Double potential step chronocoulometry. Part II. Measurement of the chemical reaction rate in an EC mechanism when both electrode reactant and product are adsorbed

Richard P. Van Duyne*, Thomas H. Ridgway, C. N. Reilley

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

The double potential step chronocoulometric theory for EC type electrode reactions (irreversible chemical kinetics) both with and without complications arising from the adsorption of electrode reactant and product has been verified using the reduction of azobenzene in acidic H2O-EtOH media as a model system. Hydrazobenzene has been found to adsorb on mercury electrodes to a significant extent over the potential range -0.10 V to -0.40 V vs. SCE. Both kinetic and nonkinetic charge ratios, |Qb/Qf|, have been corrected for the effects of azobenzene and hydrazobenzene. Using the adsorption corrected kinetic |Qb/Qf|, a plot of kτ vs. τ was found to be nonlinear when kτ was calculated from the previously derived EC kinetic theory; whereas no significant derivation for linearity was found for the newly derived theory. The benzidine rearrangement rate constant obtained in 1.18 M HClO4 was 4.27 s-1 in excellent agreement with previous chronoamperometric results.

Original languageEnglish (US)
Pages (from-to)283-295
Number of pages13
JournalJournal of Electroanalytical Chemistry
Volume34
Issue number2
DOIs
StatePublished - Jan 1 1972

ASJC Scopus subject areas

  • Analytical Chemistry
  • Chemical Engineering(all)
  • Electrochemistry

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