非水溶液中的介电弛豫。第2部分。-苦味酸三(正丁基)铵和碘化物在极性溶剂中的溶液

E. Cavell, P. Knight, M. A. Sheikh
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引用次数: 76

摘要

在0.2 ~ 3.0 GHz的频率范围内测量了苦克酸三(正丁基)铵和碘化物溶液在不同极性溶剂中的介电常数和损耗。所用纯溶剂在25℃时的相对静态介电常数范围为3.37 ~ 20.7。对于所研究的所有溶液,所观察到的介电常数的分散可以用一个松弛时间来充分描述,对于给定的溶剂,松弛时间取决于浓度和溶质的性质。在假设偶极子占据球形腔的情况下,用Bottcher理论从色散振幅计算出的视偶极矩分别为12.3±0.4 D和11.2±0.6 D。这些值表明弛豫偶极子是离子对。用不同关系对内场效应校正后的介电弛豫时间与用Debye-Stokes方程从溶质的偏摩尔体积和溶剂的粘度计算得到的介电弛豫时间进行了比较。这两种盐在1,2-二氯乙烷中的溶液的密度数据包括在内,并从这些数据,盐的部分摩尔体积已被评估。
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Dielectric relaxation in non aqueous solutions. Part 2.—Solutions of tri(n-butyl)ammonium picrate and iodide in polar solvents
The permittivity and loss of solutions of tri(n-butyl)ammonium picrate and iodide in various polar solvents have been measured at a number of frequencies between 0.2 and 3.0 GHz. The relative static permittivities of the pure solvents used range from 3.37 to 20.7 at 25°C. For all the solutions investigated, the observed dispersion of permittivity is adequately described by a single relaxation time, which for a given solvent depends on the concentration as well as the nature of the solute. Apparent dipole moments evaluated from the dispersion amplitude by means of Bottcher's theory, on the assumption that the dipole occupies a spherical cavity, are 12.3±0.4 D and 11.2±0.6 D for the picrate and iodide respectively. These values indicate that the relaxing dipole is an ion pair. Dielectric relaxation times corrected for internal field effects by different relations are compared with those calculated from the partial molar volume of the solute and the viscosity of the solvent by means of the Debye-Stokes equation. Density data for solutions of the two salts in 1,2-dichloroethane are included and from these data, partial molar volumes of the salts have been evaluated.
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