electrochemical behaviour of u(v1) nitrate in chloroform at a mercury electrode the dependence on supporting electrolyte

the mechanistic aspects of the electrochemical reduction of u(v1) nitrate at a mercury electrode in chloroform, using three different supporting electrolytes, are described. in the presence of tetrabutylarnmonium perchlorate (tbap) as a neutral electrolyte, uo (no ) , reduced in two irreversible electrochemical steps to form a u(v1)-u(v) binuclear complex and u(iv), respectively. in the presence of 0.75 m piperidinium perchlorate (pp) + 0.25 m piperidine (p) as supporting electrolyte, the reduction of u0 ( no ) occurred according to a one-electron irreversible process to u (v). the same behaviour was observed in the presence of 0.5 m tributylamrnonium perchlorate + 0.3 m tributylamine. the diffusion coefficients of u(vi) and u(vi)- u(v) binuclear complex determined by chronoamperometric measurement are 8.8 cm s and 5.37 10 cm s respectively