Journal of Hazardous Materials 169 (2009) 1127–1133

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Journal of Hazardous Materials

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Effect of pH and chloride concentration on the removal of hexavalent chromium

in a batch electrocoagulation reactor
M.G. Arroyo, V. Pérez-Herranz ∗ , M.T. Montañés, J. García-Antón, J.L. Guiñón
Departamento de Ingeniería Química y Nuclear, Universidad Politécnica de Valencia, Camino de Vera s/n, 46022 Valencia, Spain

a r t i c l e i n f o a b s t r a c t

Article history: In this work, the effect of pH and chloride ions concentration on the removal of Cr(VI) from wastewater
Received 4 December 2008 by batch electrocoagulation using iron plate electrodes has been investigated. The initial solution pH
Received in revised form 17 April 2009 was adjusted with different concentrations of H2 SO4 . The presence of chloride ions enhances the anode
Accepted 20 April 2009
dissolution due to pitting corrosion. Fe2+ ions formed during the anode dissolution cause the reduction
Available online 3 May 2009
of Cr(VI) to form Cr(III), which are co-precipitated with Fe3+ ions at relatively low pH.
The reduction degree of Cr(VI) to Cr(III) and the solubility of metal hydroxide species (both chromic and
Keywords:
iron hydroxides) depend on pH. At higher concentrations of H2 SO4 , the reduction of Cr(VI) to Cr(III) by
Hexavalent chromium
Electrocoagulation
Fe2+ ions is preferred, but the coagulation of Fe3+ and Cr(III) is favoured at the lower H2 SO4 concentrations.
pH
Chloride ions © 2009 Elsevier B.V. All rights reserved.

1. Introduction tion [12], biosorption [13–15], membrane separation [16–18] and

Chromium salts are used in many industries such as leather
tanning, electroplating, wood preservation, manufacture of dyes,
paper, and fertilizers, industries that employ Cr(VI) as corrosion
inhibitor and industrial operations involving the use of ferrous and
nonferrous metals. These industries generate residues in which
chromium can appear in solution as Cr(III) and Cr(VI) compounds.
The characteristic of these two species differs considerably: com-
pounds of Cr(VI) have been related as very toxic, mainly due to
their confirmed carcinogenic action, whereas Cr(III) is essential for
the maintenance of the metabolism of lipids, glucose and proteins
[1].
Due to the high toxicity of hexavalent chromium, its concen-
tration in industrial effluents is strictly controlled before being
discarded into sewages or rivers, which is a major environmental
issue, affecting every industrialized country in the world [2]. Dis-
charge consents are, however, site specific and are dependent upon
the dilution capabilities of the water body into which the effluent
is discharged [3].
To meet environmental regulations, effluents or water contami-
nated with hexavalent chromium must be treated before discharge.
The elimination of chromium from residual wastewaters is a chal-
lenge for the control of the contamination. Conventional chromium
removal methods include adsorption [4–6], chemical precipitation
[7–9], biological degradation [10], ion exchange [11], solvent extrac-
∗ Corresponding author. Tel.: +34 96 3877632; fax: +34 96 3877639.
E-mail address: vperez@iqn.upv.es (V. Pérez-Herranz).
electrochemical methods [3,19–22]. Electrochemical based meth-
ods allow controlled and rapid reactions, smaller systems become
viable and, instead of using chemicals and micro-organisms, the
systems employ only electrons to facilitate water treatment. Among
the electrochemical methods, electrocoagulation (EC) is a simple,
efficient and economical method for wastewater treatment, as it
offers the possibility to be easily distributed, and require minimum
amount and number of chemicals, thus reducing the amount of
sludge which must be disposed [23]. In this process, robust and
compact instrumentation is easily achievable, and hence, it will
have the potential to replace sophisticated processes that require
large volumes and number of chemicals [24].
Electrocoagulation has been applied for the treatment of
wastewater containing heavy metals [25–29], including hexava-
lent chromium [30–32]. However, only a few authors have focused
on the variables that are crucial to the improvement of the perfor-
mance of this application. In this work, the effect of pH and chloride
ions concentration on the electrocoagulation efficiency in removing
hexavalent chromium from the chromium plating industries using
iron electrodes has been studied.
2. Background
Electrocoagulation is a process consisting of creating metallic
hydroxide flocks within the wastewater by electrodissolution of sol-
uble anodes, usually made of iron or aluminum [33]. The generation
of metallic cations takes place at the anode, due to the electro-
chemical oxidation of the iron or aluminum, whereas at the cathode
the production of H2 typically occurs. The generated gas helps the

0304-3894/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2009.04.089
1128 M.G. Arroyo et al. / Journal of Hazardous Materials 169 (2009) 1127–1133
flotation of flocculated particles, and therefore the process some-
times is named as electroflocculation [34].
EC involves three successive stages [24]:
• Formation of coagulants by electrolytic oxidation of the anode.
• Destabilization of the contaminants, particulate suspension, and
breaking of emulsions.
• Aggregation of the destabilized phases to form flocks.
In the case of the treatment by EC of hexavalent chromium solu-
tions, when a potential difference is applied to the electrodes of the
EC reactor from an external power source, the following electro-
chemical reactions can take place:
• If iron is employed as anode material, its electrochemical oxida-
tion generates Fe2+ ions:
Fe → Fe2+ + 2e−
On the other hand, if the anode potential is sufficiently high,
secondary reactions may occur at the anode surface, such as the
oxidation of H2 O and Cl− ions:
2H2 O → 4H+ + O2 + 4e−
2Cl− → Cl2 + 2e−
Chloride ions can be added to the solution to increase its con-
ductivity for minimizing the energy consumption and to prevent
the passivation of the iron anode by hexavalent chromium, as
Cl− ions catalyze the dissolution of iron by pitting corrosion [35].
Therefore the presence of Cl− ions can improve the removal effi-
ciency of Cr(VI).
• In the cathode, the simultaneous reduction of water and hexava-
lent chromium, in the form of dichromate, can take place:
2H2 O + 2e− → H2 + 2OH−
Cr2 O7 2− + 14H+ + 6e− → 2Cr3+ + 7H2 O
In addition to the electrochemical reactions mentioned previ-
ously, Fe2+ ions produced in the anode, can directly reduce Cr(VI)
to Cr(III) according to the following reaction:
Cr2 O7 2− + 14H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ + 7H2 O
Depending on the solution pH, the generated Fe3+ ions
will immediately undergo further spontaneous reactions to
produce various monomeric and/or polymeric metal hydrox-
ides complexes, such as Fe(OH)3 , Fe(OH)4 − , Fe(H2 O)3 (OH)3 ,
Fe(H2 O)6 3+ , Fe(H2 O)5 (OH)2+ , Fe(H2 O)4 (OH)2 + , Fe2 (H2 O)8 (OH)2 4+
and Fe2 (H2 O)6 (OH)4 2+ [36]. These compounds remain in the aque-
ous stream as a gelatinous suspension, which can remove the
pollutants from wastewater either by complexation or by electro-
static attraction, followed by coagulation. On the other hand, the
increase of the solution pH due to hydroxyl ions which are pro-
duced at the cathode in reaction (5) causes the co-precipitation of
Cr(III) and Fe(III) as Crx Fe1−x (OH)3 between pH 2 and 6 [37], acting
synergistically to remove the pollutants from water. At higher pH,
Cr3+ ions can precipitate as Cr(OH)3 .
In addition, the following physiochemical reactions may also
take place in the EC cell [24]:
• Cathodic reduction of impurities present in wastewater.
• Discharge and coagulation of colloidal particles.
• Electrophoretic migration of the ions in solution.
• Electroflotation of the coagulated particles by O2 and H2 bubbles
produced at the electrodes.
• Reduction of metal ions at the cathode.
• Other electrochemical and chemical processes.
(1)
Fig. 1. Scheme of the experimental arrangement. (1) Power supply, (2) voltmeter,
(3) electrocoagulation reactor, (4) anode and (5) cathode.
Therefore, pH and chloride ions concentration can have a great
(2) influence on the removal efficiency of hexavalent chromium by
(3) electrocoagulation because the reduction of Cr(VI) to Cr(III) by Fe2+
ions is preferred to occur in acidic conditions, but the coagulation of
Fe3+ and Cr(III) is favourable in alkali conditions. On the other hand,
the presence of chloride ions improves the dissolution of iron by pit-
ting corrosion and avoids the electrode passivation. Then the effect
of these two variables on the removal of hexavalent chromium by
electrocoagulation must be optimized.
3. Experimental
Fig. 1 shows a scheme of the experimental arrangement.
(4) Batch electrocoagulation experiments were carried out in a 1 L
(5) reactor using vertically positioned electrodes dipped in the solu-
tion. The anode was made of flat plate iron with dimensions of
140 mm × 8 mm × 3 mm, while the cathode was a flat plate AISI 316
stainless steel with dimensions of 140 mm × 8 mm × 1 mm, both
electrodes having a submerged surface area of 80 cm2 . The elec-
(6) trode spacing was 18 mm. Electrodes were connected to a DC power
supply (GRELCO model GVD 305). Electrocoagulation experiments
were performed at a constant current of 0.5 A. A digital voltmeter
was used to measure the cell voltage.
Electrocoagulation experiments were run for 5 h. Prior to each
experiment, the electrodes were abraded with sand-paper to
remove scale, then treated with a solution of HNO3 10% in order
to reject any effect due to the different prehistory of the elec-
trodes, washed with distilled water, dried and then, the anode
was weighted. Samples were drawn periodically from the solu-
tion. pH was measured using a CRISON micro pH 2000 pH
meter, conductivity was measured using a CRISON micro CM
2200 conductivity meter. Total chromium and iron concentra-
tions were determined by atomic absorption spectrophotometry
on a PerkinElmer model Aanalyst 100 atomic absorption spec-
trophotometer with air–acetylene flame at 428.9 and 372.0 nm
wavelengths, respectively, 0.2 nm spectral bandwidth and operat-
ing current of 10 mA. The concentration of Cr(VI) was determined
by titration with a Fe2+ standard solution. The Cr(III) concentration
was then calculated from the difference between the total Cr and
Cr(VI) concentrations.
After each experiment the anode was cleaned with diluted HNO3
and distilled water in order to remove the oxide layer formed on
the electrode surface during the electrocoagulation process and
weighted. Then, the cleaning solution was analysed by atomic
absorption spectrophotometry as described previously in order
 M.G. Arroyo et al. / Journal of Hazardous Materials 169 (2009) 1127–1133 1129

to determine the amount of iron adhered to the electrode sur-

face.
Wastewater used in the experiments was prepared synthetically
by dissolving analytical grade reagents provided from PANREAC
in distilled water. Electrocoagulation experiments were performed
with 0.05 M solutions of Cr(VI) prepared by dissolving the proper
amount of CrO3 in distilled water. In order to increase the conductiv-
ity of the solution, and to prevent the passivation of the electrodes,
NaCl in concentrations of 0, 0.1, 0.2, 0.5, 0.7, 0.9 and 1.0 g/L was
added to the solution. On the other hand, H2 SO4 in concentrations
of 0, 0.001, 0.01, 0.1 M was used to adjust the initial pH of the solu-
tion. All the experiments were carried out at room temperature
without stirring.

4. Results and discussion

Fig. 2. Progress of the fraction of Cr(VI) reduced to Cr+3 for different concentrations
During EC, many processes of Cr(VI) removal can take place of H2 SO4 and NaCl.
simultaneously: chemical reduction of Cr(VI) to Cr(III) and subse-
quent precipitation of the trivalent chromium hydroxide, cathodic
reduction and adsorption, sweep coagulation, co-precipitation as electrolyte concentration is an effective parameter on the treatment
[Crx Fex−1 ](OH)3 . Cathodic reduction contributes to remove a frac- efficiency of both processes, the reduction of hexavalent chromium
tion of Cr(VI) from solution mainly at the start of the experiment. and its removal by precipitation, especially at low H2 SO4 concen-
In this case, charge loading not only determines the amount of iron trations. In the absence of chloride ions, the reduction of chromium
coagulant produced in the process, but also affects the reduction and its removal are less than 20% due to the partial iron anode passi-
reaction of Cr(VI) to Cr(III). In addition, in the EC reaction unit, the vation, which prevents the generation of Fe2+ and Fe3+ , which cause,
iron electrodes dissolve into solution as ferrous cations that cause respectively, the reduction of Cr(VI) to Cr(III) and the coagulation.
the chemical reduction of Cr(VI) to produce Cr3+ and Fe3+ according
to reaction (6). Thus, chemical reduction of hexavalent chromium is
coupled to EC due to the presence of Fe2+ ions, which play a double
role as a catalyst and a coagulant.
Also, it has been established that the influent pH and the
presence of chloride ions as supporting electrolyte are important
operating factors influencing the performance of EC processes, as
the presence of chloride ions improve the dissolution of iron by
pitting corrosion and avoids the anode passivation, while the reduc-
tion degree of Cr(VI) and the solubility of metal hydroxide species
(both chromic and iron hydroxides) depend on pH, since the reduc-
tion of Cr(VI) to Cr(III) by Fe2+ ions is preferred to occur in acidic
conditions, but the coagulation of Fe3+ and Cr3+ is favourable in
alkali conditions.
Therefore, the effect of pH and supporting electrolyte on the
reduction of Cr(VI) to Cr(III) and its removal by EC using iron plate
electrodes was investigated simultaneously. The variation of the
fraction of Cr(VI) reduced to Cr(III), XCr(VI) , and the fraction of total
Cr removed by precipitation, XtotalCr , versus time are presented in Fig. 3. Progress of the fraction of total Cr removed by precipitation for different
Figs. 2 and 3, respectively, for different concentrations of H2 SO4 and concentrations of H2 SO4 and NaCl.

NaCl.
For a given current density applied to the EC reactor, the reduc-
tion of Cr(VI) to Cr(III) and its removal by EC are dependent on H2 SO4
and Cl− concentrations. As can be seen in Fig. 2, for all concentra-
tions of sulphuric acid and chloride ions, the fraction of hexavalent
chromium reduced to Cr(III), increases with time. After 5 h of EC,
XCr(VI) varies from 15% in absence of chloride ions and 0.001 M
H2 SO4 to 85% at the higher concentrations of Cl− and H2 SO4 . How-
ever, as shown in Fig. 3, the fraction of chromium removed by
precipitation, XtotalCr , remains almost constant over time except for
0.001 M of sulphuric acid and 1 g/L of NaCl, in which case, after the
second hour of operation, XtotalCr is growing rapidly over time due to
the co-precipitation of iron and chromium as a result of the increase
in the pH of the solution. In these last conditions, around 60% of the
initial Cr(VI) present in the solution is removed after approximately
5 h.
The values of XCr(VI) and XtotalCr obtained after 5 h of operation
are presented in Figs. 4 and 5, respectively, for different concentra- Fig. 4. Effect of H2 SO4 and NaCl concentrations on the fraction of Cr(VI) reduced to
tions of H2 SO4 and NaCl. As can be seen in these figures, supporting Cr3+ .
1130 M.G. Arroyo et al. / Journal of Hazardous Materials 169 (2009) 1127–1133

Fig. 5. Effect of H2 SO4 and NaCl concentrations on the fraction of Cr(VI) removed by Fig. 6. Effect of H2 SO4 on the evolution of pH with time. [NaCl] = 1 g/L.
precipitation.

and ferric ions generate various monomeric and polymeric metal

However, when chloride ions are present in the solution both the hydroxides which cause an increase of the solution pH [27].
reduction of Cr(VI) to Cr(III) and their removal are favoured. Figs. 8 and 9 show the changing concentration of iron in solution
For a given NaCl concentration, XCr(VI) increases from 60% for the during EC for different concentrations of H2 SO4 and NaCl, respec-
lower H2 SO4 concentration of 0.001 M to 90% for the higher H2 SO4 tively. The iron concentration in the solution increases over time,
concentration of 0.1 M, while XtotalCr decreases from 60% for the reach a maximum, which depends on the initial H2 SO4 and NaCl
lower H2 SO4 concentration of 0.001 M to 5% for the higher H2 SO4 concentrations, and falls when the solution pH is higher than 3 due
concentration of 0.1 M. Thus, an increase in H2 SO4 concentration to the co-precipitation of Fe3+ /Cr3+ hydroxides between pH 2 and
produces an increase in the fraction of Cr(VI) reduced to Cr(III)
(Fig. 4) and a decrease in the fraction of chromium removed (Fig. 5),
as the chemical reduction of Cr(VI) by Fe2+ ions is favoured at low
pH and the precipitation of Cr3+ /Fe3+ hydroxides is favoured at high
pH. At the higher concentrations of H2 SO4 , although Cr(VI) ions are
reduced to Cr(III), they remain dissolved in water.
Finally, it can be mentioned that in the absence of H2 SO4 and
NaCl the removal of Cr(VI) by EC is not possible, since in these con-
ditions the anode is passivated, there is no generation of Fe2+ ions,
and the reduction of Cr(VI) to Cr(III) and the precipitation of the
Cr3+ /Fe3+ hydroxides do not take place.
The addition of NaCl increases the solution conductivity and pre-
vents the anode passivation. Chloride ions catalyze the dissolution
of the electrode material by the pitting corrosion phenomenon,
which is a type of localized corrosion caused by a high chloride
concentration in the solution [35]. Therefore the presence of NaCl
improves the removal efficiency of Cr(VI) by increasing the avail-
able metal coagulant in solution. However, for NaCl concentrations
Fig. 7. Effect of supporting electrolyte on the evolution of pH with time.
greater than 0.7 g/L, the removal efficiency decreases (Fig. 5) as
[H2 SO4 ] = 0.001 M.
chloride ions increase the solubility of chromium tri-hydroxide and
its effect is stronger than the passivating action of chloride on the
electrode [28].
A typical progress of pH change for various initial concentra-
tions of H2 SO4 and NaCl can be seen in Figs. 6 and 7. Initial pH
values in the range 1–1.5 were obtained. With progress of EC, the
solution pH increases to final values between 3 and 6, depending on
the initial concentrations of H2 SO4 and NaCl. In this pH range, the
co-precipitation of Cr(III) and Fe(III) as Crx Fe1−x (OH)3 takes place
[37]. As can be seen in Fig. 6, for a given concentration of NaCl, the
solution pH reached at the end of the EC process increases with the
decrease of the initial concentration of H2 SO4 , so the higher Cr(VI)
removal efficiencies are obtained at low concentrations of H2 SO4
as shown in Fig. 5. On the other hand, as shown in Fig. 7, for a given
concentration of H2 SO4 , the solution pH does not vary significantly
with the concentration of NaCl, except in the absence of NaCl, in
which case, the solution pH remains almost constant with time,
since in these conditions the anode is passivated and the reactions
that lead to the removal of chromium are inhibited. When chloride Fig. 8. Effect of H2 SO4 on the evolution of the residual iron concentration with time.
ions are added to the solution, the anode dissolution is enhanced, [NaCl] = 1 g/L.
 M.G. Arroyo et al. / Journal of Hazardous Materials 169 (2009) 1127–1133
Fig. 9. Effect of supporting electrolyte on the evolution of the residual iron concen-
tration with time. [H2 SO4 ] = 0.001 M.
6 [37]. For a given H2 SO4 concentration, residual iron in solution is
higher with the concentration of NaCl as shown in Fig. 9, and this
result in a higher solution pH, which helps in precipitating Cr(III)
and Fe3+ as insoluble hydroxides, which is a favourable factor in
improving the fraction of Cr(VI) removed.
At the end of the EC process relatively low residual Fe concen-
tration was obtained, especially at the higher NaCl concentration
and the lower H2 SO4 concentration, as a consequence of the higher
pH reached in these conditions.
The residual concentration of Fe ions in solution can be esti-
mated from the speciation diagram of Fe(III) shown in Fig. 10 [38].
This figure shows the concentration of Fe species in soluble form,
in equilibrium with the amorphous hydroxide. Although the most
stable solid form is goethite for iron, this reaches equilibrium very
slowly, and it is usual to consider amorphous precipitates, since this
form quite rapidly and is much more relevant in practical applica-
tions of coagulants. As can be seen in Fig. 10, the dominant species
in solution changes from Fe3+ to Fe(OH)4 − over a range of more
than 8 pH units, and intermediate species, such as Fe(OH)2 + and
Fe(OH)3 , can represent more than 90% of soluble forms at interme-
diate pH values. These calculations can be affected by the presence
of chloride and sulphate anions, which form complexes with Fe.
However, it has been established that the addition of chloride and
Fig. 10. Speciation diagram of Fe(III) as a function of pH.
1131
sulphate ions to the solution makes only a slight difference to the
solubility equilibrium of Fe, and the magnitude of the increase of
solubility due to the formation of complexes is very small com-
pared with the change of pH [39]. As well as the simple monomeric
hydrolysis products considered above, Fe3+ ions can form a range
of polynuclear species although they do not greatly affect solution
compositions, such as those shown in Fig. 10 [40]. From the stand-
point of coagulation, the total amount of soluble metal species is
important.
The initial increase in the iron concentration over time, shown
in Figs. 8 and 9, is because the pH is initially very low, and the
iron solubility in these conditions is the highest, as can be seen
in the speciation diagram of Fig. 10. The maximum concentration
of iron in the solution is reached when this concentration coin-
cides with the solubility limit at a given pH. From this point, the
solution pH increases and the concentration of iron decreases. The
maximum concentration of iron in the solution, reached at pH 3,
is around 0.7 mg/L (1.25 × 10−5 M), as shown in Figs. 8 and 9; this
value approximately coincides with the solubility of iron at pH 3
shown in Fig. 10.
Once the evolution of pH and the concentration of iron in the
solution have been studied, a possible mechanism for electroco-
agulation of Cr(III) can be proposed. Although the mode of action
of metal coagulants is broadly understood, there are still some
uncertainties, with regard to the nature of the active species and
the role of dissolved salts in water, specially in the case of iron
where there are redox as well as hydrolytic reactions to consider
and the subject becomes quite complex. The mechanisms of action
of prehydrolyzed forms are also by no means fully understood, but
depending on the coagulant dosage, the following situations can
take place [38]:
• At very low coagulant dosage particles remain stable.
• Sufficient dosage of coagulant gives charge neutralisation and
hence coagulation.
• Higher dosage gives charge neutralisation and restabilisation.
• Still higher dosage gives hydroxide precipitate and sweep floccu-
lation.
At the pH reached in the electrocoagulation reactor, between
2 and 5.5, the speciation diagram of Fig. 10 shows that the domi-
nant species in solution are positively charged, and then it is not
possible a simple charge neutralization mechanism to explain the
electrocoagulation of chromium, as Cr3+ ions will be repelled by
the positively charged iron complexes. Therefore, are the coagu-
lant dosage and the composition of the solution, which justifies
that chromium can be eliminated by EC. Solution chemistry has
considerable influence on coagulation by hydrolysing metal ions.
The presence of highly charged anions, such as sulphate, can have
a large effect on hydroxide precipitation. Sulphate can reduce the
positive charge of the precipitate in the acid region, so that large
flocs are formed over a wide pH range [41]. This could facilitate the
adsorption of Cr(III) ions on the amorphous metal hydroxide pre-
cipitate. On the other hand, the great amount of coagulant formed
by electrooxidation of the iron anode would facilitate the process of
sweep flocculation due to extensive hydroxide precipitation. It has
long been recognized that, in many cases, optimal removal of par-
ticles from water is achieved under conditions of rapid hydroxide
precipitation. Although precise mechanism is still not fully under-
stood, it is clear that impurity particles are enmeshed in the growing
precipitate and hence can be removed from water by sedimenta-
tion. This process has become known as sweep flocculation, since
particles are “swept out” of water by an amorphous hydroxide
precipitate. This process generally gives considerably improved par-
ticle removal than when particles are destabilized just by charge
neutralization.
1132 M.G. Arroyo et al. / Journal of Hazardous Materials 169 (2009) 1127–1133
Fig. 11. Effect of NaCl on the fraction of the oxidized iron present in the sludge and
in the solution. [H2 SO4 ] = 0.001 M.
Figs. 11 and 12 present the effect of NaCl on the distribution
of the fraction of Fe in sludge and in solution at the end of the
EC process for 0.001 M H2 SO4 and 0.1 M H2 SO4 , respectively. For
the lowest H2 SO4 concentration of 0.001 M (Fig. 11), the fraction of
total Fe in sludge and in solution remain almost constant with the
concentration of NaCl, while for the highest H2 SO4 concentration
of 0.1 M (Fig. 12), the fraction of total Fe in sludge increases and the
fraction of total Fe in solution decreases with the increase of the
NaCl concentration. On the other hand, for a given concentration of
NaCl, the fraction of total Fe in sludge at the end of the EC process
increases and the fraction of total Fe in solution decreases with
the decrease of the H2 SO4 concentration, since higher final pH is
reached at the lower initial concentration of H2 SO4 . Finally, it can be
mentioned that a fraction of the iron anode oxidized, to complete
the 100%, remains adhered on the electrode as iron oxides. This
fraction of the oxidized iron adhered to the electrode surface is
about 20% for 0.001 M H2 SO4 and 5% for 0.1 M H2 SO4 , and does
not contribute to the EC process.
Fig. 13 shows the effect of H2 SO4 and NaCl concentrations on the
current efficiency obtained at the end of the EC experiments for the
electrochemical dissolution of the iron anode. As can be seen in this
figure, total iron dissolution found from experimentations is higher
than that predicted from Faraday’s law, and current efficiency val-
ues higher than 100% are obtained. Current efficiency relates the
actual amounts of anodic metal dissolution to that expected theo-
Fig. 12. Effect of NaCl on the fraction of the oxidized iron present in the sludge and
in the solution. [H2 SO4 ] = 0.1 M.
Fig. 13. Effect of H2 SO4 and NaCl concentrations on current efficiency for the elec-
trochemical dissolution of the iron anode.
retically from Faraday’s law:
mzF
= (7)
MIt
where  is the current efficiency, m is the electrode mass lost at the
end of the EC process, z is the number of electrons transferred in
the electrode reaction, here for Fe, z = 2, F is the Faraday’s constant
(96,486 C/mol), M is the atomic weight of iron, I is the current passed
and t is the duration time of the EC experiment.
These high values of current efficiency can be due to the com-
bined effect of protons and chloride ions which act synergistically
catalyzing the anode dissolution. In acidic pH the electrode is
attacked by H+ and enhances Fe dissolution:
Fe + 2H+ → Fe2+ + H2 (8)
Also chloride ions catalyze the dissolution of the electrode mate-
rial by pitting corrosion as commented previously. Only in absence
of chloride ions and low H2 SO4 concentrations, the current effi-
ciency was lower than 100%.
5. Conclusions
In this work, the effect of pH and chloride ions concentra-
tion on the removal of hexavalent chromium from wastewater
by batch electrocoagulation using iron plate electrodes has been
investigated. The initial solution pH was adjusted with different
concentrations of H2 SO4 . The removal of hexavalent chromium by
electrocoagulation involves two stages: the reduction of Cr(VI) to
Cr(III) in the cathode or by the Fe2+ ions generated from the oxida-
tion of the iron anode and the subsequent co-precipitation of the
Fe3+ /Cr3+ hydroxides.
At high concentrations of H2 SO4 the reduction of Cr(VI) to Cr(III)
is favoured, but in these conditions there is no precipitation of
chromium due to the low pH values reached in the solution. The
precipitation of Fe3+ /Cr3+ hydroxides takes place at pH higher than
3, these pH values being reached at the lower initial concentrations
of H2 SO4 .
Chloride ions that enhance the anode dissolution by pitting cor-
rosion, which favours the reduction of Cr(VI) to Cr(III) and the
subsequent precipitation of Fe3+ /Cr3+ hydroxides, especially at low
concentrations of H2 SO4 .
High current efficiencies, greater than 100%, are obtained for
the anode oxidation due to the synergistic effect of chloride ions
and protons, which catalyze the anode dissolution, especially at
the higher concentrations of H2 SO4 . However, part of the oxidized
anode remains adhered on the electrode surface in the form of
iron oxides, which reduces the fraction of hexavalent chromium
 M.G. Arroyo et al. / Journal of Hazardous Materials 169 (2009) 1127–1133
removed, as part of the Fe2+ ions generated do not pass to the solu-
tion. This phenomenon occurs mainly at the lower concentrations
of H2 SO4 .
Acknowledgements
M.G. Arroyo is grateful to the CONACYT (México) for a postgradu-
ate grant (Ref.: 206331). This work was supported by the Ministerio
de Ciencia e Innovación, convention no. PET2007 0197 02.
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