Vila J, Rilo E, Segade L, Cabeza O, Varela L M
Departamento de Física, Universidade da Coruña, Campus da Zapateira s/n, Spain.
Phys Rev E Stat Nonlin Soft Matter Phys. 2005 Mar;71(3 Pt 1):031201. doi: 10.1103/PhysRevE.71.031201. Epub 2005 Mar 17.
We present experimental measurements of the specific electrical conductivity (sigma) in aqueous solutions of aluminum salts at different temperatures, covering all salt concentrations from saturation to infinite dilution. The salts employed were AlCl(3), AlBr(3), AlI(3), and Al(NO(3))(3), which present a 1:3 relationship between the electrical charges of anion and cation. In addition, we have measured the density in all ranges of concentrations of the four aqueous electrolyte solutions at 298.15 K. The measured densities show an almost linear behavior with concentration, and we have fitted it to a second order polynomial with very high degree of approximation. The measurement of the specific conductivity at constant temperature reveals the existence of maxima in the conductivity vs concentration curves at molar concentrations around 1.5M for the three halide solutions studied, and at approximately 2M for the nitrate. We present a theoretical foundation for the existence of these maxima, based on the classical Debye-Hu ckel-Onsager hydrodynamic mean-field framework for electrical transport and its high concentration extensions, and also a brief consideration of ionic frictional coefficients using mode-coupling theory. We also found that the calculated values of the equivalent conductance vary in an approximately linear way with the square root of the concentration at concentrations as high as those where the maximum of sigma appears. Finally, and for completeness, we have measured the temperature dependence of the electrical conductivity at selected concentrations from 283 to 353 K, and performed a fit to an exponential equation of the Vogel-Fulcher-Tamman type. The values of the calculated temperatures of null mobility of the four salts are reported.
我们展示了在不同温度下铝盐水溶液中比电导率(σ)的实验测量结果,涵盖了从饱和到无限稀释的所有盐浓度范围。所使用的盐为AlCl₃、AlBr₃、AlI₃和Al(NO₃)₃,它们的阴离子和阳离子电荷之间呈现1:3的关系。此外,我们还测量了这四种水电解质溶液在298.15 K下所有浓度范围内的密度。测量得到的密度随浓度呈现几乎线性的行为,我们将其拟合为一个具有非常高近似度的二阶多项式。在恒温下对比电导率的测量揭示,在所研究的三种卤化物溶液中,电导率与浓度曲线在摩尔浓度约为1.5 M处存在最大值,而硝酸盐溶液在约2 M处存在最大值。我们基于经典的德拜 - 休克尔 - 昂萨格流体动力学平均场电输运框架及其高浓度扩展,为这些最大值的存在提供了理论基础,同时还使用模式耦合理论简要考虑了离子摩擦系数。我们还发现,在高达出现σ最大值的浓度范围内,等效电导率的计算值随浓度的平方根近似线性变化。最后,为了完整起见,我们测量了在283至353 K选定浓度下电导率的温度依赖性,并对Vogel - Fulcher - Tamman类型的指数方程进行了拟合。报告了四种盐的零迁移率计算温度值。