Electrochemistry of Transition Metal Ions in Acetonitrile.
Final technical rept.,
MASSACHUSETTS UNIV AMHERST DEPT OF CHEMISTRY
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A new method for purification of acetonitrile was required using reduction of impurities with sodium and calcium hydride prior to distillation. On electrolytic reduction the products formed react with solvent, electrolyte and residual water which is so difficult to remove. The dissociation properties were determined for a series of useable polarographic electrolytes such as alkali and tetraalkylammonium halides, perchlorates, tetrafluoroborates, and trifluoracetate. They undertook a study of the properties of the electrical double layer in acetonitrile at a mercury interface which shows extensive adsorption of both anions and cations on the electrode again complicating electrolytic data. Also studied was the electrolytic properties in acetonitrile of copperII and copperI as a model case for reduction through lower oxidation states to the metal. These ions could be precisely coulometrically reduced to the lower states as in water and the precision was great enough to determine diffusion coefficients for the respective species by the Cottrell method. Author
- Physical Chemistry