Fractional Walden Rule for Electrolytes in Supercooled Disaccharide Aqueous Solutions

• Published in: The journal of physical chemistry. B Vol. 113; no. 16; pp. 5500 - 5507
• Main Authors: Longinotti, M. Paula, Corti, Horacio R
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 23-04-2009
• Subjects: B: Statistical Mechanics, Thermodynamics, Medium Effects; Cesium - chemistry; Chlorides - chemistry; Cold Temperature; Disaccharides - chemistry; Electric Conductivity; Electrolytes - chemistry; Potassium Chloride - chemistry; Quaternary Ammonium Compounds - chemistry; Solutions; Viscosity; Water - chemistry
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp810253s

The electrical conductivity of CsCl, KCl, Bu4NBr, and Bu4NI was studied in stable and supercooled (metastable) sucrose and trehalose aqueous solutions over a wide viscosity range. The results indicate that large positive deviations from the Walden rule occur in these systems due to the higher tendency of the ions to move in water-rich regions, as previously observed for NaCl and MgCl2. The electrical molar conductivity viscosity dependence can be described with a fractional Walden rule (Ληα = constant), where α is a decoupling parameter which increases with ionic size and varies between 0.61 and 0.74 for all of the studied electrolytes. Using the electrical molar conductivity dependence of ion−ion interactions, an effective dielectric constant was calculated for a trehalose 39 wt% aqueous solution as a function of temperature. Above 278 K, the effective and the bulk solution dielectric constants are similar, but at lower temperatures, where the carbohydrate becomes less mobile than water, the effective dielectric constant approaches the dielectric constant of water. We also conclude that the solute−solvent dielectric friction contribution can be neglected, reinforcing the idea that the observed breakdown of the Walden rule is due to the existence of local microheterogeneities. The Walden plots for the studied ionic solutes show a decoupling similar to that found for the diffusion of water in the same solutions.