Dithizone adsorption at matal electodes. Electrochemical characterization of dithizone anion at a silver electrode

Jeanne E Pemberton, Richard P. Buck

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The redox behavior of the anion of diphenylthiocarbazone (dithizone) has been investigated at a silver electrode in alkaline media. The dithizone anion is reduced at the azo group at silver, but the observed voltammetric wave is split into surface and bulk components due to the adsorption of the anion at the silver surface. The product of this electrode reaction, the correponding hydrazo species, is also adsorbed at silver surface, but to a lesser extent. The cathodic processes for the dithizone anion reduction are complicated in alkaline solutions prepared with alkali hydroxides by the electrodeposition of alkali metals onto the silver surface and the subsequent formation of alkali metal-silver intermetallic compounds. The dithizone anion can also be oxidized at silver to form the corresponding disulfide compound. This disulfide, which is insoluble in the aqueous systems, adsorbs at the silver surface in multilayer quantities. This disulfide film passivates the silver electrode towards surface oxidation until potentials >ca. 400-500 mV (vs. Ag/AgCl) are reached.

Original languageEnglish (US)
Pages (from-to)291-309
Number of pages19
JournalJournal of Electroanalytical Chemistry
Volume132
Issue numberC
DOIs
StatePublished - Jan 25 1982
Externally publishedYes

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Dithizone
Silver
Anions
Negative ions
Adsorption
Electrodes
Disulfides
Alkali Metals
Alkali metals
Silver Compounds
Hydroxides
Alkalies
Electrodeposition
Intermetallics
Multilayers
Oxidation

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Analytical Chemistry
  • Electrochemistry

Cite this

Dithizone adsorption at matal electodes. Electrochemical characterization of dithizone anion at a silver electrode. / Pemberton, Jeanne E; Buck, Richard P.

In: Journal of Electroanalytical Chemistry, Vol. 132, No. C, 25.01.1982, p. 291-309.

Research output: Contribution to journalArticle

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N2 - The redox behavior of the anion of diphenylthiocarbazone (dithizone) has been investigated at a silver electrode in alkaline media. The dithizone anion is reduced at the azo group at silver, but the observed voltammetric wave is split into surface and bulk components due to the adsorption of the anion at the silver surface. The product of this electrode reaction, the correponding hydrazo species, is also adsorbed at silver surface, but to a lesser extent. The cathodic processes for the dithizone anion reduction are complicated in alkaline solutions prepared with alkali hydroxides by the electrodeposition of alkali metals onto the silver surface and the subsequent formation of alkali metal-silver intermetallic compounds. The dithizone anion can also be oxidized at silver to form the corresponding disulfide compound. This disulfide, which is insoluble in the aqueous systems, adsorbs at the silver surface in multilayer quantities. This disulfide film passivates the silver electrode towards surface oxidation until potentials >ca. 400-500 mV (vs. Ag/AgCl) are reached.

AB - The redox behavior of the anion of diphenylthiocarbazone (dithizone) has been investigated at a silver electrode in alkaline media. The dithizone anion is reduced at the azo group at silver, but the observed voltammetric wave is split into surface and bulk components due to the adsorption of the anion at the silver surface. The product of this electrode reaction, the correponding hydrazo species, is also adsorbed at silver surface, but to a lesser extent. The cathodic processes for the dithizone anion reduction are complicated in alkaline solutions prepared with alkali hydroxides by the electrodeposition of alkali metals onto the silver surface and the subsequent formation of alkali metal-silver intermetallic compounds. The dithizone anion can also be oxidized at silver to form the corresponding disulfide compound. This disulfide, which is insoluble in the aqueous systems, adsorbs at the silver surface in multilayer quantities. This disulfide film passivates the silver electrode towards surface oxidation until potentials >ca. 400-500 mV (vs. Ag/AgCl) are reached.

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