MilliporeSigma
  • Home
  • Search Results
  • Molecular and system parameters governing mass and charge transport in polar liquids and electrolytes.

Molecular and system parameters governing mass and charge transport in polar liquids and electrolytes.

The journal of physical chemistry. B (2012-07-31)
Matt Petrowsky, Allison Fleshman, Mohd Ismail, Daniel T Glatzhofer, Dharshani N Bopege, Roger Frech
ABSTRACT

Onsager's model of the dielectric constant is used to provide a molecular-level picture of how the dielectric constant affects mass and charge transport in organic liquids and organic liquid electrolytes. Specifically, the molecular and system parameters governing transport are the molecular dipole moment μ and the solvent dipole density N. The compensated Arrhenius formalism (CAF) writes the temperature-dependent ionic conductivity or diffusion coefficient as an Arrhenius-like expression that also includes a static dielectric constant (ε(s)) dependence in the exponential prefactor. The temperature dependence of ε(s) and therefore the temperature dependence of the exponential prefactor is due to the quantity N/T, where T is the temperature. Using the procedure described in the CAF, values of the activation energy can be obtained by scaling out the N/T dependence instead of the ε(s) dependence. It has been previously shown that a plot of the prefactors versus ε(s) results in a master curve, and here it is shown that a master curve also results by plotting the prefactors against N/T. Therefore, the CAF can be applied by using temperature-dependent density data instead of temperature-dependent dielectric constant data. This application is demonstrated for diffusion data of n-nitriles, n-thiols, n-acetates, and 2-ketones, as well as conductivity data for dilute tetrabutylammonium triflate-nitrile electrolytes.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Tetrabutylammonium bisulfate solution, ~55% in H2O
Sigma-Aldrich
Tetrabutylammonium fluoride solution, 75 wt. % in H2O
Sigma-Aldrich
Tetrabutylammonium nitrate, 97%
Sigma-Aldrich
Tetrabutylammonium fluoride solution, 1.0 M in THF
Sigma-Aldrich
Tetrabutylammonium bromide solution, 50 wt. % in H2O
Sigma-Aldrich
Tetrabutylammonium iodide, reagent grade, 98%
Sigma-Aldrich
Tetrabutylammonium bromide, ACS reagent, ≥98.0%
Supelco
Tetrabutylammonium bromide, suitable for ion pair chromatography, LiChropur, ≥99.0%
Sigma-Aldrich
Tetrabutylammonium chloride, ≥97.0% (NT)
Sigma-Aldrich
Tetrabutylammonium bisulfate, puriss., ≥99.0% (T)
Supelco
Tetrabutylammonium iodide, suitable for ion pair chromatography, LiChropur, ≥99.0%
Supelco
Tetrabutylammonium bisulfate, suitable for ion pair chromatography, LiChropur, ≥99.0%
Supelco
Tetrabutylammonium chloride, suitable for ion pair chromatography, LiChropur, ≥99.0%
Sigma-Aldrich
Tetrabutylammonium iodide, ≥99.0% (AT)
Supelco
Tetrabutylammonium bisulfate solution, suitable for ion pair chromatography, LiChropur, concentrate, ampule
Sigma-Aldrich
Tetrabutylammonium phosphate monobasic, puriss., ≥99.0% (T)
Sigma-Aldrich
Tetrabutylammonium azide
Sigma-Aldrich
Tetrabutylammonium hydroxide solution, 1.0 M in methanol
Sigma-Aldrich
Tetrabutylammonium hydroxide solution, 40 wt. % in H2O
Sigma-Aldrich
Tetrabutylammonium hydrogensulfate, 97%
Sigma-Aldrich
Tetrabutylammonium phosphate monobasic solution, 1.0 M in H2O
Sigma-Aldrich
Tetrabutylammonium cyanide, 95%
Sigma-Aldrich
Tetrabutylammonium hydroxide solution, 54.0-56.0% in H2O
Sigma-Aldrich
Tetrabutylammonium hydroxide solution, technical, ~40% in H2O (~1.5 M)
Sigma-Aldrich
Tetrabutylammonium perchlorate, ≥95.0% (T)
Supelco
Tetrabutylammonium perchlorate, for electrochemical analysis, ≥99.0%
Supelco
Tetrabutylammonium hydroxide solution, ~40% in water, suitable for ion chromatography
Supelco
Tetrabutylammonium phosphate monobasic solution, suitable for ion pair chromatography, LiChropur, concentrate, ampule
Sigma-Aldrich
Tetrabutylammonium cyanide, technical, ≥80%