and partial molar properties and FTIR spectra. The measurements of density and speed of sound of ethyl acetate + polyethylene glycols (PEG 200, PEG 300, PEG 400 and PEG 600) binary mixtures have been carried out over whole composition range at temperature from 293.15 K to 323.15 K and pressure, p = 100 kPa. The ρ and u data have been used to calculate excess properties, viz., excess molar volume, excess isentropic compressibility, excess intermolecular free length, excess speed of sound and excess molar isentropic compressibility. In addition, the partial molar volume/compressibility; excess partial molar volume/compressibility of the components over the entire composition range, and at infinite dilution have also been calculated. The variations in these properties with composition and temperature have been conversed in terms of existing intermolecular interactions in these mixtures. The ethyl acetate-PEG interactions in these mixtures follow the order: PEG 600 > PEG 400 > PEG 300 > PEG 200. The speeds of sound were estimated theoretically by using the scaled particle theory and were compared with the experimental values. Furthermore, FT-IR spectra of pure ethyl acetate, PEG 200 and their equimolar mixture were also recorded and analysed to confirm the prevailing intermolecular interactions.
通过过量和部分摩尔特性以及傅立叶变换红外光谱，研究了醋酸乙酯 + 聚乙二醇（PEG）混合物中的分子间相互作用。在温度为 293.15 K 至 323.15 K 和压力为 p = 100 kPa 的整个组成范围内，对醋酸乙酯 + 聚乙二醇（PEG 200、PEG 300、PEG 400 和 PEG 600）二元混合物的密度和声速进行了测量。ρ 和 u 数据用于计算过量特性，即过量摩尔体积、过量等熵压缩性、过量分子间自由长度、过量声速和过量摩尔等熵压缩性。此外，还计算了各组分在整个成分范围内和无限稀释时的部分摩尔体积/压缩性、过量部分摩尔体积/压缩性。根据这些混合物中现有的分子间相互作用，对这些特性随成分和温度的变化进行了分析。在这些混合物中，乙酸乙酯与 PEG 之间的相互作用顺序如下：PEG 600 > PEG 400 > PEG 300 > PEG 200。利用缩放粒子理论对声速进行了理论估算，并与实验值进行了比较。此外，还记录并分析了纯乙酸乙酯、PEG 200 及其等摩尔混合物的傅立叶变换红外光谱，以确认分子间的相互作用。
{"title":"Unveiling the intermolecular interactions in ethyl acetate + polyethylene glycol 200/300/400/600 binary mixtures by using densities, speeds of sound, excess properties and FTIR spectra at different temperatures","authors":"","doi":"10.1016/j.jct.2024.107391","DOIUrl":"10.1016/j.jct.2024.107391","url":null,"abstract":"<div><div>The intermolecular interactions in ethyl acetate + polyethylene glycols (PEG) mixtures were examined by means of the excess and partial molar properties and FTIR spectra. The measurements of density and speed of sound of ethyl acetate + polyethylene glycols (PEG 200, PEG 300, PEG 400 and PEG 600) binary mixtures have been carried out over whole composition range at temperature from 293.15 K to 323.15 K and pressure, p = 100 kPa. The <em>ρ</em> and <em>u</em> data have been used to calculate excess properties, <em>viz.</em>, excess molar volume, excess isentropic compressibility, excess intermolecular free length, excess speed of sound and excess molar isentropic compressibility. In addition, the partial molar volume/compressibility; excess partial molar volume/compressibility of the components over the entire composition range, and at infinite dilution have also been calculated. The variations in these properties with composition and temperature have been conversed in terms of existing intermolecular interactions in these mixtures. The ethyl acetate-PEG interactions in these mixtures follow the order: PEG 600 > PEG 400 > PEG 300 > PEG 200. The speeds of sound were estimated theoretically by using the scaled particle theory and were compared with the experimental values. Furthermore, FT-IR spectra of pure ethyl acetate, PEG 200 and their equimolar mixture were also recorded and analysed to confirm the prevailing intermolecular interactions.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142328298","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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