{"title":"二甲醚-乙醇在 (293.2-313.2) K 和 1.00 MPa 下的液相体积特性和介电特性","authors":"Taka-aki Hoshina, Kazunori Sato, Masaki Okada, Tomoya Tsuji, Toshihiko Hiaki","doi":"10.1007/s10953-023-01329-5","DOIUrl":null,"url":null,"abstract":"<div><p>Density and dielectric spectra have been measured in the liquid phase of dimethyl ether (DME)–ethanol by an oscillating U-tube densimeter and a complex dielectric spectrometer under 1.00 MPa. The density was measured at 303.15 and 313.15 K and converted to the excess molar volume. The excess molar volumes were no smaller than − 0.880 and − 0.909 cm<sup>3</sup>·mol<sup>–1</sup> at 303.15 and 313.15 K, respectively. The mole fraction dependence can be correlated with the Redlich–Kister equation, whose minimum was found to be around 0.58 for the mole fraction of DME. The dielectric constant and the dielectric relaxation time were evaluated from the complex dielectric spectra in the frequency range from 0.5 to 18 GHz at (293.2–313.2) K and 1.00 MPa. The dielectric constants and the relaxation time were decreased with the mole fraction of DME, and the latter tended to be around 25 ps in the mole fraction range higher than 0.6. The logarithmic dielectric constants can be correlated with a similar function to the Hildebrand equation with the volume fraction. The effective Kirkwood <i>g</i>-factor was evaluated at 293.2–313.2 K and 1.00 MPa. The <i>g</i>-factors were given by two linear functions crossed around 0.6 for the mole fraction of DME. Considering an atomic composition (C<sub>2</sub>H<sub>6</sub>O), the molecular sizes are not so different for DME and ethanol. Then, the solution structure was thought to be microscopically changed around 0.6 for the mole fraction of DME. The mole fraction will be utilized to switch the solubility to extract amphipathic compounds.</p></div>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4000,"publicationDate":"2023-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Volumetric and Dielectric Properties in Liquid Phase of Dimethyl Ether–Ethanol at (293.2–313.2) K and 1.00 MPa\",\"authors\":\"Taka-aki Hoshina, Kazunori Sato, Masaki Okada, Tomoya Tsuji, Toshihiko Hiaki\",\"doi\":\"10.1007/s10953-023-01329-5\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Density and dielectric spectra have been measured in the liquid phase of dimethyl ether (DME)–ethanol by an oscillating U-tube densimeter and a complex dielectric spectrometer under 1.00 MPa. The density was measured at 303.15 and 313.15 K and converted to the excess molar volume. The excess molar volumes were no smaller than − 0.880 and − 0.909 cm<sup>3</sup>·mol<sup>–1</sup> at 303.15 and 313.15 K, respectively. The mole fraction dependence can be correlated with the Redlich–Kister equation, whose minimum was found to be around 0.58 for the mole fraction of DME. The dielectric constant and the dielectric relaxation time were evaluated from the complex dielectric spectra in the frequency range from 0.5 to 18 GHz at (293.2–313.2) K and 1.00 MPa. The dielectric constants and the relaxation time were decreased with the mole fraction of DME, and the latter tended to be around 25 ps in the mole fraction range higher than 0.6. The logarithmic dielectric constants can be correlated with a similar function to the Hildebrand equation with the volume fraction. The effective Kirkwood <i>g</i>-factor was evaluated at 293.2–313.2 K and 1.00 MPa. The <i>g</i>-factors were given by two linear functions crossed around 0.6 for the mole fraction of DME. Considering an atomic composition (C<sub>2</sub>H<sub>6</sub>O), the molecular sizes are not so different for DME and ethanol. Then, the solution structure was thought to be microscopically changed around 0.6 for the mole fraction of DME. 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引用次数: 0
摘要
使用振荡 U 型管密度计和复合介电光谱仪在 1.00 兆帕下测量了二甲醚(DME)-乙醇液相中的密度和介电光谱。密度是在 303.15 和 313.15 K 时测量的,并转换为过量摩尔体积。在 303.15 和 313.15 K 时,过剩摩尔体积分别不小于 - 0.880 和 - 0.909 cm3-mol-1。摩尔分数相关性可与 Redlich-Kister 方程联系起来,发现二甲醚摩尔分数的最小值约为 0.58。在 (293.2-313.2) K 和 1.00 MPa 条件下,根据 0.5 至 18 GHz 频率范围内的复介电常数和介电弛豫时间进行了评估。介电常数和弛豫时间随着二甲醚分子分数的增加而减小,在分子分数大于 0.6 的范围内,弛豫时间趋于 25 ps 左右。介电常数的对数与体积分数的希尔德布兰德方程的函数相似。在 293.2-313.2 K 和 1.00 MPa 下评估了有效的柯克伍德 g 因子。对于二甲醚的摩尔分数,g 系数由两个在 0.6 附近交叉的线性函数给出。考虑到原子成分(C2H6O),二甲醚和乙醇的分子大小相差不大。因此,我们认为二甲醚的摩尔分数在 0.6 左右时,溶液结构会发生微观变化。摩尔分数将被用来改变提取两性化合物的溶解度。
Volumetric and Dielectric Properties in Liquid Phase of Dimethyl Ether–Ethanol at (293.2–313.2) K and 1.00 MPa
Density and dielectric spectra have been measured in the liquid phase of dimethyl ether (DME)–ethanol by an oscillating U-tube densimeter and a complex dielectric spectrometer under 1.00 MPa. The density was measured at 303.15 and 313.15 K and converted to the excess molar volume. The excess molar volumes were no smaller than − 0.880 and − 0.909 cm3·mol–1 at 303.15 and 313.15 K, respectively. The mole fraction dependence can be correlated with the Redlich–Kister equation, whose minimum was found to be around 0.58 for the mole fraction of DME. The dielectric constant and the dielectric relaxation time were evaluated from the complex dielectric spectra in the frequency range from 0.5 to 18 GHz at (293.2–313.2) K and 1.00 MPa. The dielectric constants and the relaxation time were decreased with the mole fraction of DME, and the latter tended to be around 25 ps in the mole fraction range higher than 0.6. The logarithmic dielectric constants can be correlated with a similar function to the Hildebrand equation with the volume fraction. The effective Kirkwood g-factor was evaluated at 293.2–313.2 K and 1.00 MPa. The g-factors were given by two linear functions crossed around 0.6 for the mole fraction of DME. Considering an atomic composition (C2H6O), the molecular sizes are not so different for DME and ethanol. Then, the solution structure was thought to be microscopically changed around 0.6 for the mole fraction of DME. The mole fraction will be utilized to switch the solubility to extract amphipathic compounds.
期刊介绍:
Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance.
Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.