Evaluation of Nitrate and Nitrite Reduction Kinetics Related to Liquid-Air-Interface Corrosion.

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Title: Evaluation of Nitrate and Nitrite Reduction Kinetics Related to Liquid-Air-Interface Corrosion.
Authors: Li, Xiaoji1, Gui, F.2, Cong, Hongbo2, Brossia, C.S.2, Frankel, G.S.1
Source: Electrochimica Acta. Jan2014, Vol. 117, p299-309. 11p.
Subjects: Nitrates, Chemical kinetics, Corrosion & anti-corrosives, Interfaces (Physical sciences), Carbon steel, Radioactive wastes
Abstract: Abstract: Liquid-air interface (LAI) corrosion has been a concern for causing leaks in the carbon steel tanks used for holding high-level radioactive liquid waste. To assist in understanding the mechanism of LAI corrosion, the kinetics of nitrate and nitrite reduction reactions were investigated electrochemically. Cyclic voltammetry and cathodic polarization measurements indicated that the nitrite reduction reaction exhibited faster kinetics than the nitrate reduction reaction at higher cathodic overpotential. However, the primary reduction reaction at the open circuit potential under aerated conditions was the oxygen reduction reaction. The reduction of residual oxygen was also the dominant cathodic reaction at open circuit potential in deaerated conditions. Moreover, the kinetics of oxygen reduction on steel electrodes were significantly influenced by the sample immersion conditions (partial vs. full) for aerated liquid nuclear waste simulants, but not for deaerated conditions. Lastly, the gaseous products formed during LAI corrosion were analyzed using the gas detector tube method and gas chromatography-mass spectrometry and found to contain NH3, NO2 and NO. However, the results suggested that these products were caused by the local acidification generated by the hydrolysis of cations after LAI corrosion underwent extensive propagation, instead of being directly reduced in alkaline conditions. Thus, the results in this work showed that the kinetics of nitrate and nitrite reduction could not generate a salt concentration cell in the meniscus region to cause LAI corrosion. [Copyright &y& Elsevier]
Copyright of Electrochimica Acta is the property of Pergamon Press - An Imprint of Elsevier Science and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
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DbLabel: Engineering Source
An: 94409277
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PubTypeId: academicJournal
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  Data: <searchLink fieldCode="JN" term="%22Electrochimica+Acta%22">Electrochimica Acta</searchLink>. Jan2014, Vol. 117, p299-309. 11p.
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  Data: <searchLink fieldCode="DE" term="%22Nitrates%22">Nitrates</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+kinetics%22">Chemical kinetics</searchLink><br /><searchLink fieldCode="DE" term="%22Corrosion+%26+anti-corrosives%22">Corrosion & anti-corrosives</searchLink><br /><searchLink fieldCode="DE" term="%22Interfaces+%28Physical+sciences%29%22">Interfaces (Physical sciences)</searchLink><br /><searchLink fieldCode="DE" term="%22Carbon+steel%22">Carbon steel</searchLink><br /><searchLink fieldCode="DE" term="%22Radioactive+wastes%22">Radioactive wastes</searchLink>
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  Data: Abstract: Liquid-air interface (LAI) corrosion has been a concern for causing leaks in the carbon steel tanks used for holding high-level radioactive liquid waste. To assist in understanding the mechanism of LAI corrosion, the kinetics of nitrate and nitrite reduction reactions were investigated electrochemically. Cyclic voltammetry and cathodic polarization measurements indicated that the nitrite reduction reaction exhibited faster kinetics than the nitrate reduction reaction at higher cathodic overpotential. However, the primary reduction reaction at the open circuit potential under aerated conditions was the oxygen reduction reaction. The reduction of residual oxygen was also the dominant cathodic reaction at open circuit potential in deaerated conditions. Moreover, the kinetics of oxygen reduction on steel electrodes were significantly influenced by the sample immersion conditions (partial vs. full) for aerated liquid nuclear waste simulants, but not for deaerated conditions. Lastly, the gaseous products formed during LAI corrosion were analyzed using the gas detector tube method and gas chromatography-mass spectrometry and found to contain NH3, NO2 and NO. However, the results suggested that these products were caused by the local acidification generated by the hydrolysis of cations after LAI corrosion underwent extensive propagation, instead of being directly reduced in alkaline conditions. Thus, the results in this work showed that the kinetics of nitrate and nitrite reduction could not generate a salt concentration cell in the meniscus region to cause LAI corrosion. [Copyright &y& Elsevier]
– Name: AbstractSuppliedCopyright
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  Data: <i>Copyright of Electrochimica Acta is the property of Pergamon Press - An Imprint of Elsevier Science and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1016/j.electacta.2013.11.136
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        Text: English
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        Type: general
      – SubjectFull: Chemical kinetics
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      – SubjectFull: Corrosion & anti-corrosives
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      – SubjectFull: Radioactive wastes
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              Text: Jan2014
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