Effect of the Supporting-Electrolyte Cation on the Chloroplatinite Ion Reduction at a Dropping Mercury Electrode

The effect of nature and concentration of supporting-electrolyte cations (Li⁺, Na⁺, Cs⁺, (CH₃)₄N⁺, Ca²⁺, Ba²⁺) on electroreduction kinetics of PtCl^2- ₄at a dropping mercury electrode is studied. The electroreduction wave for PtCl^2- ₄is complicated by a polarographic maximum of first kind followed by a pronounced plateau of limiting current, after which the current passes through a minimum. The electroreduction occurs probably via two different mechanisms and presumably involves the same species, because the charge z _iof discharging species, determined by the Frumkin–Petrii method, remains virtually constant (z _i –1) on both descending (E= –0.6 to –1.0 V vs. SCE) and ascending (–1.3 to –1.6 V) branches of polarization curves and is independent of the nature of the supporting-electrolyte cation. The mechanism is presumably changed by a changed orientation of discharging species relative to the electrode surface.