Asymmetric electrode kinetics induced by concurrent metal-ligand bond dissociation

Richard T. Carlin, Thom Sullivan, John W. Sherman, Craig A. Aspinwall

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

The electrochemistry of the Cu(II)/Cu(I) couple under nitrogen and carbon monoxide has been investigated in the ambient-temperature molten salt AlCl3:MEICl (MEICl = 1-methyl-3-ethyl-imidazolium chloride) at a 250 μm tungsten disk electrode. Under nitrogen, the couple exhibits reversible electrode kinetics; however, under carbon monoxide, a Cu(I)CO complex is formed and the Cu(II)/Cu(I) couple displays asymmetric, quasi-reversible electrode kinetics. Pulse voltammetric data were fit with a nonlinear least-squares fitting program to give an apparent standard rate constant (k0a) of 1.5 × 10-3 cm s-1 and an anodic transfer coefficient (β) of 0.12-0.17 for the oxidation of the Cu(I)CO complex. The change from reversible to quasi-reversible electrode kinetics is attributed to the concurrent dissociation of the Cu(I)CO bond during the electron transfer process.

Original languageEnglish (US)
Pages (from-to)927-934
Number of pages8
JournalElectrochimica Acta
Volume38
Issue number7
DOIs
StatePublished - May 1993
Externally publishedYes

Keywords

  • carbon monoxide
  • copper
  • kinetics
  • microelectrodes
  • molten salts

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Electrochemistry

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