Method-independent representation of polarographic and voltammetric measurement results of reversible redox couples

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Abstract

A set of transformations is proposed by which the results of all kinds of polarographic and voltammetric measurements involving linear, semi-infinite diffusion of reversible redox couples can be presented in the form of a unified, standardized W = n2F2(co*√Do + cR*√DR)/{4RT cosh2 [nF (Edc - E 1 2)/2RT]} function, which can be identified as the coefficient of the specific Warburg-admittance of the redox couple. Using these transformations the measured I(E) functions, voltammograms, polarograms, DPP's, a.c. polarograms etc., become independent of the E(t) function and the type of electrode used. Many electroanalytical methods are based on the measurement of diffusion controlled currents of redox reactions and on their potential dependence. The quantity which is measured in voltammetric, impedance and polarographic techniques depends on many parameters of the actual measurement method. Our suggestion is that the measurement parameters should be removed from the results by appropriate transformations (given in Table 1), thereby enabling a method-independent representation of experimental data to be given. This is achieved if the raw data of the measurements are transformed to W(Edc) which depends solely on potential and solution bulk parameters (see eqn. (15)).

Original languageEnglish
Pages (from-to)229-234
Number of pages6
JournalJournal of Electroanalytical Chemistry
Volume364
Issue number1-2
DOIs
Publication statusPublished - Jan 31 1994

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Redox reactions
Oxidation-Reduction
Electrodes

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Analytical Chemistry
  • Electrochemistry

Cite this

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title = "Method-independent representation of polarographic and voltammetric measurement results of reversible redox couples",
abstract = "A set of transformations is proposed by which the results of all kinds of polarographic and voltammetric measurements involving linear, semi-infinite diffusion of reversible redox couples can be presented in the form of a unified, standardized W = n2F2(co*√Do + cR*√DR)/{4RT cosh2 [nF (Edc - E 1 2)/2RT]} function, which can be identified as the coefficient of the specific Warburg-admittance of the redox couple. Using these transformations the measured I(E) functions, voltammograms, polarograms, DPP's, a.c. polarograms etc., become independent of the E(t) function and the type of electrode used. Many electroanalytical methods are based on the measurement of diffusion controlled currents of redox reactions and on their potential dependence. The quantity which is measured in voltammetric, impedance and polarographic techniques depends on many parameters of the actual measurement method. Our suggestion is that the measurement parameters should be removed from the results by appropriate transformations (given in Table 1), thereby enabling a method-independent representation of experimental data to be given. This is achieved if the raw data of the measurements are transformed to W(Edc) which depends solely on potential and solution bulk parameters (see eqn. (15)).",
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N2 - A set of transformations is proposed by which the results of all kinds of polarographic and voltammetric measurements involving linear, semi-infinite diffusion of reversible redox couples can be presented in the form of a unified, standardized W = n2F2(co*√Do + cR*√DR)/{4RT cosh2 [nF (Edc - E 1 2)/2RT]} function, which can be identified as the coefficient of the specific Warburg-admittance of the redox couple. Using these transformations the measured I(E) functions, voltammograms, polarograms, DPP's, a.c. polarograms etc., become independent of the E(t) function and the type of electrode used. Many electroanalytical methods are based on the measurement of diffusion controlled currents of redox reactions and on their potential dependence. The quantity which is measured in voltammetric, impedance and polarographic techniques depends on many parameters of the actual measurement method. Our suggestion is that the measurement parameters should be removed from the results by appropriate transformations (given in Table 1), thereby enabling a method-independent representation of experimental data to be given. This is achieved if the raw data of the measurements are transformed to W(Edc) which depends solely on potential and solution bulk parameters (see eqn. (15)).

AB - A set of transformations is proposed by which the results of all kinds of polarographic and voltammetric measurements involving linear, semi-infinite diffusion of reversible redox couples can be presented in the form of a unified, standardized W = n2F2(co*√Do + cR*√DR)/{4RT cosh2 [nF (Edc - E 1 2)/2RT]} function, which can be identified as the coefficient of the specific Warburg-admittance of the redox couple. Using these transformations the measured I(E) functions, voltammograms, polarograms, DPP's, a.c. polarograms etc., become independent of the E(t) function and the type of electrode used. Many electroanalytical methods are based on the measurement of diffusion controlled currents of redox reactions and on their potential dependence. The quantity which is measured in voltammetric, impedance and polarographic techniques depends on many parameters of the actual measurement method. Our suggestion is that the measurement parameters should be removed from the results by appropriate transformations (given in Table 1), thereby enabling a method-independent representation of experimental data to be given. This is achieved if the raw data of the measurements are transformed to W(Edc) which depends solely on potential and solution bulk parameters (see eqn. (15)).

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