Journal of Hazardous Materials 169 (2009) 11271133

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

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

in a batch electrocoagulation reactor

M.G. Arroyo, V. Prez-Herranz , M.T. Montans,

J. Garca-Antn, J.L. Guinn
Departamento de Ingeniera Qumica y Nuclear, Universidad Politcnica de Valencia, Camino de Vera s/n, 46022 Valencia, Spain

a r t i c l e

i n f o

Article history:
Received 4 December 2008
Received in revised form 17 April 2009
Accepted 20 April 2009
Available online 3 May 2009
Keywords:
Hexavalent chromium
Electrocoagulation
pH
Chloride ions

a b s t r a c t
In this work, the effect of pH and chloride ions concentration on the removal of Cr(VI) 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 presence of chloride ions enhances the anode
dissolution due to pitting corrosion. Fe2+ ions formed during the anode dissolution cause the reduction
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
iron hydroxides) depend on pH. At higher concentrations of H2 SO4 , the reduction of Cr(VI) to Cr(III) by
Fe2+ ions is preferred, but the coagulation of Fe3+ and Cr(III) is favoured at the lower H2 SO4 concentrations.

1. Introduction
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: compounds of Cr(VI) have been related as very toxic, mainly due to
their conrmed 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 concentration in industrial efuents is strictly controlled before being
discarded into sewages or rivers, which is a major environmental
issue, affecting every industrialized country in the world [2]. Discharge consents are, however, site specic and are dependent upon
the dilution capabilities of the water body into which the efuent
is discharged [3].
To meet environmental regulations, efuents or water contaminated with hexavalent chromium must be treated before discharge.
The elimination of chromium from residual wastewaters is a challenge for the control of the contamination. Conventional chromium
removal methods include adsorption [46], chemical precipitation
[79], 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. Prez-Herranz).
0304-3894/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2009.04.089

2009 Elsevier B.V. All rights reserved.

tion [12], biosorption [1315], membrane separation [1618] and

electrochemical methods [3,1922]. Electrochemical based methods 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,
efcient 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 [2529], including hexavalent chromium [3032]. However, only a few authors have focused
on the variables that are crucial to the improvement of the performance of this application. In this work, the effect of pH and chloride
ions concentration on the electrocoagulation efciency 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 ocks within the wastewater by electrodissolution of soluble anodes, usually made of iron or aluminum [33]. The generation
of metallic cations takes place at the anode, due to the electrochemical oxidation of the iron or aluminum, whereas at the cathode
the production of H2 typically occurs. The generated gas helps the

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M.G. Arroyo et al. / Journal of Hazardous Materials 169 (2009) 11271133

otation of occulated particles, and therefore the process sometimes is named as electroocculation [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 ocks.
In the case of the treatment by EC of hexavalent chromium solutions, when a potential difference is applied to the electrodes of the
EC reactor from an external power source, the following electrochemical reactions can take place:
If iron is employed as anode material, its electrochemical oxidation generates Fe2+ ions:
Fe Fe2+ + 2e

(1)

On the other hand, if the anode potential is sufciently high,

secondary reactions may occur at the anode surface, such as the
oxidation of H2 O and Cl ions:
2H2 O 4H+ + O2 + 4e

(2)

2Cl Cl2 + 2e

(3)

Chloride ions can be added to the solution to increase its conductivity 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 efciency of Cr(VI).
In the cathode, the simultaneous reduction of water and hexavalent chromium, in the form of dichromate, can take place:
2H2 O + 2e H2 + 2OH

(4)

Cr2 O7 2 + 14H+ + 6e 2Cr3+ + 7H2 O

(5)

In addition to the electrochemical reactions mentioned previously, 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

(6)

Depending on the solution pH, the generated Fe3+ ions

will immediately undergo further spontaneous reactions to
produce various monomeric and/or polymeric metal hydroxides 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 aqueous stream as a gelatinous suspension, which can remove the
pollutants from wastewater either by complexation or by electrostatic attraction, followed by coagulation. On the other hand, the
increase of the solution pH due to hydroxyl ions which are produced at the cathode in reaction (5) causes the co-precipitation of
Cr(III) and Fe(III) as Crx Fe1x (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.
Electrootation 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.

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

inuence on the removal efciency of hexavalent chromium by
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 pitting 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.
Batch electrocoagulation experiments were carried out in a 1 L
reactor using vertically positioned electrodes dipped in the solution. The anode was made of at plate iron with dimensions of
140 mm 8 mm 3 mm, while the cathode was a at 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 electrode 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 electrodes, washed with distilled water, dried and then, the anode
was weighted. Samples were drawn periodically from the solution. 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 concentrations were determined by atomic absorption spectrophotometry
on a PerkinElmer model Aanalyst 100 atomic absorption spectrophotometer with airacetylene ame at 428.9 and 372.0 nm
wavelengths, respectively, 0.2 nm spectral bandwidth and operating 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) 11271133

1129

to determine the amount of iron adhered to the electrode surface.

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 conductivity 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 solution. All the experiments were carried out at room temperature
without stirring.

4. Results and discussion

During EC, many processes of Cr(VI) removal can take place
simultaneously: chemical reduction of Cr(VI) to Cr(III) and subsequent precipitation of the trivalent chromium hydroxide, cathodic
reduction and adsorption, sweep coagulation, co-precipitation as
[Crx Fex1 ](OH)3 . Cathodic reduction contributes to remove a fraction of Cr(VI) from solution mainly at the start of the experiment.
In this case, charge loading not only determines the amount of iron
coagulant produced in the process, but also affects the reduction
reaction of Cr(VI) to Cr(III). In addition, in the EC reaction unit, the
iron electrodes dissolve into solution as ferrous cations that cause
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 inuent pH and the
presence of chloride ions as supporting electrolyte are important
operating factors inuencing 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 reduction degree of Cr(VI) and the solubility of metal hydroxide species
(both chromic and iron hydroxides) depend on pH, since the reduction 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
Figs. 2 and 3, respectively, for different concentrations of H2 SO4 and
NaCl.
For a given current density applied to the EC reactor, the reduction 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 concentrations 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 . However, 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 concentrations of H2 SO4 and NaCl. As can be seen in these gures, supporting

Fig. 2. Progress of the fraction of Cr(VI) reduced to Cr+3 for different concentrations
of H2 SO4 and NaCl.

electrolyte concentration is an effective parameter on the treatment

efciency of both processes, the reduction of hexavalent chromium
and its removal by precipitation, especially at low H2 SO4 concentrations. In the absence of chloride ions, the reduction of chromium
and its removal are less than 20% due to the partial iron anode passivation, which prevents the generation of Fe2+ and Fe3+ , which cause,
respectively, the reduction of Cr(VI) to Cr(III) and the coagulation.

Fig. 3. Progress of the fraction of total Cr removed by precipitation for different

concentrations of H2 SO4 and NaCl.

Fig. 4. Effect of H2 SO4 and NaCl concentrations on the fraction of Cr(VI) reduced to
Cr3+ .

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M.G. Arroyo et al. / Journal of Hazardous Materials 169 (2009) 11271133

Fig. 5. Effect of H2 SO4 and NaCl concentrations on the fraction of Cr(VI) removed by
precipitation.

However, when chloride ions are present in the solution both the
reduction of Cr(VI) to Cr(III) and their removal are favoured.
For a given NaCl concentration, XCr(VI) increases from 60% for the
lower H2 SO4 concentration of 0.001 M to 90% for the higher H2 SO4
concentration of 0.1 M, while XtotalCr decreases from 60% for the
lower H2 SO4 concentration of 0.001 M to 5% for the higher H2 SO4
concentration of 0.1 M. Thus, an increase in H2 SO4 concentration
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 conditions 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 prevents 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 efciency of Cr(VI) by increasing the available metal coagulant in solution. However, for NaCl concentrations
greater than 0.7 g/L, the removal efciency decreases (Fig. 5) as
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 concentrations of H2 SO4 and NaCl can be seen in Figs. 6 and 7. Initial pH
values in the range 11.5 were obtained. With progress of EC, the
solution pH increases to nal 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 Fe1x (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 efciencies 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 signicantly
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
ions are added to the solution, the anode dissolution is enhanced,

Fig. 6. Effect of H2 SO4 on the evolution of pH with time. [NaCl] = 1 g/L.

and ferric ions generate various monomeric and polymeric metal

hydroxides which cause an increase of the solution pH [27].
Figs. 8 and 9 show the changing concentration of iron in solution
during EC for different concentrations of H2 SO4 and NaCl, respectively. The iron concentration in the solution increases over time,
reach a maximum, which depends on the initial H2 SO4 and NaCl
concentrations, and falls when the solution pH is higher than 3 due
to the co-precipitation of Fe3+ /Cr3+ hydroxides between pH 2 and

Fig. 7. Effect of supporting electrolyte on the evolution of pH with time.

[H2 SO4 ] = 0.001 M.

Fig. 8. Effect of H2 SO4 on the evolution of the residual iron concentration with time.
[NaCl] = 1 g/L.

M.G. Arroyo et al. / Journal of Hazardous Materials 169 (2009) 11271133

Fig. 9. Effect of supporting electrolyte on the evolution of the residual iron concentration 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 concentration 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 estimated from the speciation diagram of Fe(III) shown in Fig. 10 [38].
This gure 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 applications 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 intermediate 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 compared 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 standpoint 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 coincides 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 (1.25 105 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 electrocoagulation 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.
Sufcient dosage of coagulant gives charge neutralisation and
hence coagulation.
Higher dosage gives charge neutralisation and restabilisation.
Still higher dosage gives hydroxide precipitate and sweep occulation.
At the pH reached in the electrocoagulation reactor, between
2 and 5.5, the speciation diagram of Fig. 10 shows that the dominant 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 coagulant dosage and the composition of the solution, which justies
that chromium can be eliminated by EC. Solution chemistry has
considerable inuence 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
ocs are formed over a wide pH range [41]. This could facilitate the
adsorption of Cr(III) ions on the amorphous metal hydroxide precipitate. On the other hand, the great amount of coagulant formed
by electrooxidation of the iron anode would facilitate the process of
sweep occulation due to extensive hydroxide precipitation. It has
long been recognized that, in many cases, optimal removal of particles from water is achieved under conditions of rapid hydroxide
precipitation. Although precise mechanism is still not fully understood, it is clear that impurity particles are enmeshed in the growing
precipitate and hence can be removed from water by sedimentation. This process has become known as sweep occulation, since
particles are swept out of water by an amorphous hydroxide
precipitate. This process generally gives considerably improved particle removal than when particles are destabilized just by charge
neutralization.

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M.G. Arroyo et al. / Journal of Hazardous Materials 169 (2009) 11271133

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.

Fig. 13. Effect of H2 SO4 and NaCl concentrations on current efciency for the electrochemical dissolution of the iron anode.

retically from Faradays law:

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 nal 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 efciency obtained at the end of the EC experiments for the
electrochemical dissolution of the iron anode. As can be seen in this
gure, total iron dissolution found from experimentations is higher
than that predicted from Faradays law, and current efciency values higher than 100% are obtained. Current efciency 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.

=

mzF
MIt

(7)

where  is the current efciency, 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 Faradays 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 efciency can be due to the combined 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 material by pitting corrosion as commented previously. Only in absence
of chloride ions and low H2 SO4 concentrations, the current efciency was lower than 100%.
5. Conclusions
In this work, the effect of pH and chloride ions concentration 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 oxidation 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 corrosion, 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 efciencies, 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) 11271133

removed, as part of the Fe2+ ions generated do not pass to the solution. This phenomenon occurs mainly at the lower concentrations
of H2 SO4 .
Acknowledgements
M.G. Arroyo is grateful to the CONACYT (Mxico) for a postgraduate grant (Ref.: 206331). This work was supported by the Ministerio
de Ciencia e Innovacin, convention no. PET2007 0197 02.
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