{"title":"新型醚官能化[Co(NCS)4]2-顺磁离子液体的热力学性质","authors":"Qiang Yan, Wenxu Zhu, Xiaoxue Ma, Na Liu, Yucheng Liu, Meichen Xia","doi":"10.1007/s11581-024-05785-x","DOIUrl":null,"url":null,"abstract":"<div><p>A series of ether-functionalized paramagnetic ionic liquids, 1-(2-methoxyethyl)-3-alkylimidazolium tetra thiocyanate cobalt [C<sub><i>n</i></sub>2O1IM]<sub>2</sub>[Co(NCS)<sub>4</sub>] (<i>n</i> = 1, 2, 3), was synthesized and characterized. The density, surface tension, refractive index, and electrical conductivity of these ionic liquids were measured at 293.15 to 343.15 K at intervals of 5 K, and their thermal expansion coefficients <i>α</i> were calculated. The molecular volume was obtained by measuring the pore volume and porosity. Based on Glasser theory, the standard entropy <i>S</i><sub>0</sub> (298 K), lattice energy<i> U</i><sub>POT</sub>, surface entropy <i>S</i><sub>a</sub>, and surface enthalpy, <i>H</i> of the ionic liquids were calculated, and the reason why the ionic liquid is in a molten state at room temperature was explained from the perspective of lattice energy. The molar surface Gibbs energy was introduced to improve the traditional Eötvös equation, which was combined with the refractive index to estimate the surface tension, obtaining a fitting index exceeding 0.99. Finally, the relationship between the electrical conductivity of the ionic liquids and temperature was investigated, and the activation energy, molar electrical conductivity, and electrical conductivity diffusion coefficient of the ionic liquids were obtained. The relationship between their properties was summarized. Compared with previously reported ionic liquids using 1-(2-methoxyethyl)-3-methylimidazolium as a cation, this type of ionic liquid has higher density and a smaller coefficient of thermal expansion.</p></div>","PeriodicalId":599,"journal":{"name":"Ionics","volume":"30 11","pages":"7113 - 7123"},"PeriodicalIF":2.4000,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Thermodynamic properties of new ether-functionalized [Co(NCS)4]2− paramagnetic ionic liquids\",\"authors\":\"Qiang Yan, Wenxu Zhu, Xiaoxue Ma, Na Liu, Yucheng Liu, Meichen Xia\",\"doi\":\"10.1007/s11581-024-05785-x\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>A series of ether-functionalized paramagnetic ionic liquids, 1-(2-methoxyethyl)-3-alkylimidazolium tetra thiocyanate cobalt [C<sub><i>n</i></sub>2O1IM]<sub>2</sub>[Co(NCS)<sub>4</sub>] (<i>n</i> = 1, 2, 3), was synthesized and characterized. The density, surface tension, refractive index, and electrical conductivity of these ionic liquids were measured at 293.15 to 343.15 K at intervals of 5 K, and their thermal expansion coefficients <i>α</i> were calculated. The molecular volume was obtained by measuring the pore volume and porosity. Based on Glasser theory, the standard entropy <i>S</i><sub>0</sub> (298 K), lattice energy<i> U</i><sub>POT</sub>, surface entropy <i>S</i><sub>a</sub>, and surface enthalpy, <i>H</i> of the ionic liquids were calculated, and the reason why the ionic liquid is in a molten state at room temperature was explained from the perspective of lattice energy. The molar surface Gibbs energy was introduced to improve the traditional Eötvös equation, which was combined with the refractive index to estimate the surface tension, obtaining a fitting index exceeding 0.99. Finally, the relationship between the electrical conductivity of the ionic liquids and temperature was investigated, and the activation energy, molar electrical conductivity, and electrical conductivity diffusion coefficient of the ionic liquids were obtained. The relationship between their properties was summarized. Compared with previously reported ionic liquids using 1-(2-methoxyethyl)-3-methylimidazolium as a cation, this type of ionic liquid has higher density and a smaller coefficient of thermal expansion.</p></div>\",\"PeriodicalId\":599,\"journal\":{\"name\":\"Ionics\",\"volume\":\"30 11\",\"pages\":\"7113 - 7123\"},\"PeriodicalIF\":2.4000,\"publicationDate\":\"2024-08-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Ionics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11581-024-05785-x\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Ionics","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11581-024-05785-x","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
合成并表征了一系列醚官能化顺磁性离子液体--1-(2-甲氧基乙基)-3-烷基咪唑四硫氰酸钴[Cn2O1IM]2[Co(NCS)4](n = 1、2、3)。在 293.15 至 343.15 K 温度下,以 5 K 为间隔测量了这些离子液体的密度、表面张力、折射率和电导率,并计算了它们的热膨胀系数 α。分子体积是通过测量孔体积和孔隙率得到的。根据 Glasser 理论,计算了离子液体的标准熵 S0(298 K)、晶格能 UPOT、表面熵 Sa 和表面焓 H,并从晶格能的角度解释了离子液体在室温下处于熔融状态的原因。引入摩尔表面吉布斯能改进了传统的 Eötvös 公式,并结合折射率估算了表面张力,得到了超过 0.99 的拟合指数。最后,研究了离子液体的电导率与温度的关系,得到了离子液体的活化能、摩尔电导率和电导扩散系数。总结了离子液体特性之间的关系。与之前报道的以 1-(2-甲氧基乙基)-3-甲基咪唑鎓为阳离子的离子液体相比,这种离子液体的密度更高,热膨胀系数更小。
Thermodynamic properties of new ether-functionalized [Co(NCS)4]2− paramagnetic ionic liquids
A series of ether-functionalized paramagnetic ionic liquids, 1-(2-methoxyethyl)-3-alkylimidazolium tetra thiocyanate cobalt [Cn2O1IM]2[Co(NCS)4] (n = 1, 2, 3), was synthesized and characterized. The density, surface tension, refractive index, and electrical conductivity of these ionic liquids were measured at 293.15 to 343.15 K at intervals of 5 K, and their thermal expansion coefficients α were calculated. The molecular volume was obtained by measuring the pore volume and porosity. Based on Glasser theory, the standard entropy S0 (298 K), lattice energy UPOT, surface entropy Sa, and surface enthalpy, H of the ionic liquids were calculated, and the reason why the ionic liquid is in a molten state at room temperature was explained from the perspective of lattice energy. The molar surface Gibbs energy was introduced to improve the traditional Eötvös equation, which was combined with the refractive index to estimate the surface tension, obtaining a fitting index exceeding 0.99. Finally, the relationship between the electrical conductivity of the ionic liquids and temperature was investigated, and the activation energy, molar electrical conductivity, and electrical conductivity diffusion coefficient of the ionic liquids were obtained. The relationship between their properties was summarized. Compared with previously reported ionic liquids using 1-(2-methoxyethyl)-3-methylimidazolium as a cation, this type of ionic liquid has higher density and a smaller coefficient of thermal expansion.
期刊介绍:
Ionics is publishing original results in the fields of science and technology of ionic motion. This includes theoretical, experimental and practical work on electrolytes, electrode, ionic/electronic interfaces, ionic transport aspects of corrosion, galvanic cells, e.g. for thermodynamic and kinetic studies, batteries, fuel cells, sensors and electrochromics. Fast solid ionic conductors are presently providing new opportunities in view of several advantages, in addition to conventional liquid electrolytes.