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Anodic Dissolution of Pure Aluminum during

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Article in Industrial & Engineering Chemistry Research December 2011

DOI: 10.1021/ie201206d

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 ARTICLE

pubs.acs.org/IECR

Anodic Dissolution of Pure Aluminum during Electrocoagulation

Process: Influence of Supporting Electrolyte, Initial pH, and Current
Density
Khaled Mansouri, Karim Ibrik, Nasr Bensalah,*,, and Ahmed Abdel-Wahab

Department of Chemistry, Faculty of Sciences of Gabes, University of Gabes, Cite Erriadh, Zrig 6072, Gabes, Tunisia

Department of Chemical Engineering, Texas A&M University at Qatar, Education City, P.O. Box 23874, Doha, Qatar

ABSTRACT: In this work, eects 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 eects 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 Faradays Law. The excess in dissolved aluminum produced during
galvanostatic electrolyses is primary due to the chemical dissolution of aluminum, which is more signicant at highly alkaline
conditions. A nal pH of value around pH 9 was observed in the presence of NaCl for pH values in the range pH 4
11 which can be
explained by buering eects of aluminum hydroxides.

1. INTRODUCTION surface has also been suggested by some researchers.14
16

The passivity of aluminum sacricial electrodes was extremely
problematic for the treatment of industrial euents by
electrocoagulation.1
4 Passive lms are readily formed on the
surface of aluminum and its alloys in open air and in water.5,6 The
corrosion resistance of aluminum depends largely on the forma-
tion of a native oxide lm on its surface. The aluminum oxide lm
is relatively chemically inert, exhibiting the passive behavior of
aluminum. The formation of this passive lm that adheres to the
anode surface prevents the dissolution of aluminum and restricts
charge transfer between solution and electrodes. Passivation of
sacricial anodes leads to excessive consumption of electricity
and reduces the eciency of wastewater treatment by electroco-
agulation.
The rate of corrosion of sacricial aluminum anodes depends
mainly on two mechanisms: formation and build-up of a passive
aluminum-oxide layer and subsequent partial destruction of that
layer through pitting.7
12 Aluminum is much more susceptible to
pitting than other metals, and a variety of anions that may exist in
the solution can bring about pitting. In most practical cases of
aluminum corrosion, the chemical reaction of anions adsorbed
on the surface of the aluminum oxide lm with cationic Al species
in the oxide lattice signicantly aect the overall aluminum
dissolution reaction. This chemical reaction causes the local
breakdown of the passive oxide lm, which is often followed by
pitting corrosion.11
13
Few researchers14
21 have suggested the addition of support-
ing electrolytes, such as sodium chloride (NaCl), to reduce the
passivation of working electrodes and to increase the conductiv-
ity of the medium. Additionally, application of a sinusoidal
intensity to prevent the formation of a deposit on electrode
However, literature lacks attention to the eect of experimental
parameters such as nature and concentration of supporting
electrolyte, pH, and current density on the rate of destruction
of the aluminum protective lm that forms on sacricial alumi-
num anodes, which in turn inuences the overall rate of the
electrochemical reactions and mechanisms involved in electro-
coagulation.22
27 The aim of this study is to obtain information
on the corrosion behavior of aluminum sacricial anodes and
evaluate the eects of supporting electrolyte nature and con-
centration, pH, and current density on electrochemical dissolu-
tion of aluminum. Two main experimental sets were carried out
to achieve the objective of this study. First, the corrosion
behavior of an aluminum anode in dierent electrolytes (NaCl,
Na2SO4, and NaH2PO4) was examined using potentiodynamic
polarization tests. Second, the eect of pH and current density
parameters on the electrochemical dissolution of aluminum
was studied using galvanostatic electrolysis of aluminum
electrodes.
2. MATERIALS AND METHODS
2.1. Chemicals and Analytical Methods. All reagents used
were of analytical grade obtained from Fulka or Acros. Relevant
aqueous solutions were prepared by dissolving lab grade reagents
(NaCl, Na2SO4, NaH2PO4) in deionized water obtained from a
Received: June 6, 2011
Accepted: October 5, 2011
Revised: October 3, 2011
Published: October 05, 2011

r 2011 American Chemical Society 13362 dx.doi.org/10.1021/ie201206d | Ind. Eng. Chem. Res. 2011, 50, 1336213372
Industrial & Engineering Chemistry Research
Milli-Q system (Molsheim, France), with resistivity >18 m at
25 C. Working electrodes were comprised of aluminum plates
cut from a pure aluminum sheet (99.99% purity) of 2 mm
thickness. Prior to each experiment, the aluminum working
electrode was manually finished using successively finer grades
of abrasive paper, polished with 0.3 m alumina, rinsed with
1.5 M HCl followed by rinsing with deionized water, and then
dried before immersion in the electrolyte solution. Samples were
taken periodically and analyzed for dissolved aluminum concen-
tration and pH value. Concentration of dissolved aluminum
during galvanostatic electrolysis was determined by atomic absorp-
tion spectrometry (Zeeman spectrophotometer HITACHI
Z-6100) after acidification using nitric acid (4 N HNO3 ).
The pH of the aqueous solutions was measured using inoLab
WTW pH-meter, equipped with a combined glass electrode
(METROHM). The conductivity was measured using a con-
ductivity meter (MeterLab, type CDM230) equipped with a
conductivity cell comprised of two platinum electrodes. Mor-
phological observations of the aluminum electrode surfaces were
conducted using a metallurgical trinocular microscope (AuxiLab,
model ZUZI 173/2) after galvanostatic electrolyses.
2.2. Potentiodynamic Polarization and Potentiostatic Cur-
rent/Time Measurements. Potentiodynamic tests were used to
evaluate the pitting behavior and passivity of aluminum in
0.1
0.4 M NaCl, 0.1 M Na2SO4, and 0.1 M NaH2PO4 aqueous
solutions. Potentiodynamic polarization experiments of alumi-
num were performed with a three-electrode cell (Radiometer
C145/170) using a potentiostat/galvanostat (PGZ 301 20 V 1A)
controlled by Voltalab 40 software to allow data acquisition. A
platinum plate and a saturated calomel electrode (SCE) were
respectively used as auxiliary and reference electrodes. The
working electrode was a 1 cm2 pure aluminum plate (99.99%)
inserted into a PTFE sample holder (Radiometer PEK 29). The
electrochemical potential was scanned positively starting from

2.0 V up to +2.0 V vs SCE at a scan rate of 0.5 mV s
1. The
potentiostatic current/time transient measurements were carried
out after a two step procedure as follows: the working electrode
was first held at the starting potential
2.0 V/SCE for 1 min to
attain a reproducible electroreduced electrode surface; then the
electrode was suddenly polarized in the positive direction to a
potential equal Epit for 30 min, after that current transient was
recorded.
2.3. Electrochemical Impedance Spectroscopy. Electro-
chemical impedance spectroscopy (EIS) measurements were
carried out using a potentiostat/galvanostat (PGZ 301 20 V 1A)
controlled by Voltalab 40 software to allow data acquisition of
corrosion potentials (Ecorr) of aluminum electrodes immersed in
aerated solutions. After determination of steady-state current at
Ecorr, peak-to-peak sine wave voltages (10 mV) were super-
imposed on the resting potential at frequencies between 100 kHz
and 10 mHz. The EIS diagrams are shown in Nyquist form
(shown where. If they are shown in a figure, please indicate the
figure no.).
2.4. Galvanostatic Electrolyses. Anodic dissolution of alu-
minum was carried out under galvanostatic conditions. The
electrolyses experiments were performed in a one compartment
thermostatted electrolytic cell (parallel rectangular aluminum
electrodes, 24 cm2, interelectrode gap 2 cm). Aluminum electro-
des were connected to a digital DC power supply (Monacor PS-
430) operating under galvanostatic options, providing current
and voltage in the range of 0
30 A and 0
20 V, respectively.
The cell voltage was recorded using a potentiometer. During the
13363
ARTICLE
Figure 1. Changes of open circuit potential with time during immersion
of aluminum plate in aerated deionized water. Operating conditions:
anode: pure Al specimen (1 cm2); reference electrode: SCE; T = 25 C.
galvanostatic electrolyses process, the aqueous solution (0.2 dm3)
was vigorously stirred using a magnetic stir bar (200 rpm), and
the temperature was held constant at 25 C. Aqueous solution
pH was adjusted using 0.1 M NaOH or HCl to achieve the
desired initial pH values for each experiment.
3. RESULTS AND DISCUSSION
3.1. Study of Aluminum Corrosion by Potentiodynamic
Polarization. In order to better understand the influence of
supporting electrolyte on the electrochemical corrosion of
aluminum, open circuit potential and potentiodynamic polariza-
tion experiments were performed in an attempt to explain the
phenomena occurring on the anode surface. Figure 1 displays the
changes of an aluminum electrode in the open-circuit potential
(OCP) with immersion time in deionized water at room
temperature. The OCP instantly increased from an initial value
of
795 mV/SCE to a value of
670 mV/SCE, and it remained
constant at this value with minor fluctuations with time around
this value. The immediate increase of OCP can be explained by
the growth of Al(OH)3 film on the surface of the Al electrode.
The fluctuation of the OCP can be attributed to the changes of
pH near the Al electrode surface. Based on these results, a
corrosion potential value (Ecorr) of
670 ( 5 mV/SCE can be
deduced for pure Al in aerated aqueous solutions. This value is
very similar to those reported in the literature.28,29
Figure 2 shows anodic and cathotic potentiodynamic polariza-
tion curves obtained from pure Al plates at a scan rate of 0.5
mV s
1 in aerated aqueous solution without supporting electro-
lyte. As can be seen from Figure 2, both anodic and cathodic
branches display a typical Tafel behavior. Accurate evaluation of
corrosion potential (Ecorr) and corrosion current density (jcorr)
was made using the Tafel extrapolation method30,31 and pre-
sented in Figure 2. The anodic polarization curve shows an
extremely active dissolution followed by a limitation at high
current densities. Corrosion potential (Ecorr) of aluminum as
determined by the Tafel extrapolation method is very compar-
able to that determined previously by open circuit potential
measurements: Ecorr=
668 mV/SCE. Corrosion current (jcorr)
of aluminum electrode was equal to 2.6 A cm
2.
Figure 3-a shows potentiodynamic polarization curves obtained
from an aluminum plate in aerated aqueous solutions containing
0.1 M of NaCl, Na2SO4, or NaH2PO4 under alkaline conditions
(pH = 9) at a scan rate of 0.5 mV s
1. The potentiodynamic
dx.doi.org/10.1021/ie201206d |Ind. Eng. Chem. Res. 2011, 50, 1336213372
Industrial & Engineering Chemistry Research
Figure 2. Potentiodynamic polarization curve of aluminum in aerated
deionized water, and extrapolation Tafel method. Operating conditions:
anode: pure Al specimen (1 cm2); cathode: Pt wire; reference electrode:
SCE; pH = 7; scan rate: 0.5 mV s
1; T = 25 C.
polarization plot without supporting electrolyte was also pre-
sented in the same gure for comparison (in this case the current
density is expressed in A cm
2). Figure 3 shows that the anodic
electrode behavior in the presence of supporting electrolyte was
completely dierent from that observed in aerated deionized
water without supporting electrolyte. Also, the behavior of the
anodic polarization branches in the presence of supporting
electrolyte do not display the expected log/linear Tafel behavior
over the whole applied range of potential. The observed curva-
ture of the anodic branch may be attributed to the deposition of
corrosion products on the aluminum surface to form a non-
passive surface lm. Aluminum showed a classical passive region
in which current remained almost unaected by the change in
applied potential. This can be observed as a current density
plateau in Figure 3-b. However, the current density increased
abruptly after reaching a certain value of electrode potential
which is the pitting potential (Epit). The pitting corrosion was
preceded by uniform thinning of the hydroxide/oxide protective
lm that prevails over pitting corrosion prior to the pitting
potential. After reaching Epit, current density continued to
increase very slightly with increasing potential. As can be
observed, the nature of the electrolyte greatly aects corrosion
current density and corrosion potential. The values of corrosion
current density and corrosion potential in solutions containing
dierent electrolytes are shown in Table 1.
The presence of NaCl or Na2SO4 shifted the corrosion potential
toward more negative values, indicating that corrosion of aluminum
is catalyzed by the presence NaCl or Na2SO4. In contrast, the
presence of NaH2PO4 increased the corrosion potential, which
indicates that the presence of NaH2PO4 inhibits the corrosion of
aluminum. Moreover, the experimental results indicated that the
corrosion rate of aluminum is highest in the presence of NaCl
because the corrosion current density is the largest.
Figure 4 shows the Nyquist plot obtained on pure aluminum in
aqueous solutions containing 0.1 M of NaCl, Na2SO4, or NaH2PO4.
The shapes of the Nyquist plots corresponding to these conditions
include one small semicircle at the high frequency region, one
depressed semicircle, and a diusion tail which appears inclined
to the Real Impedance axis at 45 at the low frequency region. In
general, the capacitance no longer aects the total impedance
value in the diusion tail portion. The diusion process can be
13364
ARTICLE
Figure 3. (a) Potentiodynamic polarization curves of aluminum in
aerated aqueous solutions containing dierent supporting electrolytes.
(b) Dierent parts of polarization curve: charge transfer, anodic
passivation, and pitting corrosion. Operating conditions: anode: pure
Al specimen (1 cm2); cathode: Pt wire; reference electrode: SCE; pH =
9; electrolyte concentration: 0.1 M; scan rate: 0.5 mV s
1; T = 25 C.
caused by the diusion of Al3+ ions, which is produced by the
anodic reaction, from the metal surface to the bulk solution.
Therefore, the results presented in Figure 4 show that the
diusion tail at impedance plot which indicates the beginning
of metastable pitting. In addition, the depressed semicircle could
be due to microscopic surface roughness and the presence of a
porous corrosion product lm. The diameter of low frequency
semicircle changes among supporting electrolytes. The diameter
of the semicircle in the presence of NaCl is smaller than that in
the presence of NaH2PO4 or Na2SO4 which suggests that the
passive lm formed on pure aluminum in the presence of
NaH2PO4 or Na2SO4 is more protective to corrosion. This is
in accordance with the results of polarization curves.
These observations can be summarized as follows:
- The addition of supporting electrolyte increases the ionic con-
ductivity of the solution, which is a determining factor in any
electrochemical process. The increase in conductivity has a
signicant inuence on the kinetic parameters of electrochem-
ical reactions and it increases the corrosion rate of aluminum.
- For alkaline pH conditions, the corrosion of aluminum leads
to the formation of a porous layer consisting of amorphous
Al(OH)3 and crystalline Al2O3 on the surface of the anode.4,17,26
This layer is characterized by a heterogeneous structure and
irregular pores. This layer signicantly reduces the corrosion
rate of aluminum, but it cannot fully protect the aluminum
surface. The increase of anode potential damages this layer
dx.doi.org/10.1021/ie201206d |Ind. Eng. Chem. Res. 2011, 50, 1336213372
Industrial & Engineering Chemistry Research ARTICLE

Table 1. Results of Potentiodynamic Polarization of Alumi-

num Determined by the Tafel Extrapolation Method in the
Presence of Dierent Supporting Electrolytesa
corrosion potential corrosion current
electrolyte Ecorr (mV) density jcorr (A cm
2)

without supporting electrolyte
668 2.6

0.1 M NaCl
1212.7 21
0.1 M Na2SO4
1056.0 8.7
0.1 M NaH2PO4
518.5 4
a
Experimental conditions: pH = 9; electrolyte concentration: 0.1 M;
scan rate: 0.5 mV s1; T = 25 C.

Figure 5. (a) Electrochemical impedance spectroscopy spectra and (b)

Figure 4. Electrochemical impedance spectroscopy spectra obtained on
pure aluminum in aerated aqueous solutions containing dierent
supporting electrolytes. Operating conditions: anode: Al specimen
(1 cm2); cathode: Pt wire; reference electrode: SCE; pH = 9; electrolyte
concentration: 0.1 M; scan rate: 0.5 mV s
1; T = 25 C.
potentiostatic current density transients at pitting potentials obtained
from pure aluminum in aerated aqueous solutions containing dierent
concentrations of NaCl. Operating conditions: anode: pure Al specimen
(1 cm2); cathode: Pt wire; reference electrode: SCE; pH = 9; scan rate:
0.5 mV s
1; T = 25 C.

through the diusion of anionic species toward the anode by

migration. Anionic exchange reactions between hydroxide ions in Figure 5-b initially remained constant with time at a value close to
and anions of the supporting electrolyte occur and form soluble zero up to an induction time of about 600 s, and then it rapidly
aluminum complexes. This exchange also causes the direct increased to a certain value at which it remained constant. The
dissolution of the passive layer of Al(OH)3 and Al2O3. All of ascending current after induction time can be attributed to the
these phenomena constitute the pitting corrosion of aluminum. growth of pit. It is noted that the pitting of pure aluminum increased
by increasing chloride ions concentration. These ions are character-
Pitting corrosion is responsible for the increase in current
ized by their ability to penetrate through the Al(OH)3/Al2O3 lm
density right after the passivation plateau, as shown in Figure 3-b.
forming soluble complexes.26
28 The increase of chloride concen-
The pitting potential of aluminum is the potential of passivation
tration further decreases corrosion potential and minimizes the
breakdown for which there is an acceleration of the corrosion
dierence between pitting potential and corrosion potential as can
process by diusion of anions through the pores of the Al(OH)3
be observed from Table 2. At a potential close to Epit, Cl
ions are
layer. It appears that pitting corrosion depends greatly on the
strongly adsorbed, and polarization curves show an increase in the
nature of supporting electrolyte because the value of potential
current density. This indicates an enhanced promotion of the pas-
Epit varies among dierent electrolytes. In the presence of NaCl,
sive lm hydration and hence its degradation as described by the
pitting corrosion occurs at a much lower potential than that in the
following reactions
presence of Na2SO4 or NaH2PO4 electrolytes. This is most likely
due to the size of chloride ions, which are relatively smaller than Al2 O3 6Cl
6H / 2AlCl3 3H2 O
sulfate and phosphate ions.
Figure 5-a and -b provides typical Nyquist plots and potentio- AlOH3 Cl
/ AlOH2 Cl OH

static anodic current transients, respectively obtained from pure
aluminum specimen at a potentials equal to open circuit potential AlOH2 Cl Cl
/ AlOHCl2 OH

in aerated aqueous solutions containing dierent NaCl concen-
trations. The results presented in Figure 5-a show that the diameter
of low frequency semicircle increased with NaCl concentration AlOHCl2 Cl / AlCl3 OH

suggesting that the passivity of the oxide lm decreases with NaCl
concentration increase. However, the anodic current density shown AlCl3 Cl
/ AlCl4

13365 dx.doi.org/10.1021/ie201206d |Ind. Eng. Chem. Res. 2011, 50, 1336213372

Industrial & Engineering Chemistry Research ARTICLE

Table 2. Corrosion and Pitting Potentials Obtained from

Potentiodynamic Polarization Curves of Aluminum in the
Presence of NaCl at Dierent Concentrationsa
corrosion potential pitting potential
electrolyte Ecorr (mV) Epit (mV) Epit-Ecorr (mV)

without electrolyte
668.0 - -

0.1 M NaCl
1212.7
646.0 566.7
0.15 M NaCl
1223.8
662.0 561.8
0.2 M NaCl
1255.5
707.0 548.5
a
Experimental conditions: pH = 9; scan rate: 0.5 mV s
1; T = 25 C.

In the presence of sulfate ions, the observed pitting was much

lower than that observed in the presence of chloride ions. In the
case of solutions containing sulfate, the passive layer of Al(OH)3/
Al2O3 is partially dissolved, and consequently the rate of elec-
trochemical corrosion of aluminum is lower. Whereas in the
presence of phosphate ions, no pitting was observed due to the
formation of insoluble complexes of AlPO4 that further inhibit
the corrosion of aluminum.32
35
Figure 6-a shows potentiodynamic polarization curves for pure
aluminum immersed in 0.1 M NaCl aerated aqueous solutions at
dierent pH values of 2, 5, 7, 9, and 11. Similar behavior of
potentiodynamic polarization was observed for all tested pH
values. However, a shift of corrosion potential was observed
when pH was changed from neutral pH to acidic or alkaline pH
values. Indeed the corrosion potential in neutral solution is the
lowest. The beginning of pitting is not visible in these cases since
the pitting potentials Epit coincided with the corrosion potentials Figure 6. (a) Potentiodynamic polarization curves and (b) electro-
Ecorr. From these results, it can be concluded that the main chemical impedance spectroscopy spectra obtained on pure aluminum
degradation mechanism in 0.1 M NaCl aerated aqueous solu- in NaCl aerated aqueous solutions at dierent initial pH values.
tions of pH values 2, 5, and 7 is pitting corrosion and the pitting Operating conditions: anode: pure Al specimen (1 cm2); cathode: Pt
potential is independent of pH over this pH range. On the wire; reference electrode: SCE; electrolyte concentration: 0.1 M; scan
rate: 0.5 mV s
1; T = 25 C.
contrary, in case of alkaline solutions (pH values of 9 and 11), the
values of corrosion potential Ecorr were observed to be lowered to
more cathodic values without a change in the pitting potential. These results indicate the signicance of supporting electro-
Further, the decrease in the corrosion potential Ecorr values, lyte in aluminum corrosion. It has been observed that the
compared to those of acidic and neutral pH, indicate the loss of corrosion of aluminum is more favorable in the presence of
passivity of aluminum due either to thinning of surface oxide chloride ions than that in the presence of sulfate or phosphate
ions. The phosphate ions inhibit corrosion of aluminum
layer by hydroxide ions (OH
) attack (alkaline chemical dis-
through the formation of a protective layer of aluminum
solution) or to the absence of the primary oxide lm.17,26 EIS
phosphate (phosphatation).
spectra of Figure 6-b show that increasing pH from 2 to 7 has no
3.2. Electrochemical and Chemical Dissolution of Alumi-
inuence on Nyquist plots. However a decrease of diameter of
num. According to the literature,36
38 efficiency of the
semicircle at high frequency was observed for pH 9 and 11. This
electrocoagulation process in treating wastewaters depends
conrms that thinning of surface oxide layer by hydroxide ions
largely on the amount and speciation of aluminum dissolved
occurs at alkaline conditions.
during the electrochemical treatment process. In order to
Furthermore, morphological observations by optical mi-
evaluate the dissolution of aluminum during galvanostatic
croscope of aluminum electrode surfaces before and after
anodic polarization at a constant current density of 10 electrolyses, the amount of aluminum dissolved (mexp) was
mA cm
2 in aqueous solutions containing 0.1 M of NaCl, measured and compared to the calculated theoretical amount
Na2SO4, or NaH2PO4 at pH 9 are shown in Figure 7. This expected to be dissolved (mth) using Faradays law. Figure 8
gure shows that large localized pitting corrosion was clearly presents comparison between theoretical and experimental
observable on the surface of aluminum plate polarized in the aluminum concentration dissolved at different specific elec-
presence of NaCl. However, in the case of Na2SO4, uniform trical charges (A.h.L
1) during galvanostatic electrolysis of 0.1
distributed pitting corrosion was observed. In contrast, the M NaCl aerated aqueous solution using aluminum electrodes
aluminum plate polarized in the presence of NaH2PO4 was at a current density of 10 mA cm
2. Theoretical aluminum
completely covered with a white porous layer, which is most concentration (in g L
1) was calculated using Faradays law,
likely an insoluble layer of AlPO4. It appears that this layer assuming that the provided electrical energy was entirely used
was of dierent nature and structure and was thicker than the only to oxidize Al to Al3+ according to the following reaction:
layers observed in the presence of the other two electrolytes. Al / Al3+ + 3e
.
13366 dx.doi.org/10.1021/ie201206d |Ind. Eng. Chem. Res. 2011, 50, 1336213372
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 cm
2 in
aqueous solutions containing 0.1 M NaCl, Na2SO4, and NaH2PO4 at pH 9.

According to Faradays law, the electrical charge q is calculated

using the following equation
mAl q  MAl
q 3F w mAl w Al
MAl 3F
q  MAl

3FV
During galvanostatic electrolyses, the current density is con-
stant; thus electrical charge (q) and specic electrical charge (Q)
are dened respectively by the following equations: q(A.s) = I  t
and Q(A.h.L
1) = (I  t)/(3600  V).
The theoretical amount of dissolved aluminum is then given
by the following equation
I  t  MAl 3600  Q  MAl
Alg L-1
3FV 3F
Figure 8. Changes of theoretical and experimental concentrations of
0:366  Q A h L
1 aluminum dissolved during galvanostatic electrolysis with specic electrical
charge. Operating conditions: initial pH = 7, j = 10 mA cm
2, supporting
where [Al] is the amount of aluminum generated (in g dm
3); I electrolytes: 0.1 M NaCl.
is the current intensity (in A); t is electrolysis-time (in s); M is the
molecular weight of aluminum (M = 26.98 g mol
1); F is the As can be seen from Figure 8, both theoretical and experi-
Faraday constant (F = 96487 C mol
1); V is the electrolyte mental amounts of aluminum at a current density of 10 m A cm
2
volume (V = 0.2 dm
3); and Q is the specic electrical charge (in increase linearly with increasing specic electrical charge for Q e
A h dm
3). 2.5 A h L
1. At the beginning of galvanostatic electrolysis,
13367 dx.doi.org/10.1021/ie201206d |Ind. Eng. Chem. Res. 2011, 50, 1336213372
Industrial & Engineering Chemistry Research
Figure 9. (a) Inuence of current density on the changes of aluminum
concentration dissolved during galvanostatic electrolyses with specic
electrical charge. (b) Photos of samples taken during anodic dissolution
of aluminum. Operating conditions: initial pH = 7, j = 10 mA cm
2,
supporting electrolytes: 0.1 M NaCl.
measured concentrations of aluminum correlate well with theo-
retical concentrations calculated from the aforementioned equa-
tions. However, for specic electrical charge greater than 0.5 A h
L
1, experimental values exceeded theoretical values and the gap
between the two broadened with the increase of specic electrical
charge. It should be noted that similar results were reported by
other authors.36
39
Figure 9-a demonstrates the inuence of current density on
the change of measured aluminum concentration with specic
electrical charge during galvanostatic electrolyses of 0.1 M NaCl
aqueous aerated solutions at pH 7. As can be seen, dierent
current densities did not signicantly aect the amount of
aluminum dissolved by anodic oxidation of the metal. Indeed,
comparable amounts of aluminum were measured at dierent
current densities after consuming the same amount of electrical
specic charge. This could be explained by the fact that the
increase in current density lead to the involvement of secondary
reactions that can occur in parallel with anodic dissolution of
metal, such as oxygen evolution and formation of hypochlorite
ions from anodic oxidation of chloride ions.25
27 These side
reactions decrease the eectiveness of anodic dissolution of
aluminum. Furthermore, it was observed that increasing the
current density resulted in an increased rate of hydrogen pro-
duction and a decrease in size of H2 bubbles generated at the
cathode. Additionally, Figure 9-b conrmed the formation of
Al(OH)3 solid precipitate during anodic dissolution of alumi-
num. Generated Al3+ ions react with hydroxide ions (OH
) to
produce Al(OH)3 solid, which was visually observed in the reactors.
The amount of white precipitate increased with time, which is in
13368
ARTICLE
Figure 10. (a) Change of aluminum concentration with time during
immersion of aluminum plates (24 cm2) in 0.1 M NaCl aqueous
solutions at pH 9. (b) Changes of dissolved aluminum concentration
with pH during 60 min immersion of aluminum plates (24 cm2) in 0.1 M
NaCl aqueous solution.
agreement with the measured amount of aluminum dissolved
during galvanostatic electrolyses. These results proved that
galvanostatic electrolysis of 0.1 M NaCl aqueous solutions using
aluminum electrodes at neutral pH leads to the formation of Al3+
ions at the anode and the production hydrogen gas at the
cathode.
The gap between measured aluminum concentrations during
galvanostatic electrolysis and the theoretical amounts of alumi-
num as shown in Figure 8 can be attributed to chemical
dissolution of aluminum electrodes by corrosion in addition to
anodic dissolution of aluminum. Several researchers have also
reported the same behavior.12
21 However, to conrm this
assumption, it is necessary to evaluate the chemical dissolution
of aluminum in water. A set of experiments was conducted in
which aluminum plates of known weights were immersed in
slightly alkaline 0.1 M NaCl aqueous solutions (pH = 9). These
conditions were selected to mimic pH conditions near the
cathode where the chemical dissolution of aluminum is most
likely to occur. Figure 10 shows changes of aluminum concen-
tration with time, as determined by the gravimetric method
during immersion of identical aluminum plates (24 cm2) in 0.1 M
NaCl aqueous solutions at pH 9. As can be observed, aluminum
concentration increased linearly with time up to 480 min, after
which it reached a plateau at about 0.014 g L
1 for the rest of the
operating time. This behavior may be explained by the formation
of a protective layer of aluminum hydroxide/oxide (Al(OH)3/
Al2O3) on the aluminum electrode surface, which inhibits further
chemical dissolution of aluminum.1
4 The formation of this
dx.doi.org/10.1021/ie201206d |Ind. Eng. Chem. Res. 2011, 50, 1336213372
Industrial & Engineering Chemistry Research ARTICLE

protective layer in aerated solutions can be given by the following

reactions
Al / Al3 3e

2H2 O 2e
/ H2 2OH

The overall chemical reaction is

2Al 3H2 O f 2AlOH3sd H2
Also, in the presence of dissolved oxygen aluminum can be
directly oxidized into aluminum oxide, as shown by the following
reaction
4Al 3O2aq f 2Al2 O3sd
These results conrmed that aluminum can be chemically
dissolved, but the amount dissolved by chemical oxidation with
dissolved oxygen at pH 9 is negligible compared to that dissolved
by anodic oxidation. As such, chemical dissolution under these
operating conditions is not sucient to explain the gap observed
in Figure 8. The gap could be possibly explained by the fact that
the operating conditions present during the chemical dissolution
of aluminum are dierent from the actual hydrodynamic condi-
tions and pH in the vicinity of aluminum electrodes used during
galvanostatic electrolysis. Particularly, the pH conditions at the
cathode are strongly alkaline due to the reduction of water into
H2 forming OH
ions. To better understand the signicance of
chemical dissolution of aluminum in the electrocoagulation
process, it is necessary to evaluate the inuence of initial pH
on the chemical dissolution of aluminum. Figure 10-b presents
concentrations of dissolved aluminum at various initial pH values
during 60 min immersion of identical aluminum plates (24 cm2)
in 0.1 M NaCl aerated aqueous solutions. This gure clearly
shows that pH had a signicant inuence on the amount of
chemically dissolved aluminum. The chemical dissolution of
aluminum was negligible for pH < 10. However, for higher pH
values, the concentration of aluminum dissolved in aqueous Figure 11. Inuence of (a) initial pH, (b) current density, and (c)
solutions increased with an increasing pH value from approxi- supporting electrolyte on changes of pH vs time during galvanostatic
mately 0.03 g L
1 at pH 11 to 0.5 g L
1 at pH 12.5. These results electrolysis using aluminum electrodes.
demonstrate that the chemical dissolution of aluminum in the
electrocoagulation process depends largely on pH in the vicinity plates. Based on the literature,40
45 it was reported that initial
of electrodes. Nevertheless, it is dicult to identify exactly the pH pH, current density, and nature of supporting electrolyte are the
conditions at electrodes surfaces, which makes it complex to main parameters that can cause pH changes during galvanostatic
accurately quantify the amount of aluminum chemically dis- electrolysis.
solved. These results indicate that dissolved concentrations of 3.2.1. Influence of Initial pH on Solution pH during Galvano-
aluminum measured during galvanostatic electrolyses using static Electrolysis Using Aluminum Electrodes. Figure 11-a
aluminum electrodes are attained by both electrochemical and presents the changes of pH vs time during galvanostatic electro-
chemical dissolution. The importance of chemical dissolution lyses of 0.1 M NaCl aqueous solutions of different initial pH
depends largely on pH conditions close to electrodes surfaces. values using aluminum plates as electrodes at a current density of
Superfaradic excess of dissolved aluminum is primarily related to 10 mA cm
2. This figure shows that pH changes over time
the chemical dissolution of aluminum, which is more signicant depend on the initial pH value of the electrolyzed solution. These
at pH > 11. Canizares et al.36
39 also demonstrated that the rate results demonstrate that regardless of initial pH value, the pH
of chemical dissolution of aluminum in water is pH dependent, evolution versus time follows two stages: a stage of rapid pH
and it is higher for pH values above 12. change over time and a stage in which pH remains almost
3.3. Influence of Experimental Parameters on Solution pH constant. It is noteworthy that the curve of pH vs time is
during Galvanostatic Electrolyses Using Aluminum Electro- ascending for solutions of initial pH lower or equal to 9 and is
des. The preceding results showed that solution pH influences descending in alkaline solutions (pH > 9). For acidic initial pH
the rate of aluminum dissolution during galvanostatic electrolysis conditions, the increase in pH can be explained by the formation
of aqueous solutions using aluminum electrodes. This led us to of OH
ions from the reduction of H+ or H2O on the surface of
investigate the influence of experimental parameters on the changes the cathode.30,31 In these circumstances, it appears that hydrox-
of pH during galvanostatic electrolysis between two aluminum ide ions formed at the cathode were not completely involved in
13369 dx.doi.org/10.1021/ie201206d |Ind. Eng. Chem. Res. 2011, 50, 1336213372
Industrial & Engineering Chemistry Research
the formation of hydroxo-aluminum species. Rather, the excess
of OH
ions increased the pH of the medium. In contrast, for
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

and Al(OH)52
. It should be taken into account that in highly
alkaline conditions, the amount of Al3+ ions obtained by chemical
dissolution plays a significant role in the total amount of
aluminum ions generated in situ. By the end of electrolysis, the
majority of aqueous solutions stabilize at a pH value close to 9. As
can be observed, the closer the initial pH is to 9, the more rapid
the stabilization of pH. The stabilization of pH to a value close to
9 for all initial values of pH can be explained by a buffering effect
of hydroxo-aluminum species that balances the quasi-static
variation of the hydroxyl ions concentration through the forma-
tion of monomeric and polymeric complexes of aluminum
hydroxides. Several acid
base pairs can be formed in the
medium which buffer the pH to a value around pH 9.
3.2.2. Influence of Current Density on Solution pH during
Galvanostatic Electrolysis Using Aluminum Electrodes.
Figure 11-b presents the changes of pH vs time during galvano-
static electrolyses at different current densities of 0.1 M NaCl
aqueous solutions using aluminum plates as electrodes at initial
pH 9. No significant change of pH with time was observed using
different current densities, and similar profiles were obtained for
all applied current densities. At the start of electrolysis, the pH
dropped by one unit, and then it increases with time until it
reaches a value close to its initial value of pH 9) and eventually
stabilizes. This insignificant change of pH caused by changing
current density during galvanostatic electrolysis can be explained
by the fact that increasing the current density in the studied range
results only in an increase of both the rate of the aluminum anode
dissolution and production of H2 at the cathode surface.
3.2.3. Effect of Supporting Electrolyte on Solution pH during
Galvanostatic Electrolysis Using Aluminum Electrodes.
Figure 11-c presents the variation of pH vs time during galvano-
static electrolyses of aqueous solutions containing different
supporting electrolytes (NaCl, Na2SO4, or NaH2PO4) using
aluminum electrodes at a current density of 6 mA cm
2.
Figure 11-c clearly indicates that the nature of the supporting
electrolyte has a significant effect on the variation of pH with time
during galvanostatic electrolysis. In the presence of NaH2PO4,
pH increased continuously until it reached a value of 11.4.
Whereas in the presence of NaCl or Na2SO4, pH decreased
slightly at the beginning and then increased gradually until it
was stabilized at 9.3 and 10, respectively. These variations are
probably due to the nature and stability of aluminum complexes
formed in each electrolyte. In particular, the presence of
NaH2PO4 in the solution leads to the formation of stable
complexes with Al3+ ions (Al(PO4), AlH(PO4)+, and AlH2-
(PO4)2+).32
35 As such, a major part of Al3+ ions formed during
electrolysis reacts with phosphate ions. This leads to an excess
of OH
available in the solution, which increases solution pH
with time.
It is notable that in the presence of Na2SO4 or NaH2PO4, pH
of the solution stabilized at a value greater than pH 10, which
facilitates the dissolution of Al(OH)3 into anionic hydroxo-
aluminum species such as Al(OH)4
and Al(OH)52
and the
formation of these species makes occulation and electropreci-
pitation dicult to occur. While in the case of NaCl, pH remains
in the range between 8.3 and 9.3 throughout the experiment. In
this pH range, amorphous aluminum hydroxide (Al(OH)3) is
13370
ARTICLE
precipitated, which has a large surface area that is benecial for
coagulation by adsorption.39
45
4. CONCLUSION
The inuence of supporting electrolyte, initial pH, and current
density on anodic dissolution of pure aluminum during electro-
coagulation process was evaluated. The main conclusions of this
work can be summarized in the following points:
- Potentiodynamic polarization experiments showed that
aluminum corrosion is largely dependent on supporting
electrolyte and initial pH conditions. The presence of NaCl
or Na2SO4 shifted the corrosion potential toward more
negative values, indicating that corrosion of aluminum is
catalyzed by the presence NaCl or Na2SO4. However, in the
presence of NaCl, pitting corrosion occurs at a much lower
potential than that in the presence of Na2SO4. In contrast,
the presence of NaH2PO4 increased the corrosion potential,
which indicates that the presence of NaH2PO4 inhibits the
corrosion of aluminum. EIS and potentiostatic anodic
current transients conrmed that pitting corrosion kinetics
is accelerated by pH increase and the presence NaCl.
Morphological observations proved that large localized
pitting corrosion was clearly observable on the surface of
aluminum plate polarized in the presence of NaCl. However,
in the case of Na2SO4, small uniformly distributed pitting
corrosion was observed. In contrast, the aluminum plate
polarized in the presence of NaH2PO4 was completely
covered with a layer of AlPO4.
- Galvanostatic electrolyses demonstrated that measured con-
centrations of aluminum were slightly higher than theore-
tical values calculated using Faradays law and the gap
between them enlarged with the increase in specic electrical
charge. Super-Faradic excess of dissolved aluminum is
primarily related to the chemical dissolution of aluminum,
which is more signicant at highly alkaline conditions. These
results indicate that the amount of dissolved aluminum is
basically related to pH conditions. Changes of pH during
galvanostatic electrolysis mainly depend on initial pH and
the nature of supporting electrolyte. In the presence of
NaH2PO4, the pH increased continuously until it reached a
value of 11.4. Whereas in the presence of NaCl or Na2SO4,
pH decreased slightly at the beginning and then increased
gradually until it stabilized at 9.3 and 10, respectively.
- For acidic initial pH conditions, pH increases during elec-
trolyses; however, it decreases for solutions with initial pH
higher than 9. These results can be due to the nature of
hydroxo-aluminum species formed during anodic dissolu-
tion of aluminum. In acidic and neutral conditions, it appears
that hydroxide ions formed at the cathode were not com-
pletely involved in the formation of cationic and neutral
hydroxo-aluminum species and the excess of OH
ions
increased the pH of the medium. In contrast, the decrease of
pH in highly alkaline conditions could be attributed to the
consumption of higher amounts of OH
ions to form
anionic hydroxo-aluminum species such as Al(OH)4
and
Al(OH)52
. The stabilization of pH to a value close to 9 for
slightly acid, neutral, and alkaline initial values of pH can be
explained by a buering eect of hydroxo-aluminum species
that balances the quasi-static variation of the concentration
of hydroxyl ions through the formation of monomeric and
polymeric complexes of aluminum hydroxides.
dx.doi.org/10.1021/ie201206d |Ind. Eng. Chem. Res. 2011, 50, 1336213372
Industrial & Engineering Chemistry Research
AUTHOR INFORMATION
Corresponding Author
*Phone: +21675392600. Fax: +21675392421. E-mail: nasr.
bensalah@issatgb.rnu.tn and/or nasr.bensalah@qatar.tamu.edu.
ACKNOWLEDGMENT
The authors acknowledge Texas A&M University at Qatar and
Qatar Foundation for providing partial nancial support to
accomplish this research work.
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