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ABSTRACT: In this work, effects of some experimental parameters (supporting electrolyte, initial pH, and current density) on
aluminum corrosion and anodic dissolution of aluminum during electrocoagulation process were investigated. Potentiodynamic
polarization tests, impedance spectroscopy measurements and potentisotatic current density transients were used to evaluate
corrosion parameters and verify effects of supporting electrolyte and initial pH on aluminum corrosion. The presence of NaCl and
Na2SO4 shifted the corrosion potential toward more cathodic potentials, indicating that corrosion of aluminum is catalyzed by the
presence NaCl and Na2SO4. On the contrary, the presence of NaH2PO4 increased the corrosion potential, which indicates that the
presence of NaH2PO4 inhibits the corrosion of aluminum. Galvanostatic electrolyses demonstrated that measured concentrations of
aluminum exceeded theoretical values calculated using Faraday’s Law. The excess in dissolved aluminum produced during
galvanostatic electrolyses is primary due to the chemical dissolution of aluminum, which is more significant at highly alkaline
conditions. A final pH of value around pH 9 was observed in the presence of NaCl for pH values in the range pH 411 which can be
explained by buffering effects of aluminum hydroxides.
r 2011 American Chemical Society 13362 dx.doi.org/10.1021/ie201206d | Ind. Eng. Chem. Res. 2011, 50, 13362–13372
Industrial & Engineering Chemistry Research ARTICLE
Figure 7. Optical microscope photos (400) of aluminum morphology before and after anodic polarization at current density j = 10 mA cm2 in
aqueous solutions containing 0.1 M NaCl, Na2SO4, and NaH2PO4 at pH 9.
the formation of hydroxo-aluminum species. Rather, the excess precipitated, which has a large surface area that is beneficial for
of OH ions increased the pH of the medium. In contrast, for coagulation by adsorption.3945
solutions with initial pH higher than 9, the decrease in pH could
be attributed to the consumption of higher amounts of OH ions
to form anionic hydroxo-aluminum species such as Al(OH)4 4. CONCLUSION
and Al(OH)52. It should be taken into account that in highly The influence of supporting electrolyte, initial pH, and current
alkaline conditions, the amount of Al3+ ions obtained by chemical density on anodic dissolution of pure aluminum during electro-
dissolution plays a significant role in the total amount of coagulation process was evaluated. The main conclusions of this
aluminum ions generated in situ. By the end of electrolysis, the work can be summarized in the following points:
majority of aqueous solutions stabilize at a pH value close to 9. As - Potentiodynamic polarization experiments showed that
can be observed, the closer the initial pH is to 9, the more rapid aluminum corrosion is largely dependent on supporting
the stabilization of pH. The stabilization of pH to a value close to electrolyte and initial pH conditions. The presence of NaCl
9 for all initial values of pH can be explained by a buffering effect or Na2SO4 shifted the corrosion potential toward more
of hydroxo-aluminum species that balances the quasi-static negative values, indicating that corrosion of aluminum is
variation of the hydroxyl ions concentration through the forma- catalyzed by the presence NaCl or Na2SO4. However, in the
tion of monomeric and polymeric complexes of aluminum presence of NaCl, pitting corrosion occurs at a much lower
hydroxides. Several acidbase pairs can be formed in the potential than that in the presence of Na2SO4. In contrast,
medium which buffer the pH to a value around pH 9. the presence of NaH2PO4 increased the corrosion potential,
3.2.2. Influence of Current Density on Solution pH during which indicates that the presence of NaH2PO4 inhibits the
Galvanostatic Electrolysis Using Aluminum Electrodes. corrosion of aluminum. EIS and potentiostatic anodic
Figure 11-b presents the changes of pH vs time during galvano- current transients confirmed that pitting corrosion kinetics
static electrolyses at different current densities of 0.1 M NaCl is accelerated by pH increase and the presence NaCl.
aqueous solutions using aluminum plates as electrodes at initial Morphological observations proved that large localized
pH 9. No significant change of pH with time was observed using pitting corrosion was clearly observable on the surface of
different current densities, and similar profiles were obtained for aluminum plate polarized in the presence of NaCl. However,
all applied current densities. At the start of electrolysis, the pH in the case of Na2SO4, small uniformly distributed pitting
dropped by one unit, and then it increases with time until it corrosion was observed. In contrast, the aluminum plate
reaches a value close to its initial value of pH 9) and eventually polarized in the presence of NaH2PO4 was completely
stabilizes. This insignificant change of pH caused by changing covered with a layer of AlPO4.
current density during galvanostatic electrolysis can be explained - Galvanostatic electrolyses demonstrated that measured con-
by the fact that increasing the current density in the studied range centrations of aluminum were slightly higher than theore-
results only in an increase of both the rate of the aluminum anode tical values calculated using Faraday’s law and the gap
dissolution and production of H2 at the cathode surface. between them enlarged with the increase in specific electrical
3.2.3. Effect of Supporting Electrolyte on Solution pH during charge. Super-Faradic excess of dissolved aluminum is
Galvanostatic Electrolysis Using Aluminum Electrodes. primarily related to the chemical dissolution of aluminum,
Figure 11-c presents the variation of pH vs time during galvano- which is more significant at highly alkaline conditions. These
static electrolyses of aqueous solutions containing different results indicate that the amount of dissolved aluminum is
supporting electrolytes (NaCl, Na2SO4, or NaH2PO4) using basically related to pH conditions. Changes of pH during
aluminum electrodes at a current density of 6 mA cm2. galvanostatic electrolysis mainly depend on initial pH and
Figure 11-c clearly indicates that the nature of the supporting the nature of supporting electrolyte. In the presence of
electrolyte has a significant effect on the variation of pH with time NaH2PO4, the pH increased continuously until it reached a
during galvanostatic electrolysis. In the presence of NaH2PO4, value of 11.4. Whereas in the presence of NaCl or Na2SO4,
pH increased continuously until it reached a value of 11.4. pH decreased slightly at the beginning and then increased
Whereas in the presence of NaCl or Na2SO4, pH decreased gradually until it stabilized at 9.3 and 10, respectively.
slightly at the beginning and then increased gradually until it - For acidic initial pH conditions, pH increases during elec-
was stabilized at 9.3 and 10, respectively. These variations are trolyses; however, it decreases for solutions with initial pH
probably due to the nature and stability of aluminum complexes higher than 9. These results can be due to the nature of
formed in each electrolyte. In particular, the presence of hydroxo-aluminum species formed during anodic dissolu-
NaH2PO4 in the solution leads to the formation of stable tion of aluminum. In acidic and neutral conditions, it appears
complexes with Al3+ ions (Al(PO4), AlH(PO4)+, and AlH2- that hydroxide ions formed at the cathode were not com-
(PO4)2+).3235 As such, a major part of Al3+ ions formed during pletely involved in the formation of cationic and neutral
electrolysis reacts with phosphate ions. This leads to an excess hydroxo-aluminum species and the excess of OH ions
of OH available in the solution, which increases solution pH increased the pH of the medium. In contrast, the decrease of
with time. pH in highly alkaline conditions could be attributed to the
It is notable that in the presence of Na2SO4 or NaH2PO4, pH consumption of higher amounts of OH ions to form
of the solution stabilized at a value greater than pH 10, which anionic hydroxo-aluminum species such as Al(OH)4 and
facilitates the dissolution of Al(OH)3 into anionic hydroxo- Al(OH)52. The stabilization of pH to a value close to 9 for
aluminum species such as Al(OH)4 and Al(OH)52 and the slightly acid, neutral, and alkaline initial values of pH can be
formation of these species makes flocculation and electropreci- explained by a buffering effect of hydroxo-aluminum species
pitation difficult to occur. While in the case of NaCl, pH remains that balances the quasi-static variation of the concentration
in the range between 8.3 and 9.3 throughout the experiment. In of hydroxyl ions through the formation of monomeric and
this pH range, amorphous aluminum hydroxide (Al(OH)3) is polymeric complexes of aluminum hydroxides.
13370 dx.doi.org/10.1021/ie201206d |Ind. Eng. Chem. Res. 2011, 50, 13362–13372
Industrial & Engineering Chemistry Research ARTICLE
’ AUTHOR INFORMATION (19) Mollah, M. Y.; Morkovsky, P. G.; Gomes, A. G.; Kesmez, M.;
Parga, J. Fundamentals, Present and Future Perspectives of Electro-
Corresponding Author coagulation. J. Hazard. Mater. 2004, 114, 199–210.
*Phone: +21675392600. Fax: +21675392421. E-mail: nasr. (20) Yousuf, M.; Mollah, A.; Schennach, R.; Parga, J. R.; Cocke, D. L.
bensalah@issatgb.rnu.tn and/or nasr.bensalah@qatar.tamu.edu. Electrocoagulation (EC)-science and applications. J. Hazard. Mater.
2001, B84, 29–41.
(21) Barrera-Diaz, C.; Bilyeu, B.; Roa, G.; Bernal-Martinez, L. Physi-
’ ACKNOWLEDGMENT cochemical Aspects of Electrocoagulation. Sep. Purif. Rev. 2011, 40, 1–24.
(22) Hanay, O.; Hasar, H. Effect of anions on removing Cu2+, Mn2+
The authors acknowledge Texas A&M University at Qatar and and Zn2+ in electrocoagulation process using aluminum electrodes.
Qatar Foundation for providing partial financial support to J. Hazard. Mater. 2011, 189, 572–576.
accomplish this research work. (23) Pyun, S. I.; Moon, S. M.; Ahn, S. H.; Kim, S. S. Effects of Cl,
NO3, and SO42‑ ions on anodic dissolution of pure aluminum in
alkaline solution. Corros. Sci. 1999, 41, 653–667.
’ REFERENCES (24) Arroyo, M. G.; Perez-Herranz, V.; Montanes, M. T.; Garcia-
(1) Jiang, J. Q. Study on the anodic passivation of the electrocoagu- Anton, J.; Gunion, J. L. Effect of pH and chloride concentration on the
lation in water treatment process. Water Treat. 1986, 3, 344–352. removal of hexavalent chromium in a batch electrocoagulation reactor
(2) Giovanardia, R.; Fontanesib, C.; Dallabarbac, W. Adsorption of J. Hazard. Mater. 2009, 169, 1127–1133.
organic compounds at the aluminium oxide/aqueous solution interface (25) Izquierdo, C. J.; Canizares, P.; Rodrigo, M. A.; Leclerc, J. P.;
during the aluminium anodizing process. Electrochim. Acta 2011, 56, Valentin, G.; Lapicque, F. Effect of the nature of the supporting
3128–3138. electrolyte on the treatment of soluble oils by electrocoagulation.
(3) Xiong, W.; Qi, G. T.; Guo, X. P.; Lu, Z. L. Anodic dissolution of Desalination 2010, 255, 15–20.
Al sacrificial anodes in NaCl solution containing Ce. Corros. Sci. 2011, (26) Trompette, J. L.; Vergnes, H. On the crucial influence of some
53, 1298–1303. supporting electrolytes during electrocoagulation in the presence of
(4) Bockris, J. O. M.; Minevski, L. V. On the mechanism of the aluminum electrodes. J. Hazard. Mater. 2009, 163, 1282–1288.
passivity of aluminum and aluminum alloys. J. Electroanal. Chem. 1993, (27) Zaid, B.; Saidi, D.; Benzaid, A.; Hadji, S. Effects of pH and
349, 375–414. chloride concentration on pitting corrosion of AA6061 aluminum alloy.
(5) Koroleva, E. V.; Hashimoto, T.; Thompson, G. E.; Skeldon, P. Corros. Sci. 2008, 50, 1841–1847.
Anodic film formation on aluminum in nitric acid. J. Electrochem. Soc. (28) El Maghraby, A. A. Corrosion Inhibition of Aluminum in
2008, 155, C557–C564. Hydrochloric Acid Solution Using Potassium Iodate Inhibitor. Open
(6) Yakovleva, N. M.; Anicai, L.; Yakovlev, A. N.; Dima, L.; Ya., E.; Corros. J. 2009, 2, 189–196.
Khanina, M.; Buda, E.; Chupakhina, A. Structural study of anodic films (29) Huang, T. S.; Franklet, G. S. Effects of temper and potential on
formed on aluminum in nitric acid electrolyte. Thin Solid Films 2002, localized corrosion kinetics of Aluminum alloy 7075. Corrosion 2007,
416, 16–23. 63, 731–743.
(7) Burstein, G. T.; Organ, R. M. Repassivation and pitting of freshly (30) Mansfeld, F. Tafel slopes and corrosion rates obtained in the
generated aluminium surfaces in acidic nitrate solution. Corros. Sci. 2005, pre-Tafel region of polarization curves. Corros. Sci. 2005, 47, 3178–3186.
47, 2932–2955. (31) Elsener, B. Corrosion rate of steel in concrete—Measurements
(8) Amin, M. A.; Abd El-Rehim, S. S.; El-Sherbini, E. F.; Mahmoud, beyond the Tafel law. Corros. Sci. 2005, 47, 3019–3033.
S. R.; Abbas, M. N. Pitting corrosion studies on Al and AlZn alloys in (32) Kuo, H. S.; Tsai, W. T. Electrochemical Behavior of Aluminum
SCN solutions. Electrochim. Acta 2009, 54, 4288–4296. during Chemical Mechanical Polishing in Phosphoric Acid Base Slurry.
(9) McCafferty, E. Pit initiation on aluminum as a queuing process J. Electrochem. Soc. 2000, 147, 149–154.
J. Electrochem. Soc. 2010, 157, C382–C387. (33) Lee, H.; Isaacs, H. S. Inhibition Effects of Chromate, Phosphate,
(10) McCafferty, E. Sequence of steps in the pitting of aluminum by Sulfate, and Borate on Chloride Pitting Corrosion of Al. J. Korean
chloride ions. Corros. Sci. 2003, 45, 1421–1438. Electrochem. Soc. 2008, 11, 184–189.
(11) Ren, J.; Zuo, Y. Study of electrochemical behavior and mor- (34) Szklarska-Smialowska, Z. Pitting corrosion of aluminum. Cor-
phology of pitting on anodized 2024 aluminum alloy. Surf. Coat. Technol. ros. Sci. 1999, 41, 1743–1767.
2004, 182, 237–241. (35) Na, K. H.; Pyun, S. I. Effects of sulphate, nitrate and phosphate
(12) Soltis, J.; Laycock, N. J.; Krouse, D. Temperature dependence on pit initiation of pure aluminum in HCl-based solution. Corros. Sci.
of the pitting potential of high purity aluminium in chloride containing 2007, 49, 2663–2675.
solutions. Corros. Sci. 2011, 53, 7–10. (36) Canizares, P.; Martinez, F.; Jimenez, C.; Lobato, J.; Rodrigo,
(13) Ren, J.; Zuo, Y. The growth mechanism of pits in NaCl solution M. A. Comparison of the aluminum speciation in chemical and electro-
under anodic films on aluminum. Surf. Coat. Technol. 2005, 191, chemical dosing processes. Ind. Eng. Chem. Res. 2006, 45, 8749–8756.
311–316. (37) Canizares, P.; Martinez, F.; Rodrigo, M. A.; Jimenez, C.; Saez,
(14) Mao, X.; Hong, S.; Zhu, H.; Lin, H.; Wei, L.; Gan, F. Alternating C.; Lobato, J. Modelling of wastewater electrocoagulation processes Part
pulse current in electrocoagulation for wastewater treatment to prevent II: Application to dye-polluted wastewaters and oil-in-water emulsions.
the passivation of al electrode. Chem. Mater. Sci. 2008, 23, 239–241. Sep. Purif. Technol. 2008, 60, 147–154.
(15) Vasudevan, S.; Lakshmi, J.; Sozhan, G. Effects of alternating (38) Canizares, P.; Jimenez, C.; Martinez, F.; Saez, C.; Rodrigo,
and direct current in electrocoagulation. J. Hazard. Mater. 2011, 192, M. A. Study of the electrocoagulation process using aluminium and iron
26–34. electrodes. Ind. Eng. Chem. Res. 2007, 46, 6189–6195.
(16) Eyvaz, M.; Kirlaroglu, M.; Aktas, T. S.; Yuksel, E. The effects of (39) Zhu, J.; Wu, F.; Pan, X.; Guo, J.; Wen, D. Removal of antimony
alternating current electrocoagulation on dye removal from aqueous from antimony mine flotation wastewater by electrocoagulation with
solutions. Chem. Eng. J. 2009, 153, 16–22. aluminum electrodes. J. Environ. Sci. 2011, 23, 1066–1071.
(17) Lee, W. J.; Pyun, S. I. Effects of hydroxide ion addition on (40) Emamjomeh, M. M.; Sivakumar, M. Review of pollutants
anodic dissolution of pure aluminium in chloride ion-containing solu- removed by electrocoagulation and electrocoagulation/flotation pro-
tion. Electrochim. Acta 1999, 44, 4041–4049. cesses. J. Environ. Manage. 2009, 90, 1663–1679.
(18) Holt, P. K.; Barton, G. W.; Mitchell, C. A. The future for (41) Can, O. T.; Bayramoglu, M. The effect of process conditions on
electrocoagulation as a localized water treatment technology. Chemo- the treatment of benzoquinone solution by electrocoagulation. J. Hazar.
sphere 2005, 59, 355–367. Mater. 2010, 173, 731–736.