Abstract
Self-diffusion coefficient measurements were performed for pure n-alkyl ketone liquids using the pulsed field gradient NMR spin-echo technique. Ionic conductivities and dielectric constants of 0.0055 mol·L−1 tetrabutylammonium trifluoromethanesulfonate in 2-pentanone, 2-hexanone, 2-heptanone, 2-octanone, 2-nonanone, and 2-decanone were also measured. The temperature-dependent conductivities and diffusion coefficients over the range 5–80 °C can be described using the compensated Arrhenius formalism. Compensated Arrhenius equation plots were used to calculate the average activation energy for both sets of data. The average activation energy from conductivity data is approximately equal to that from diffusion data. The data for the pure ketones and ketone-based electrolytes are compared with analogous data for pure n-alkyl acetates and n-alkyl acetate-based electrolytes.Electronic supplementary materialThe online version of this article (doi:10.1007/s10953-013-9983-z) contains supplementary material, which is available to authorized users.
Highlights
Mass and charge transport in organic liquid electrolytes have garnered interest due to the use of these electrolytes in electrochemical devices
Ionic conductivities and self-diffusion coefficients are important measures of transport phenomena, these data are conventionally described with viscosity-related models [1,2,3] that often predict results that do not agree with experiment [4,5,6]
J Solution Chem (2013) 42:584–591 from an entirely different perspective [7, 8], by postulating that the conductivity and diffusion coefficient assume an Arrhenius-like expression with static dielectric constant dependence in the exponential prefactor: rðT; esÞ 1⁄4 r0fesðTÞgexpðÀEa=RTÞ
Summary
Mass and charge transport in organic liquid electrolytes have garnered interest due to the use of these electrolytes in electrochemical devices. Ionic conductivities and self-diffusion coefficients are important measures of transport phenomena, these data are conventionally described with viscosity-related models [1,2,3] that often predict results that do not agree with experiment [4,5,6]. J Solution Chem (2013) 42:584–591 from an entirely different perspective [7, 8], by postulating that the conductivity and diffusion coefficient assume an Arrhenius-like expression with static dielectric constant (es) dependence in the exponential prefactor: rðT; esÞ 1⁄4 r0fesðTÞgexpðÀEa=RTÞ ð1Þ. Activation energies are reported for diffusion data of pure ketones and conductivity data of 0.0055 molÁL-1 tetrabutylammonium trifluoromethanesulfonate (TbaTf)–ketone solutions. Because the dielectric constant plays a prominent role in transport phenomena, it is important to compare conductivity and diffusion data between ketones and acetates
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