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Viscosities of solutions of electrolytes and nonelectrolytes inN-methylacetamide at 35° and 55°C
Authors:Peter T Thompson  Marciana Durbano  Joseph L Turner  Robert H Wood
Institution:(1) Department of Chemistry, Swarthmore College, 19081 Swarthmore, Pennsylvania;(2) Department of Chemistry, University of Delaware, 19711 Newark, DE
Abstract:The viscosities of dilute solutions of a number of tetraalkylammonium and alkali metal halides, tetraphenylarsonium chloride, sodium tetraphenylborate, and tetrabutylammonium tetrabutylborate, as well as several nonelectrolytes have been measured in the high dielectric constant solvent N-methylacetamide (NMA) at 35 and 55°C. The relative viscosities were fitted to the extended Jones-Dole equation, eegrGcy = 1 + AeegrC1/2 + BeegrC + DeegrC2. The pattern of behavior of the Beegr coefficients is roughly similar to that observed in H2O. However, the small ions have exceptionally large Beegr values in this solvent due to strong solvation effects, while the large organic ions do not display the sharp crossing of the Einstein law, Beegr=2.5 phgrV, characteristic in H2O of hydrophobic interaction. The Deegr coefficients roughly parallel the Beegr behavior and display remarkably regular ionic trends. This suggests that they arise largely from hydrodynamic origins. Nonelectrolytes have small or negative Beegr coefficients showing that the Einstein law is not applicable at the molecular level and that nonelectrolytes are poor models for structurally similar ions. A simple mixture law is presented as an alternative to the Einstein law to explain the Beegr coefficients.
Keywords:Viscosity  electrolyte  nonelectrolyte  alkali metal halide  tetraalkylammonium ions  solvation  jones and Dole equation  nonaqueous solvent  N-methylacetamide
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