Effects of Chloride Ions and Nitrate Ions on the Anodic Dissolution of Iron in Sulfuric Acid Solution
Abstract
:1. Introduction
2. Materials and Methods
3. Results
3.1. Effects of NO3− Ions and/or Cl− Ions on the Cyclic Voltammetry Curves
3.2. Effects of NO3− Ions and/or Cl− Ions on the J–T Curves
3.3. The Surface Morphologies of Electrodes after 200 s Polarization
4. Discussion
- (1)
- As NO3− ions have strong oxidation characteristics, it will promote the change of Fe(II) in the passive film into Fe(III) [25,26] (Figure 5A stepI). When CNO3− = CCl− = 0.020 mol dm−3 in the same injections, the two anions adsorbed competitively onto the passive film. Thus, Fe(III) in the film increases after the injection disturbance.
- (2)
- According to the hard and soft acids and bases (HSAB) principle [31], the hard acid Fe3+ ion combines with the hard base Cl− ion readily. Thus, in the presence of Cl− ions on the electrode surface, Fe(III) in the film changes into (FeCln)3−n and then spreads into the bulk solution quickly (Figure 5A step II and III).
5. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
- Janik-Czachor, M. An assessment of the processes leading to pit nucleation on iron. J. Electrochem. Soc. 1981, 128, 513C–519C. [Google Scholar] [CrossRef]
- Wang, C.; Chen, S.; Yang, X.; Li, L. Investigation of chloride-induced pitting processes of iron in the H2SO4 solution by the digital holography. Electrochem. Commun. 2004, 6, 1009–1015. [Google Scholar] [CrossRef]
- Punckt, C.; Bölscher, M.; Rotermund, H.H.; Mikhailov, A.S.; Organ, L.; Budiansky, N.; Scully, J.R.; Hudson, J.L. Sudden onset of pitting corrosion on stainless steel as a critical phenomenon. Science 2004, 305, 1133–1136. [Google Scholar] [CrossRef]
- Pagitsas, M.; Pavlidou, M.; Papadopoulou, S.; Sazou, D. Chlorates induce pitting corrosion of iron in sulfuric acid solutions: An analysis based on current oscillations and a point defect model. Chem. Phys. Lett. 2007, 434, 63–67. [Google Scholar] [CrossRef]
- Lin, B.; Hu, R.; Ye, C.; Li, Y.; Lin, C. A study on the initiation of pitting corrosion in carbon steel in chloride-containing media using scanning electrochemical probes. Electrochim. Acta 2010, 55, 6542–6545. [Google Scholar] [CrossRef]
- Zimer, A.M.; Rios, E.C.; Mascaro, L.H.; Pereira, E.C. Temporal series micrographs coupled with polarization curves to study pit formation under anodic polarization. Electrochem. Commun. 2011, 13, 1484–1487. [Google Scholar] [CrossRef]
- Sazou, D.; Pavlidou, M.; Pagitsas, M. Potential oscillations induced by localized corrosion of the passivity on iron in halide containing sulfuric acid media as a probe for a comparative study of the halide effect. J. Electroanal. Chem. 2012, 675, 54–67. [Google Scholar] [CrossRef]
- Gupta, R.K.; Sukiman, N.L.; Cavanaugh, M.K.; Hinton, B.R.W.; Hutchinson, C.R.; Birbilis, N. Metastable pitting characteristics of aluminium alloys measured using current transients during potentiostatic polarization. Electrochim. Acta 2012, 66, 245–254. [Google Scholar] [CrossRef]
- Yoon, H.; Ha, H.Y.; Lee, T.H.; Kim, S.D.; Jang, J.H.; Moon, J.; Kang, N. Pitting corrosion resistance and repassivation behavior of C-bearing duplex stainless steel. Metals 2019, 9, 930. [Google Scholar] [CrossRef] [Green Version]
- Wang, Z.; Gao, Z.; Chu, J.; Qiu, D.; Niu, J. Low temperature sealing process and properties of Kovar alloy to DM305 electronic glass. Metals 2020, 10, 941. [Google Scholar] [CrossRef]
- Uhlig, H.H. Adsorbed and reaction-product films on metals. J. Electrochem. Soc. 1950, 97, 215C–220C. [Google Scholar] [CrossRef]
- Macdonald Digby, D. The point defect model for the passive state. J. Electrochem. Soc. 1992, 139, 3434–3449. [Google Scholar] [CrossRef]
- Szklarska-Smialowska, Z. Mechanism of pit nucleation by electrical breakdown of the passive film. Corros. Sci. 2002, 44, 1143–1149. [Google Scholar] [CrossRef]
- Leckie, H.P.; Uhlig, H.H. Environmental factors affecting the critical potential for pitting in 18–8 stainless steel. J. Electrochem. Soc. 1966, 113, 1262–1267. [Google Scholar] [CrossRef]
- Newman, R.C.; Ajjawi, M.A.A. A micro-electrode study of the nitrate effect on pitting of stainless steels. Corros. Sci. 1986, 26, 1057–1063. [Google Scholar] [CrossRef]
- Sazou, D.; Pagitsas, M. Nitrate ion effect on the passive film breakdown and current oscillations at iron surfaces polarized in chloride-containing sulfuric acid solutions. Electrochim. Acta 2002, 47, 1567–1578. [Google Scholar] [CrossRef]
- Ma, H.; Yang, C.; Li, G.; Guo, W.; Chen, S.; Luo, J. Influence of nitrate and chloride ions on the corrosion of iron. Corrosion 2003, 59, 1112–1119. [Google Scholar] [CrossRef]
- Fujioka, E.; Nishihara, H.; Aramaki, K. The inhibition of pit nucleation and growth on the passive surface of iron in a borate buffer solution containing Cl− by oxidizing inhibitors. Corros. Sci. 1996, 38, 1915–1933. [Google Scholar] [CrossRef]
- Seyedi, M.; Mirjalili, M.; Taji, I.; Armat, O.; Moayed, M. Inhibitive effect of nitrate on pitting corrosion of 17-4ph stainless steel. Corrosion 2017, 73, 181–191. [Google Scholar] [CrossRef]
- Jegdic, B.; Bobic, B. Pitting corrosion testing of stainless steel AISI 304 in chloride solutions. Zavar. Zavarene Konstr. 2015, 60, 101–108. [Google Scholar] [CrossRef] [Green Version]
- Street, S.; Xu, W.; Amri, M.; Guo, L.; Glanvill, S.J.M.; Quinn, P.D.; Mosselmans, J.F.W.; Rau, C.; Rayment, T.; Davenport, A. The effect of nitrate on salt layers in pitting corrosion of 304l stainless steel. J. Electrochem. Soc. 2015, 162, C457–C464. [Google Scholar] [CrossRef] [Green Version]
- Zeng, M.; Wang, C.; Li, L. Designed oscillations of the Fe/H2SO4 system with the flow injection in a partially-closed environment. Electrochem. Commun. 2009, 11, 1888–1891. [Google Scholar] [CrossRef]
- Lannuzel, D.; Jong, J.D.; Schoemann, V.; Trevena, A.; Tison, J.; Chou, L. Development of a sampling and flow injection analysis technique for iron determination in the sea ice environment. Anal. Chim. Acta 2006, 556, 476–483. [Google Scholar] [CrossRef]
- Fonseca, A.; Raimundo, I.M., Jr.; Rohwedder, J.J.; Ferreira, L.O.S. Construction and evaluation of a flow injection micro-analyser based on urethane-acrylate resin. Anal. Chim. Acta 2007, 603, 159–166. [Google Scholar] [CrossRef]
- Huang, Y.H.; Zhang, T.C. Effects of low pH on nitrate reduction by iron powder. Water Res. 2004, 38, 2631–2642. [Google Scholar] [CrossRef]
- Xu, J.; Hao, Z.; Xie, C.; Lv, X.; Yang, Y.; Xu, X. Promotion effect of Fe2+ and Fe3O4 on nitrate reduction using zero-valent iron. Desalination 2012, 284, 9–13. [Google Scholar] [CrossRef]
- Engell, H.J. Stability and breakdown phenomena of passivating films. Electrochim. Acta 1977, 22, 987–993. [Google Scholar] [CrossRef]
- Sazou, D.; Pagitsas, M. Non-linear dynamics of the passivity breakdown of iron in acidic solutions. Chaos Solitons Fractals 2003, 17, 505–522. [Google Scholar] [CrossRef]
- Saraby-Reintjes, A. Theory of competitive adsorption and its application to the anodic dissolution of nickel and other iron-group metals—II, The steady state in the prepassive, passive and transpassive potential ranges. Electrochim. Acta 1985, 30, 403–417. [Google Scholar] [CrossRef]
- Burstein, G.T.; Pistorius, P.C.; Mattin, S.P. The nucleation and growth of corrosion pits on stainless steel. Corros. Sci. 1993, 35, 57–62. [Google Scholar] [CrossRef]
- Pearson, R.G. Hard and soft acids and bases. J. Am. Chem. Soc. 1963, 85, 3533–3539. [Google Scholar] [CrossRef]
- Pavlidou, M.; Pagitsas, M.; Sazou, D. Potential oscillations induced by the local breakdown of passive iron in sulfuric acid media. An evaluation of the inhibiting effect of nitrates on iron corrosion. J. Solid State Electrochem. 2015, 19, 3207–3217. [Google Scholar] [CrossRef]
- Burstein, G.T. Passivity and localized corrosion. Shreir’s Corros 2010, 2, 731–752. [Google Scholar]
Solutions | Epp (v) | Solutions | Epp (v) |
---|---|---|---|
0.5 M H2SO4 | 0.289 | 0.5 M H2SO4 + 0.02 M NaCl | none |
0.5 M H2SO4 + 0.02 M NaNO3 | 0.283 | 0.5 M H2SO4 + 0.02 M NaCl + 0.02 M NaNO3 | none |
0.5 M H2SO4 + 0.2 M NaNO3 | 0.265 | 0.5 M H2SO4 + 0.02 M NaCl + 0.2 M NaNO3 | 0.720 |
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Zhu, Y.; Zhang, J.; Wang, C.; Li, L. Effects of Chloride Ions and Nitrate Ions on the Anodic Dissolution of Iron in Sulfuric Acid Solution. Metals 2020, 10, 1118. https://doi.org/10.3390/met10091118
Zhu Y, Zhang J, Wang C, Li L. Effects of Chloride Ions and Nitrate Ions on the Anodic Dissolution of Iron in Sulfuric Acid Solution. Metals. 2020; 10(9):1118. https://doi.org/10.3390/met10091118
Chicago/Turabian StyleZhu, Yongyan, Jianli Zhang, Chao Wang, and Liang Li. 2020. "Effects of Chloride Ions and Nitrate Ions on the Anodic Dissolution of Iron in Sulfuric Acid Solution" Metals 10, no. 9: 1118. https://doi.org/10.3390/met10091118