L. V. Sheina, E. V. Karaseva, A. N. Lobov, V. S. Kolosnitsyn
{"title":"三氟甲烷磺酸锂溶液在1.3-二恶氧烷混合砜中的物理化学和电化学性质","authors":"L. V. Sheina, E. V. Karaseva, A. N. Lobov, V. S. Kolosnitsyn","doi":"10.1134/S0036024424703345","DOIUrl":null,"url":null,"abstract":"<p>A study is performed of the physicochemical properties (specific ion conductivity, viscosity, and density) of 1.0M solutions of LiSO<sub>3</sub>CF<sub>3</sub> in mixtures of sulfolane and 1.3-dioxolane in the 30–50°C range of temperatures. It is shown that the isotherms of specific ion conductivity pass through a maximum at contents of 1.3-dioxolane around 60 mol % (1.75 × 10<sup>−3</sup> Ω<sup>−1</sup> cm<sup>−1</sup>, 30°C). It is found that the viscosity and corrected (for viscosity) conductivity of the studied solutions fall as the content of 1.3-dioxolane and temperature rise. It is concluded that the activation energies of conductivity and viscous flow fall as the content of 1.3-dioxolane grows. NMR spectroscopy is used to estimate the self-diffusion coefficients of all components of the studied electrolyte solutions and calculate the transport numbers of lithium cations. It is been established that the transport numbers of lithium cations change nonlinearly, depending on the composition of the solution. The maximum value (0.56) is reached at a sulfolane : 1.3-dioxolane ratio of around 2 : 3, which correlates with the position of the maximum on the conductivity isotherm. It is shown that the melting points for 1.0 M solutions of LiSO<sub>3</sub>CF<sub>3</sub> in mixtures of sulfolane and 1.3‑dioxolane fall as the content of the latter rises. It is noted that when the content of 1.3-dioxolane is more than 50 mol %, electrolyte solutions are in a liquid phase at temperatures below −70°C.</p>","PeriodicalId":767,"journal":{"name":"Russian Journal of Physical Chemistry A","volume":"99 2","pages":"308 - 317"},"PeriodicalIF":0.7000,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1134/S0036024424703345.pdf","citationCount":"0","resultStr":"{\"title\":\"Physicochemical and Electrochemical Properties of Lithium Trifluoromethanesulfonate Solutions in Sulfolane Mixtures of 1.3-Dioxolane\",\"authors\":\"L. V. Sheina, E. V. Karaseva, A. N. Lobov, V. S. Kolosnitsyn\",\"doi\":\"10.1134/S0036024424703345\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>A study is performed of the physicochemical properties (specific ion conductivity, viscosity, and density) of 1.0M solutions of LiSO<sub>3</sub>CF<sub>3</sub> in mixtures of sulfolane and 1.3-dioxolane in the 30–50°C range of temperatures. It is shown that the isotherms of specific ion conductivity pass through a maximum at contents of 1.3-dioxolane around 60 mol % (1.75 × 10<sup>−3</sup> Ω<sup>−1</sup> cm<sup>−1</sup>, 30°C). It is found that the viscosity and corrected (for viscosity) conductivity of the studied solutions fall as the content of 1.3-dioxolane and temperature rise. It is concluded that the activation energies of conductivity and viscous flow fall as the content of 1.3-dioxolane grows. NMR spectroscopy is used to estimate the self-diffusion coefficients of all components of the studied electrolyte solutions and calculate the transport numbers of lithium cations. It is been established that the transport numbers of lithium cations change nonlinearly, depending on the composition of the solution. The maximum value (0.56) is reached at a sulfolane : 1.3-dioxolane ratio of around 2 : 3, which correlates with the position of the maximum on the conductivity isotherm. It is shown that the melting points for 1.0 M solutions of LiSO<sub>3</sub>CF<sub>3</sub> in mixtures of sulfolane and 1.3‑dioxolane fall as the content of the latter rises. It is noted that when the content of 1.3-dioxolane is more than 50 mol %, electrolyte solutions are in a liquid phase at temperatures below −70°C.</p>\",\"PeriodicalId\":767,\"journal\":{\"name\":\"Russian Journal of Physical Chemistry A\",\"volume\":\"99 2\",\"pages\":\"308 - 317\"},\"PeriodicalIF\":0.7000,\"publicationDate\":\"2025-04-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1134/S0036024424703345.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Russian Journal of Physical Chemistry A\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S0036024424703345\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Journal of Physical Chemistry A","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1134/S0036024424703345","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Physicochemical and Electrochemical Properties of Lithium Trifluoromethanesulfonate Solutions in Sulfolane Mixtures of 1.3-Dioxolane
A study is performed of the physicochemical properties (specific ion conductivity, viscosity, and density) of 1.0M solutions of LiSO3CF3 in mixtures of sulfolane and 1.3-dioxolane in the 30–50°C range of temperatures. It is shown that the isotherms of specific ion conductivity pass through a maximum at contents of 1.3-dioxolane around 60 mol % (1.75 × 10−3 Ω−1 cm−1, 30°C). It is found that the viscosity and corrected (for viscosity) conductivity of the studied solutions fall as the content of 1.3-dioxolane and temperature rise. It is concluded that the activation energies of conductivity and viscous flow fall as the content of 1.3-dioxolane grows. NMR spectroscopy is used to estimate the self-diffusion coefficients of all components of the studied electrolyte solutions and calculate the transport numbers of lithium cations. It is been established that the transport numbers of lithium cations change nonlinearly, depending on the composition of the solution. The maximum value (0.56) is reached at a sulfolane : 1.3-dioxolane ratio of around 2 : 3, which correlates with the position of the maximum on the conductivity isotherm. It is shown that the melting points for 1.0 M solutions of LiSO3CF3 in mixtures of sulfolane and 1.3‑dioxolane fall as the content of the latter rises. It is noted that when the content of 1.3-dioxolane is more than 50 mol %, electrolyte solutions are in a liquid phase at temperatures below −70°C.
期刊介绍:
Russian Journal of Physical Chemistry A. Focus on Chemistry (Zhurnal Fizicheskoi Khimii), founded in 1930, offers a comprehensive review of theoretical and experimental research from the Russian Academy of Sciences, leading research and academic centers from Russia and from all over the world.
Articles are devoted to chemical thermodynamics and thermochemistry, biophysical chemistry, photochemistry and magnetochemistry, materials structure, quantum chemistry, physical chemistry of nanomaterials and solutions, surface phenomena and adsorption, and methods and techniques of physicochemical studies.