Procedure for Evaluation of Exchange Current Density and Coverage by an Intermediate at the Reversible Potential in a Process Such as Cl2 Evolution

Tilak, B. V.; Novák, Doris; Conway, B. E.

doi:10.1149/1.2127767

Cited by 3 publications

(4 citation statements)

References 3 publications

(22 reference statements)

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“…Microkinetic current-voltage relationships for the various cases (slow discharge, slow recombination, slow electrochemical desorption, and slow chemical step) are presented in Table I, based on charge balance considerations for the adsorbed intermediates pertinent to the various cases. These involve coverage, 0 of A~d~ species which can be calculated (9) as follows. Let 0 represent the coverage of A,a~ at the overpotential n and Or that at ~ = 0.…”

Section: Modelmentioning

confidence: 99%

“…Let 0 represent the coverage of A,a~ at the overpotential n and Or that at ~ = 0. A term k~ is defined k, = 0r/1 --Or [9] For case [1], quasi-equilibrium assumption for the step A~d~ + e ~ B yields (0)…”

Section: Modelmentioning

confidence: 99%

“…1 + k~ -1 exp (h~) k~ is related to Or as given by Eq. [9] and is also equal to (kJk-2) exp (hVr~v) for case [1] where k2 and k 2 are the rate constants for the reaction Aads + e ~ B. Quasi-equilibrium for the first step is valid for cases [2], [3], and [4], i.e. One of the purposes in this study is to deduce the relationship between the experimentally accessible variables, viz., potential ~o and the total current I where ~o = ~ (x = 0).…”

Section: -[12]mentioning

confidence: 99%

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Polarization Characteristics of Porous Electrode Systems with Adsorbed Intermediates Participating in the Electrode Reaction: A Study of Limiting Tafel Slopes

Tilak

Venkatesh

Rangarajan

1989

J. Electrochem. Soc.

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Current‐potential relationships are derived for porous electrode systems following a homogeneous model and when adsorbed intermediates participate in the electrode reaction. Limiting Tafel slopes were deduced and compared with the corresponding behavior on planar electrode systems. The theoretical results showed doubling of Tafel slopes when the slow‐step is a charge‐transfer reaction and a nonlogarithmic current‐voltage behavior when the slow‐step is a chemical reaction. Comparison of the experimental results with theory for the case of oxygen reduction on carbon surfaces in alkaline media indicates that a slow chemical reaction following the initial charge‐transfer reaction to be the likely rate‐controlling step. Theoretical relationships are utilized to determine the exchange current density and the surface coverage by the adsorbed intermediates during the course of oxygen reduction from alkaline solutions on “carbon.” Tafel slope measurements on planar and porous electrodes for the same reaction are suggested as one of the diagnostic criteria for elucidating the mechanistic pathways of electrochemical reactions.

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Section: Modelmentioning

confidence: 99%

Section: Modelmentioning

confidence: 99%

Section: -[12]mentioning

confidence: 99%

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Polarization Characteristics of Porous Electrode Systems with Adsorbed Intermediates Participating in the Electrode Reaction: A Study of Limiting Tafel Slopes

Tilak

Venkatesh

Rangarajan

1989

J. Electrochem. Soc.

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“…The original dimensionally stable anodes were indeed a breakthrough, but there still was a gap in our understanding of how they worked. The Journal records many contributions [49][50][51][52][53] to this understanding ͑which reference is not to slight the tremendous amount of ''understanding'' that was being developed as proprietary information͒.…”

mentioning

confidence: 99%