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The Electrochemistry of Copper in Aqueous Sulphide Solutions

Published online by Cambridge University Press:  21 March 2011

J. Smith ,
Z. Qin ,
F. King ,
L. Werme  and
D.W. Shoesmith
J. Smith
Affiliation:
Department of Chemistry, The University of Western Ontario, London, ON, Canada, N6A 5B7
Z. Qin
Affiliation:
Department of Chemistry, The University of Western Ontario, London, ON, Canada, N6A 5B7
F. King
Affiliation:
Integrity Corrosion Consulting Ltd., 6732 Silverview Drive NW, Calgary, AB, Canada, T3B 3K8
L. Werme
Affiliation:
SKB Swedish Nuclear Fuel and Waste Management Co., Stockholm, Sweden, Box 5864, SE-102 40
D.W. Shoesmith
Affiliation:
Department of Chemistry, The University of Western Ontario, London, ON, Canada, N6A 5B7
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Abstract

Using a variety of electrochemical and surface analytical techniques, the mechanism and kinetics of Cu corrosion in anoxic, aqueous, sulphide-containing environments are being investigated. Under these conditions ([S]total = 10−4 to 3 ×10−3 mol/L), the anodicgrowth ofa film (XRD identifies Cu2S/Cu1.8S as major/minor phases, respectively) is supported by the cathodic reduction of water thereby destabilizing the copper surface. For more oxidizing conditions, the subsequent growth of a partially passivating film is observed. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry at rotating disc electrodes show film growth occurringwith negligible dissolution and under partial SH- transport control. Current-potentialrelationships as a function of [S]total give Tafel slopes of ∼ (40 mV)−1 suggesting reaction occurs via a 2step process: Aninitial rapid adsorption of SH- leading to an equilibrium surface concentration, followed by a rate determining electron transfer to form a sulphide film. It is proposed thatfilm growth propagates via transport of CuI through the film to the solution interface. The primary goal of this research is the development of a mathematical model which can be used to assess the performance of copper nuclear waste canisters in granitic repositories.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 932: Symposium – Scientific Basis for Nuclear Waste Management XXIX , 2006 , 25.1
Copyright
Copyright © Materials Research Society 2006

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References

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