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Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0002-8341-094X
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0002-9453-1333
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2015 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 44, no 36, 16045-16051 p.Article in journal (Refereed) Published
Abstract [en]

One of the main challenges for the nuclear power industry today is the disposal of spent nuclear fuel. One of the most developed methods for its long term storage is the Swedish KBS-3 concept where the spent fuel is sealed inside copper canisters and placed 500 meters down in the bedrock. Gamma radiation will penetrate the canisters and be absorbed by groundwater thereby creating oxidative radiolysis products such as hydrogen peroxide (H2O2) and hydroxyl radicals (HO[radical dot]). Both H2O2 and HO[radical dot] are able to initiate corrosion of the copper canisters. In this work the kinetics and mechanism of reactions between the stable radiolysis product, H2O2, and copper and copper oxides were studied. Also the dissolution of copper into solution after reaction with H2O2 was monitored by ICP-OES. The experiments show that both H2O2 and HO[radical dot] are present in the systems with copper and copper oxides. Nevertheless, these species do not appear to influence the dissolution of copper to the same extent as observed in recent studies in irradiated systems. This strongly suggests that aqueous radiolysis can only account for a very minor part of the observed radiation induced corrosion of copper.

Place, publisher, year, edition, pages
2015. Vol. 44, no 36, 16045-16051 p.
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-172417DOI: 10.1039/C5DT02024GISI: 000360471000033Scopus ID: 2-s2.0-84940774487OAI: oai:DiVA.org:kth-172417DiVA: diva2:847916
Note

QC 20150929. Updated from e-pub ahead of print to published.

Available from: 2015-08-21 Created: 2015-08-21 Last updated: 2017-12-04Bibliographically approved
In thesis
1. Radiation Induced Processes at Solid-Liquid Interfaces
Open this publication in new window or tab >>Radiation Induced Processes at Solid-Liquid Interfaces
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In the thesis, the reactions between water radiolysis products—H2O2, HO• and O2—with metals and metal oxides utilized in nuclear industry are studied. The reactions include not only surface reactions, e.g. redox reactions and catalytic decomposition of H2O2, but also solution reactions (Haber-Weiss reactions). To study the interfacial reactions, it is crucial to monitor the dissolution of the solid material, reactivity of H2O2 and formation of the intermediate hydroxyl radicals.Hydroxyl radicals are captured by probe (Tris or methanol) to generate CH2O which can be quantified by the modified Hantzsch method. The results from γ-irradiation experiments on homogeneous system show that the conversion yield of CH2O from hydroxyl radicals is affected by O2 and pH. A mechanism of CH2O production from Tris is proposed.Besides, the consumption rate of H2O2 in the H2O2/ZrO2/Tris system is found to be influenced by Tris. A mechanism for the catalytic decomposition of H2O2 upon ZrO2 surface is proposed which includes independent surface adsorption sites for H2O2 and Tris. Moreover, it is demonstrated that the deviation of detected CH2O concentration by the modified Hantzsch method from actual concentration increases with increasing [H2O2]0/[CH2O]0.The inhibition of sulfide on the radiation induced dissolution of UO2 is confirmed and is dependent on sulfide concentration. And the inhibition of sulfide is independent to that of H2/Pd.It is found that the reactivity of H2O2 and dynamics of CH2O formation are different for the studied materials in the H2O2/MxOy/Probe system. The kinetic parameters, such as rate constant, activation energy, frequency factors are determined.Both surface and solution reactions are observed in the aqueous W(s)/H2O2/Tris system. It is also demonstrated that Haber-Weiss reactions which produce HO• continuously are dominating. Furthermore, it is found that hydroxyl radicals are formed simultaneously during the dissolution of W in aerobic aqueous system.The knowledge conveyed by the thesis is relevant to nuclear technological applications, as well as the applications related in photocatalysis, biochemistry, corrosion science, catalysis and optics/electronics.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. xii, 74 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:39
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-172421 (URN)978-91-7595-656-5 (ISBN)
Public defence
2015-09-18, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20150826

Available from: 2015-08-26 Created: 2015-08-21 Last updated: 2015-08-26Bibliographically approved
2. Radiation induced corrosion of copper
Open this publication in new window or tab >>Radiation induced corrosion of copper
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The process of radiation induced corrosion of copper is not well understood. The most obvious situation where the knowledge of this process is crucial is in a deep repository for high level spent nuclear fuel where the fuel will be sealed inside copper canisters. The radiation will penetrate the canisters and be absorbed by the surrounding environment. In this study gamma irradiations of polished and pre-oxidized copper cubes in anoxic pure water, air of 60-100 % RH and in humid argon were performed. The copper surfaces were examined using IRAS, XPS, cathodic reduction, SEM, AFM, and Raman spectroscopy. The concentration of copper in the reaction solutions was measured using ICP-OES.  Also the formation of oxidative species caused by radiation absorption of water was studied by numerical simulations using MAKSIMA software. The corrosion of copper during gamma irradiation vastly exceeds what is expected. The production of oxidative species caused by radiation absorption of water is hundreds of times too low to explain the amount of oxidized copper. A possible explanation for this mismatch is an enhanced radiation chemical yield of HO· on the copper surface. Another one is an increased surface area due to oxidation of copper. One speculation is that HO· interacting with the copper oxide can cause oxidation of the metal. If the thermodynamic driving force is large enough then electrons can be conducted from the metal through the oxide to the oxidant. A dramatic increase in surface area together with an increased interfacial yield of HO· might explain the radiation enhanced corrosion process.   

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. vii, 77 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:57
Keyword
Corrosion, oxidation, copper, copper oxide, gamma radiation, radiolysis, hydrogen peroxide, hydroxyl radical
National Category
Physical Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-175739 (URN)978-91-7595-710-4 (ISBN)
Public defence
2015-11-18, Kollegiesalen, Brinellvägen 8, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20151022

Available from: 2015-10-22 Created: 2015-10-20 Last updated: 2015-10-22Bibliographically approved

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Björkbacka, ÅsaLeygraf, ChristoferJonsson, Mats

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