Re-defining the kinetics of redox reactions on passive metal surfaces

3Citations
Citations of this article
9Readers
Mendeley users who have this article in their library.

Abstract

It is known that the kinetics of redox reactions occurring on the surfaces of passive metals depend upon the properties of the passive film, ostensibly due to quantum mechanical tunnelling (QMT) of electrons and holes between the metal and the redox couple at the barrier layer/solution (bl/s) interface. In this paper, the tunnelling probability is used to inter-convert the exchange current densities for the redox reactions occurring at the bl/s interface and on the hypothetical bare metal surface. We review our previous work on combining QMT theory with the point defect model (PDM), which provides an analytical expression for the bl thickness as a function of voltage. By combining QMT theory and the PDM, we derive a modified form of the generalized Butler-Volmer equation that requires as input only the kinetic parameters for the redox reaction on the hypothetical bare surface and parameters contained in the PDM. The application of the theory is illustrated with reference to the corrosion of carbon steel in concrete pore solution, to calculating the corrosion potential of, and crack growth rate in, sensitized type 304 SS in boiling water reactor (BWR) coolant circuits, and the use of hydrogen oxidation on platinum to determine the thickness of the bl as a function of voltage and temperature. This illustrates a new, powerful technique for probing the formation of passive films on metal surfaces.

References Powered by Scopus

The Point Defect Model for the Passive State

1478Citations
N/AReaders
Get full text

The history of the Point Defect Model for the passive state: A brief review of film growth aspects

865Citations
N/AReaders
Get full text

Passivity - The key to our metals-based civilization

715Citations
N/AReaders
Get full text

Cited by Powered by Scopus

Electrochemical techniques and mechanisms for the corrosion of metals and alloys in sub- and supercritical aqueous systems

14Citations
N/AReaders
Get full text

A Critical Review of Radiolysis Issues in Water-Cooled Fission and Fusion Reactors: Part II, Prediction of Corrosion Damage in Operating Reactors

7Citations
N/AReaders
Get full text

Study on the passivation properties of austenitic stainless steel 316LN based on the point defect model

5Citations
N/AReaders
Get full text

Register to see more suggestions

Mendeley helps you to discover research relevant for your work.

Already have an account?

Cite

CITATION STYLE

APA

Macdonald, D. D., & Qiu, J. (2020, November 1). Re-defining the kinetics of redox reactions on passive metal surfaces. Journal of Solid State Electrochemistry. Springer Science and Business Media Deutschland GmbH. https://doi.org/10.1007/s10008-020-04791-z

Readers' Seniority

Tooltip

PhD / Post grad / Masters / Doc 3

60%

Professor / Associate Prof. 1

20%

Researcher 1

20%

Readers' Discipline

Tooltip

Materials Science 2

50%

Biochemistry, Genetics and Molecular Bi... 1

25%

Earth and Planetary Sciences 1

25%

Save time finding and organizing research with Mendeley

Sign up for free