Department of Chemistry and Biochemistry, University of Oklahoma , 101 Stephenson Parkway, Norman, Oklahoma 73019, United States.
J Phys Chem B. 2012 May 17;116(19):5760-5. doi: 10.1021/jp209205u. Epub 2012 May 4.
The temperature dependence of ionic conductivity and the static dielectric constant is examined for 0.30 m TbaTf- or LiTf-1-alcohol solutions. Above ambient temperature, the conductivity increases with temperature to a greater extent in electrolytes whose salt has a charge-protected cation. Below ambient temperature, the dielectric constant changes only slightly with temperature in electrolytes whose salt has a cation that is not charge-protected. The compensated Arrhenius formalism is used to describe the temperature-dependent conductivity in terms of the contributions from both the exponential prefactor σo and Boltzmann factor exp(-Ea/RT). This analysis explains why the conductivity decreases with increasing temperature above 65 °C for the LiTf-dodecanol electrolyte. At higher temperatures, the decrease in the exponential prefactor is greater than the increase in the Boltzmann factor.
考察了 0.30 m TbaTf- 或 LiTf-1-醇溶液中离子电导率和静态介电常数随温度的变化。在环境温度以上，盐的阳离子具有电荷保护的电解质中，电导率随温度升高的程度更大。在环境温度以下，盐的阳离子没有电荷保护的电解质中，介电常数随温度的变化很小。补偿 Arrhenius 形式主义用于根据指数前因子 σo 和玻尔兹曼因子 exp(-Ea/RT)的贡献来描述温度相关的电导率。这种分析解释了为什么在 LiTf-十二醇电解质中，电导率随着温度的升高而在 65°C 以上降低。在较高温度下，指数前因子的减小大于玻尔兹曼因子的增加。
