MEASUREMENT OF DIFFUSION COEFFICIENTS FOR REDUCTION OF COPPER(I) AND (2) IN ACETONITRILE

Values of the diffusion coefficients in the reductions Cu(II) to Cu(I) [D = 10.0·10-6 cm2 sec-1], Cu(II) to Cu(O) [D = 12.3·10-6 cm2 sec-1], and Cu(I) to Cu(O) [D = 16.4·10-6 cm2 sec-1] have been determined. Owing to the fast exchange of coordinated and uncoordinated acetonitrile molecules, the greater probability of ion-pair formation in the cupric cases, and the release of water into the diffusion layer in discharge of the cupric species, the largest diffusion coefficient was found for the cuprous species. The experimental diffusion coefficient for the cupric species is significantly smaller during reduction to Cu(I) than during reduction to the amalgam. Possible reasons for this real difference are discussed. © 1969.