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

doi:10.1016/S0022-0728(72)80402-9

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

Chemistry

Research output: Contribution to journal › Article › peer-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, |Q_b/Q_f|, have been corrected for the effects of azobenzene and hydrazobenzene. Using the adsorption corrected kinetic |Q_b/Q_f|, 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 language	English (US)
Pages (from-to)	283-295
Number of pages	13
Journal	Journal of Electroanalytical Chemistry
Volume	34
Issue number	2
DOIs	https://doi.org/10.1016/S0022-0728(72)80402-9
State	Published - Feb 1972

ASJC Scopus subject areas

Analytical Chemistry
Chemical Engineering(all)
Electrochemistry

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10.1016/S0022-0728(72)80402-9

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@article{a4e27ca48c3a42a1bf2c2f12d847b85f,

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

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.",

author = "{Van Duyne}, {Richard P.} and Ridgway, {Thomas H.} and Reilley, {C. N.}",

note = "Funding Information: The authors would like to thank Dr. R. W. Murray for stimulating discussions and Mr. Jerry Koontz for technical assistance. One of us (R. P. V.D.) gratefully acknowledges support by the National aeronautics and Space Administration for a Predoctoral Fellowship, 1967-1970. This investigation was also supported by the Advanced Research Projects Agency and the Air Force Office of Scientific Research, Grant AFOSR 69-1625.",

year = "1972",

month = feb,

doi = "10.1016/S0022-0728(72)80402-9",

language = "English (US)",

volume = "34",

pages = "283--295",

journal = "Journal of Electroanalytical Chemistry",

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publisher = "Elsevier Sequoia",

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}

Double potential step chronocoulometry. Part II. Measurement of the chemical reaction rate in an EC mechanism when both electrode reactant and product are adsorbed. / Van Duyne, Richard P.; Ridgway, Thomas H.; Reilley, C. N.
In: Journal of Electroanalytical Chemistry, Vol. 34, No. 2, 02.1972, p. 283-295.

Research output: Contribution to journal › Article › peer-review

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T1 - Double potential step chronocoulometry. Part II. Measurement of the chemical reaction rate in an EC mechanism when both electrode reactant and product are adsorbed

AU - Van Duyne, Richard P.

AU - Ridgway, Thomas H.

AU - Reilley, C. N.

N1 - Funding Information: The authors would like to thank Dr. R. W. Murray for stimulating discussions and Mr. Jerry Koontz for technical assistance. One of us (R. P. V.D.) gratefully acknowledges support by the National aeronautics and Space Administration for a Predoctoral Fellowship, 1967-1970. This investigation was also supported by the Advanced Research Projects Agency and the Air Force Office of Scientific Research, Grant AFOSR 69-1625.

PY - 1972/2

Y1 - 1972/2

N2 - 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.

AB - 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.

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

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