Mass and electron-transfer conditions for the electrochemical oxidation of hydrogen sulfide at vanadium pentoxide film modified electrode

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Abstract

A mechanistic scheme for the electrochemical oxidation of hydrogen sulfide at vanadium pentoxide film modified electrode was proposed to account for the steady-state current responses as a function of both electrode rotation rate and sulfide concentration. The mechanism indicates that the primary electron-transfer reaction is the re-oxidation of reduced vanadium species (V4+) into oxidized species (V5+) after the metal oxide film had previously been reduced by sulfide ions. The electrode reaction was found to be controlled by both mass and electron-transfer processes by which the apparent diffusion coefficient and the heterogeneous electron-transfer rate constant were evaluated applying general hydrodynamic theories. Three modes of inhibition were suggested to describe potential poisoning of the metal oxide surface sites due to sulfur adsorption. The phase boundary condition of the film for mass and electron-transfer processes is discussed also.

Original languageEnglish
Pages (from-to)223-229
Number of pages7
JournalSensors and Actuators, B: Chemical
Volume131
Issue number1
DOIs
Publication statusPublished - Apr 14 2008

Fingerprint

Hydrogen Sulfide
hydrogen sulfide
electrochemical oxidation
Electrochemical oxidation
Hydrogen sulfide
Vanadium
vanadium
mass transfer
electron transfer
Electrodes
electrodes
Electrons
Sulfides
metal oxides
sulfides
Metals
poisoning
Phase boundaries
Sulfur
Oxides

Keywords

  • Chemically modified electrodes
  • Hydrogen sulfide
  • Kinetics
  • Oxidation
  • Vanadium pentoxide

ASJC Scopus subject areas

  • Analytical Chemistry
  • Electrochemistry
  • Electrical and Electronic Engineering

Cite this

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abstract = "A mechanistic scheme for the electrochemical oxidation of hydrogen sulfide at vanadium pentoxide film modified electrode was proposed to account for the steady-state current responses as a function of both electrode rotation rate and sulfide concentration. The mechanism indicates that the primary electron-transfer reaction is the re-oxidation of reduced vanadium species (V4+) into oxidized species (V5+) after the metal oxide film had previously been reduced by sulfide ions. The electrode reaction was found to be controlled by both mass and electron-transfer processes by which the apparent diffusion coefficient and the heterogeneous electron-transfer rate constant were evaluated applying general hydrodynamic theories. Three modes of inhibition were suggested to describe potential poisoning of the metal oxide surface sites due to sulfur adsorption. The phase boundary condition of the film for mass and electron-transfer processes is discussed also.",
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AB - A mechanistic scheme for the electrochemical oxidation of hydrogen sulfide at vanadium pentoxide film modified electrode was proposed to account for the steady-state current responses as a function of both electrode rotation rate and sulfide concentration. The mechanism indicates that the primary electron-transfer reaction is the re-oxidation of reduced vanadium species (V4+) into oxidized species (V5+) after the metal oxide film had previously been reduced by sulfide ions. The electrode reaction was found to be controlled by both mass and electron-transfer processes by which the apparent diffusion coefficient and the heterogeneous electron-transfer rate constant were evaluated applying general hydrodynamic theories. Three modes of inhibition were suggested to describe potential poisoning of the metal oxide surface sites due to sulfur adsorption. The phase boundary condition of the film for mass and electron-transfer processes is discussed also.

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