Studies of the anodic oxidation of the cyanide ion in the presence of the copper ion. III. Identification of the reaction intermediate by means of ESR spectroscopy.
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The formation of the tetracyanocuprate(II) ion (Cu(CN)<SUB>4</SUB><SUP>2−</SUP>), which was expected as a reaction intermediate in the anodic oxidation of the cyanide ion in the presence of the copper ion, has been investigated by means of ESR measurement. When a potassium cyanide solution containing a small amount of copper(I) cyanide was electrolyzed, an intermediate copper(II) species was found at the anode in the dissolved state. The ESR spectrum of the intermediate in the solidified state was obtained by freezing the solution in the resonant cavity. The intermediate was identified as Cu(CN)<SUB>4</SUB><SUP>2−</SUP> by a comparison of its spectrum to that of Cu(CN)<SUB>4</SUB><SUP>2−</SUP> already reported by other authors. When the ratio of the total copper(I) concentration to the total cyanide concentration in the solution was not too small, solid copper(II) cyanide was deposited on the anode during electrolysis.
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