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Conductivities of some tetraalkylammonium salts in acetonitrile Harkness, Alan Chisholm

Abstract

The conductivities of the homologous series from tetra-methyl to tetra-n-amyl of the normal tetraalkylammonium iodides and bromides in acetonitrile at 25° C have been determined. The concentrations studied ranged from 0.006 to 0.00003 moles per litre. These salts are fairly strong electrolytes in acetonitrile. The iodides have higher conductivities and are more highly dissociated than the corresponding bromides. The conductivities decrease with increasing size of the alkyl group and the degrees of dissociation show a corresponding increase. There is a relatively large difference between the tetramethyl and tetraethyl ions and then smaller, fairly regular differences in going from tetraethyl to tetra-n-amyl. The limiting equivalent conductivities have been calculated by the methods of Shedlovsky and Fuoss. It is shown that the dissociation constants calculated by the method of Shedlovsky and those calculated by the method of Fuoss are not related in the manner predicted by these authors. Ionic conductances have been calculated by assuming that Walden's rule applies to the tetra-n-butylammonium ion. A comparison of ionic resistances in some organic solvents shows that the quaternary ammonium ions have little tendency to interact with solvent molecules.

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