Transient Convective Diffusion to a Rotating Disk Electrode as Monitored by Near-Normal Incidence Reflection Absorption Ultraviolet-Visible Spectroscopy

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Abstract

The time evolution of the integrated profile of a species generated at the surface of a rotating gold disk electrode by a potential step was monitored using UV-visible near-normal incidence reflection absorption spectroscopy. These experiments were conducted in aqueous K4[Fe(CN)6] solutions using a potential step with a large enough magnitude to achieve, at steady state, diffusion-limiting current conditions for the oxidation of [Fe(CN)8]4~with the monochromator set at 420 nm At this wavelength the ferric species displays an absorption maximum whereas the ferrous counterpart is essentially transparent. Excellent agreement was obtained between the results of these spectroscopic experiments and those calculated on the basis of the short-, and long-time solutions for transient convective diffusion to a rotating disk electrode reported in the literature without introducing any adjustable parameters. Simultaneous measurements of the current also yielded transient curves in harmony with those predicted by the theory. Possible modifications of this technique to acquire quantitative steady-state absorption spectra of the diffusion boundary layer as a function of the applied potential are discussed briefly.

Original languageEnglish
Pages (from-to)729-732
Number of pages4
JournalJournal of the Electrochemical Society
Volume140
Issue number3
DOIs
Publication statusPublished - 1993 Jan 1
Externally publishedYes

Fingerprint

Ultraviolet visible spectroscopy
Rotating disks
Electrodes
Monochromators
Absorption spectroscopy
Gold
Absorption spectra
Boundary layers
Experiments
Wavelength
Oxidation

Keywords

  • absorption
  • boundary layer turbulence
  • diffusion
  • electrochemical electrodes
  • ultraviolet spectra

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Renewable Energy, Sustainability and the Environment
  • Surfaces, Coatings and Films
  • Electrochemistry
  • Materials Chemistry

Cite this

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title = "Transient Convective Diffusion to a Rotating Disk Electrode as Monitored by Near-Normal Incidence Reflection Absorption Ultraviolet-Visible Spectroscopy",
abstract = "The time evolution of the integrated profile of a species generated at the surface of a rotating gold disk electrode by a potential step was monitored using UV-visible near-normal incidence reflection absorption spectroscopy. These experiments were conducted in aqueous K4[Fe(CN)6] solutions using a potential step with a large enough magnitude to achieve, at steady state, diffusion-limiting current conditions for the oxidation of [Fe(CN)8]4~with the monochromator set at 420 nm At this wavelength the ferric species displays an absorption maximum whereas the ferrous counterpart is essentially transparent. Excellent agreement was obtained between the results of these spectroscopic experiments and those calculated on the basis of the short-, and long-time solutions for transient convective diffusion to a rotating disk electrode reported in the literature without introducing any adjustable parameters. Simultaneous measurements of the current also yielded transient curves in harmony with those predicted by the theory. Possible modifications of this technique to acquire quantitative steady-state absorption spectra of the diffusion boundary layer as a function of the applied potential are discussed briefly.",
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T1 - Transient Convective Diffusion to a Rotating Disk Electrode as Monitored by Near-Normal Incidence Reflection Absorption Ultraviolet-Visible Spectroscopy

AU - Zhao, Ming

AU - Scherson, Daniel Alberto

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Y1 - 1993/1/1

N2 - The time evolution of the integrated profile of a species generated at the surface of a rotating gold disk electrode by a potential step was monitored using UV-visible near-normal incidence reflection absorption spectroscopy. These experiments were conducted in aqueous K4[Fe(CN)6] solutions using a potential step with a large enough magnitude to achieve, at steady state, diffusion-limiting current conditions for the oxidation of [Fe(CN)8]4~with the monochromator set at 420 nm At this wavelength the ferric species displays an absorption maximum whereas the ferrous counterpart is essentially transparent. Excellent agreement was obtained between the results of these spectroscopic experiments and those calculated on the basis of the short-, and long-time solutions for transient convective diffusion to a rotating disk electrode reported in the literature without introducing any adjustable parameters. Simultaneous measurements of the current also yielded transient curves in harmony with those predicted by the theory. Possible modifications of this technique to acquire quantitative steady-state absorption spectra of the diffusion boundary layer as a function of the applied potential are discussed briefly.

AB - The time evolution of the integrated profile of a species generated at the surface of a rotating gold disk electrode by a potential step was monitored using UV-visible near-normal incidence reflection absorption spectroscopy. These experiments were conducted in aqueous K4[Fe(CN)6] solutions using a potential step with a large enough magnitude to achieve, at steady state, diffusion-limiting current conditions for the oxidation of [Fe(CN)8]4~with the monochromator set at 420 nm At this wavelength the ferric species displays an absorption maximum whereas the ferrous counterpart is essentially transparent. Excellent agreement was obtained between the results of these spectroscopic experiments and those calculated on the basis of the short-, and long-time solutions for transient convective diffusion to a rotating disk electrode reported in the literature without introducing any adjustable parameters. Simultaneous measurements of the current also yielded transient curves in harmony with those predicted by the theory. Possible modifications of this technique to acquire quantitative steady-state absorption spectra of the diffusion boundary layer as a function of the applied potential are discussed briefly.

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