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The electrochemical behavior of the Ni(II)/Ni(Hg) system in thiosulfate solutions at mercury electrodes has been investigated by direct current (dc) polarographic, cyclic voltammetric, chronoamperometric, and anodic stripping methods. Dc polarogram of 1 × 10 -3 M nickel(II) in 0.1 M Na2S203 and 0.2 M NaC104 solution exhibits three consecutive reduction waves with the half-wave potentials of--0.60, --0.87, and --1.08 V vs. SCE, respectively. The cyclic voltammogram in the same electrolyte solution at 0.02 V s -1 gives two cathodic peaks near --0.64 and -0.91 V, respectively, the latter being followed by a catalytic hydrogen wave with the peak potential near --1.68 V, and an anodic peak near -0.45 V. On the second and subsequent cycles, the first cathodic peak disappears, and the second peak corresponding to the reduction of hydrated nickel(II) shift to less negative potentials. A mechanism which involves the reduction of Ni(II)---S20~-followed by a chemical redox reaction of a zerovalent Ni(O)--S20~-in the species giving nickel sulfide and sulfite ion, and takes into account the effect of nickel sulfide on the reduction and reoxidation processes of nickel is proposed. Nickel sulfide

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Author

Eiki Itabashi

Publisher

Elsevier Science; Elsevier ; Elsevier BV (ISSN 0022-0728)

Published

1980

Language

EN

Field

Chemistry (Physical Sciences)