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Effects of coupled homogeneous chemical reactions on the response of large-amplitude AC voltammetry: Extraction of kinetic and mechanistic information by fourier transform analysis of higher harmonic data

Journal Article


Abstract


  • Large-amplitude ac voltammograms contain a wealth of kinetic information concerning electrode processes and can provide unique mechanistic insights compared to other techniques. This paper describes the effects homogeneous chemical processes have on ac voltammetry in general and provides experimental examples using two well-known chemical systems: one simple and one complex. Oxidation of [Cp*Fe(CO)2]2 (Cp* = η5-pentamethylcyclopentadienyl) in noncoordinating media is a reversible one-electron process; in the presence of nucleophiles, however, the resulting ligand-induced disproportionation changes the process to a multiple step regeneration. The chemical kinetic parameters of the regeneration mechanism were discerned via analysis of the third and higher harmonics of Fourier-transformed ac voltammetry data. Comparison of experimental data to digital simulations provides clear evidence that the reaction proceeds via a rapid pre-equilibrium between the electrogenerated monocation and the coordinating ligand; simultaneous fitting of the first nine harmonics indicates that kf = 7500 M-1 s-1 and kr = 100 s-1, and that the unimolecular decomposition of the corresponding intermediate occurs with a rate constant of 2.2 s-1. The rapid cis+ → trans+ isomerization of the electrogenerated cis-[W(CO)2(dpe)2]+, where dpe = 1,2-diphenylphosphinoethane, was examined to illustrate the effects of a simpler EC mechanism on the higher harmonics; a rate constant of 280 s-1 was determined. These results not only shed new light on the chemistry of these systems, but provide a clear demonstration that the higher harmonics of ac voltammetry provide mechanistic insights into coupled homogeneous processes far more detailed than those that are readily accessible with dc techniques. © 2010 American Chemical Society.

UOW Authors


  •   Lee, Chong Yong
  •   Bullock, John P. (external author)
  •   Kennedy, Gareth F. (external author)
  •   Bond, Alan M. (external author)

Publication Date


  • 2010

Citation


  • Lee, C., Bullock, J. P., Kennedy, G. F. & Bond, A. M. (2010). Effects of coupled homogeneous chemical reactions on the response of large-amplitude AC voltammetry: Extraction of kinetic and mechanistic information by fourier transform analysis of higher harmonic data. The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 114 (37), 10122-10134.

Scopus Eid


  • 2-s2.0-77956734159

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/1693

Has Global Citation Frequency


Number Of Pages


  • 12

Start Page


  • 10122

End Page


  • 10134

Volume


  • 114

Issue


  • 37

Place Of Publication


  • United States

Abstract


  • Large-amplitude ac voltammograms contain a wealth of kinetic information concerning electrode processes and can provide unique mechanistic insights compared to other techniques. This paper describes the effects homogeneous chemical processes have on ac voltammetry in general and provides experimental examples using two well-known chemical systems: one simple and one complex. Oxidation of [Cp*Fe(CO)2]2 (Cp* = η5-pentamethylcyclopentadienyl) in noncoordinating media is a reversible one-electron process; in the presence of nucleophiles, however, the resulting ligand-induced disproportionation changes the process to a multiple step regeneration. The chemical kinetic parameters of the regeneration mechanism were discerned via analysis of the third and higher harmonics of Fourier-transformed ac voltammetry data. Comparison of experimental data to digital simulations provides clear evidence that the reaction proceeds via a rapid pre-equilibrium between the electrogenerated monocation and the coordinating ligand; simultaneous fitting of the first nine harmonics indicates that kf = 7500 M-1 s-1 and kr = 100 s-1, and that the unimolecular decomposition of the corresponding intermediate occurs with a rate constant of 2.2 s-1. The rapid cis+ → trans+ isomerization of the electrogenerated cis-[W(CO)2(dpe)2]+, where dpe = 1,2-diphenylphosphinoethane, was examined to illustrate the effects of a simpler EC mechanism on the higher harmonics; a rate constant of 280 s-1 was determined. These results not only shed new light on the chemistry of these systems, but provide a clear demonstration that the higher harmonics of ac voltammetry provide mechanistic insights into coupled homogeneous processes far more detailed than those that are readily accessible with dc techniques. © 2010 American Chemical Society.

UOW Authors


  •   Lee, Chong Yong
  •   Bullock, John P. (external author)
  •   Kennedy, Gareth F. (external author)
  •   Bond, Alan M. (external author)

Publication Date


  • 2010

Citation


  • Lee, C., Bullock, J. P., Kennedy, G. F. & Bond, A. M. (2010). Effects of coupled homogeneous chemical reactions on the response of large-amplitude AC voltammetry: Extraction of kinetic and mechanistic information by fourier transform analysis of higher harmonic data. The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 114 (37), 10122-10134.

Scopus Eid


  • 2-s2.0-77956734159

Ro Metadata Url


  • http://ro.uow.edu.au/aiimpapers/1693

Has Global Citation Frequency


Number Of Pages


  • 12

Start Page


  • 10122

End Page


  • 10134

Volume


  • 114

Issue


  • 37

Place Of Publication


  • United States