Catalytic polarographic current of a metal complex. VIII. Effect of weakly complexing supporting electrolytes

Josip Čaja, Hubert C. MacDonald, E. Kirowa-Eisner, Lowell R. McCoy, Harry B. Mark

Research output: Contribution to journalArticlepeer-review

Abstract

The polarographic reduction of Ni (II) in the presence of p-phenylenediamine (PPDA) has been studied in noncomplexing and in weakly complexing electrolytes. Catalytic prewaves, similar to those previously reported with o-phenylenediamine (OPDA), are observed only in the latter case. The reaction mechanism is believed to involve an aquated nickel-anion complex formed in the bulk of the solution and the adsorbed organic ligand. A good correlation is found between the prewave currents obtained with OPDA and Ni(II) in various electrolytes, and the rate of ligand exchange reported by others between corresponding nickel-anion complexes and a large organic anion. Experimental data for the PPDA and OPDA-Ni(II) systems agree qualitatively with the predictions of kinetic equations derived for an electrode reaction between a nickel-anion complex and an adsorbed ligand. Experimental data are also presented describing the polarographic results obtained with Ni(II) and isomers of the naphthalenediamines and with an inorganic ligand, N3-.

Original languageEnglish
Pages (from-to)1170-1178
Number of pages9
JournalJournal of Physical Chemistry
Volume76
Issue number8
DOIs
StatePublished - 1972
Externally publishedYes

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