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The influence of the second coordination sphere on die electroreduction of hafnium complexes to hafnium metal and the redox reaction Eu(III)+e - ⇔ Eu(II) in alkali halide melts was studied. It is shown that die large caesium cations in the melt reduce the transfer and the diffusion coefficients as well as the heterogeneous rate constants for charge transfer of harnitcn complexes. The standard rare constants for the europium redox reaction increase when going from NaCl-KCl to CsCl. The different influence of die second coordination sphere on the electrode reactions is explained by different limitation stages for electron transfer

Influence of Second Coordination Sphere on the Kinetics of Electrode Reactions in Molten Salts