Separation and Purification Technology 86 (2012) 248–254

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Separation and Purification Technology

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

Electrocoagulation of heavy metals containing model wastewater using

monopolar iron electrodes
Bassam Al Aji a, Yusuf Yavuz b,⇑, A. Savasß Koparal b
a
Damascus University, Civil Engineering Faculty, Dept. of Environmental Engineering, Syria
b
Anadolu University, Dept. of Environmental Engineering, Turkey

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 performance of batch electrocoagulation (EC) using iron electrodes with monopolar con-
Received 13 July 2011 figuration for simultaneous removal of copper (Cu), nickel (Ni), zinc (Zn) and manganese (Mn) from a
Received in revised form 28 October 2011 model wastewater was investigated. The influences of current density (from 2 to 25 mA/cm2), initial
Accepted 10 November 2011
metal concentration (from 50 to 250 mg/L) and initial pH (3, 5.68, 8.95) on removal efficiency were
Available online 20 November 2011
explored in a batch stirred cell to determine the best experimental conditions.
The results indicated that EC was very efficient to remove heavy metals from the model wastewater
Keywords:
having an initial concentration of 250 mg/L for each metal under the best experimental conditions.
Electrocoagulation
Monopolar electrode configuration
According to initial pH results, high pH values are more suitable for metal removal with EC treatment.
Iron electrode At the current density of 25 mA/cm2 with a total energy consumption of 49 kWh/m3, more than 96%
Wastewater treatment removal value was achieved for all studied metals except Mn which was 72.6%.
Heavy metal removal Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction membrane separation techniques can effectively reduce metal

ions, but their uses were limited due to a number of disadvantages
Industrial wastewaters with heavy metals are directly or indi- such as high material and operational cost, and their operational
rectly discharged increasingly into the environment, especially problems [11]. This drawback, together with the need for low cost
with the rapid development of industries such as metal plating effective treatment, has opened new challenges for water treat-
facilities, mining operations, fertilizer industries, tanneries, batter- ment technologies. Innovative, cheap and effective methods of
ies, paper industries and pesticides, etc., which contain various purifying water for human consumption as well as to clean the
kinds of toxic substances such as alkaline cleaning agents, degreas- industrial wastewater effluents before discharging into any other
ing solvents, oil, fat and heavy metals. Most of the metals such as water systems are needed [6]. The advantages of EC have encour-
copper, nickel, lead and zinc are harmful when they are discharged aged many studies on the use of this technology for the treatment
without treatment, because they are not biodegradable and tend to of several industrial effluents.
accumulate in living organisms, and many heavy metal ions are According to Rajeshwar et al. [12] benefits from using
known to be toxic or carcinogenic [1]. Due to their high toxicity, electrochemical techniques include: environmental compatibility,
industrial wastewaters are strictly regulated and have to be treated versatility, energy efficiency, safety, selectivity, amenability to
before being discharged [2]. automation, and cost effectiveness. In addition to these, the
There has been a serious environmental challenge for the pro- following advantages can be added: electrochemical based systems
duced heavy metal industry, due to pressures from public opinion allow controlled and rapid reactions, smaller systems become
and the numerous environmental regulations imposed. Various viable and instead of using chemicals and micro-organisms, the
techniques have been employed for the treatment of heavy metals, systems employ only electrons to facilitate water/wastewater
such as precipitation, adsorption [3], ion-exchange [4], electroco- treatment. Electrochemical techniques offer the possibility to be
agulation [1,5–8] and ion exchange-assisted membrane separation easily distributed, require minimum amount and number of chem-
[9,10]. Precipitation is most applicable among these techniques icals. Robust and compact instrumentation is very easily
and considered to be the most economical. However, this tech- achievable in electrochemical techniques, and hence, they will
nique produces a large amount of precipitate sludge that requires have the potential to replace sophisticated processes that require
further treatment. Reverse osmosis and ion-exchange and other large volumes and/or number of chemicals, massive containers
that are present in a typical water treatment plant, as it is also de-
picted in the study of Mollah et al. [13].
⇑ Corresponding author. Tel.: +90 222 321 35 50; fax: +90 222 323 95 01. Of the known electrochemical techniques, there is much inter-
E-mail address: [email protected] (Y. Yavuz). est in using (EC) for treatment of wastewater containing heavy

1383-5866/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2011.11.011
 B. Al Aji et al. / Separation and Purification Technology 86 (2012) 248–254 249

metals [7,14,15], phosphate [16], sulfide, sulfate and sulfite ions

[17], boron [18,19], nitrate [20,21], fluorine [22], organic matter (iii) Aggregation of the destabilized phases to form flocs.
from landfill leachate [23], suspended particles [8], and humic Anodic metal ions and hydroxide ions generated at the elec-
acids [24]. Many approaches of EC are used for the treatment of trode surfaces react in the bulk wastewater to form various
industrial wastewater such as paper wastes [25], oil wastes hydroxides and built up polymers.
[26,27], textile dyes wastes [28,29], polymeric wastes [30], chem- In addition, the following physicochemical reactions may also
ical and mechanical polishing wastes [31], phenolic wastes [32]. take place in the EC cell [45]: cathodic reduction of impurities pres-
EC has been found a promising technique in treating urban waste- ent in wastewater, discharge and coagulation of colloidal particles,
water [33], treatment of restaurant wastewater [34,35], treatment electrophoretic migration of the ions in solution, electroflotation of
of potable water [36,37], potato chips wastewater [38], treatment the coagulated particles by O2 and H2 bubbles produced at the
of laundry wastewater [39], olive mill wastewaters [40] and alco- electrodes, reduction of metal ions at the cathode, other electro-
hol distillery wastewater [41]. chemical and chemical processes.
Hence, the development of new treatment methods for efflu- If iron electrodes are used, the generated Fe(aq)3+ ions will
ents bearing heavy metals is an urgent issue. Among the methods immediately undergo further spontaneous reactions to produce
that have recently been studied, EC proved very efficient in remov- corresponding hydroxides and/or polyhydroxides, and the hydro-
ing pollutants such as organic and inorganic matters from the lysis products may form many monomeric ions Fe(OH)3 and/or
industrial wastewaters [42]. In addition, a number of scientific polymeric hydroxy complexes depending on the pH of the aqueous
works have indicated that heavy metals in the free form can be medium and co-precipitate as [M,Fe](OH)3 [46].
successfully removed by EC using aluminum, iron and cast iron According to Moreno-Casillas et al. [47] EC can be considered as
electrodes [43,44]. an accelerated corrosion process that maybe explained by a Pour-
There are few published studies using iron electrodes for the baix diagram. Authors had studied electrocoagulation mechanism
treatment of mixed pollutants. On the contrary, most of the papers for COD removal using iron electrodes. And they had benefited
in literature are dealt with the treatment of single metal. And some from Fe-Pourbaix diagram to explain their results obtained at dif-
papers are investigating the effect of other pollutants on the re- ferent pH values.
moval of a main target pollutant. However, in this study, the mixed Coagulation and EC generate sludge, and additionally EC gener-
metal solution was used in all experiments The target of the pres- ates scum. As an advantageous of EC, it is relatively a low sludge
ent study was to examine the treatability of model wastewater producing technique. Sludge formed by EC tends to be readily set-
containing heavy metals (Cu, Ni, Zn and Mn) by EC using monopo- table and easy to de-water, because it is composed of mainly
lar iron electrodes and to explore the effects of varying operating metallic oxides/hydroxides [48,49]. According to Kushwaha et al.
parameters such as the applied current density, initial pH of solu- [50] sludge and scum generated in EC can be dried and used as a
tion, initial concentration and contact time on heavy metal fuel in the boilers/incinerators, or can be used for the production
removal. of fuel-briquettes. On the other hand, the bottom ash obtained
after incineration of scum and sludge may be blended with clay
with higher ratio of clay to make fire bricks. Few studies have
2. Theory of EC shown that addition of finely divided materials, such as silica, fly
ash, etc. to clays and Portland cement not only increases heat resis-
The EC process involves many chemical and physical mecha- tance of these materials but also improves the microstructure and
nisms [13]. Generally, aluminum or iron is dissolved by anodic dis- compressive strength of cement pastes [51]. Thus, sludge and scum
solution. A range of coagulant species and hydroxides are formed generated by EC treatment of dairy wastewater can be disposed off
which destabilize and coagulate the suspended particles or precip- through chemical and physical fixation [52]. Besides, some
itate and adsorb dissolved contaminants [45]. It is generally ac- researchers have investigated the use of EC sludge for the treat-
cepted that the EC process involves three successive stages [13]: ment of other pollutants. For example, Golder et al. [53] have
(i) Formation of coagulants by electrolytic oxidation of the searched the removal of phosphate from aqueous solutions using
electrode. calcined metal hydroxide sludge wastewater generated from EC.
The main reaction occurring at the metal anode is dissolution: According to the study results [53], calcined electrocoagulated me-
MðsÞ ! MðaqÞnþ þ ne ð1Þ tal hydroxide sludge has been found as an efficient adsorbent for
phosphate removal.
Additionally, water electrolysis occurs at the cathode and
anode:
2H2 OðlÞ þ 2e ! H2 ðgÞ þ 2OH ðcathodic reactionÞ ð2Þ 3. Materials and methods

2H2 OðlÞ ! 4Hþ ðaqÞ þ O2 ðgÞ þ 4e ðanodic reactionÞ ð3Þ To demonstrate the effect of initial metallic pollutants concen-
tration and the time required for their quantitative removal, a
stock solution of 1 L containing 1000 mg for each metal was pre-
(ii) Destabilization of the contaminants, particulate suspension, pared with sulfate salts of Cu, Ni, Zn and Mn. A set of the experi-
and breaking of emulsions. ments were conducted with four different solutions containing
A direct electrochemical reduction of metal cations (Mn+) may the same concentrations of 50, 100, 150 and 250 mg/L of each me-
occur at the cathode surface: tal ion respectively by diluting the stock solution.
M nþ þ ne ! nM 0 ð4Þ Experiments were performed in two stages. In the first stage,
the effect of initial metal concentrations with different current
Furthermore, the hydroxide ions formed at the cathode increase densities on the system performance was investigated. Solutions,
the pH of the wastewater thereby inducing precipitation of metal which were prepared from CuSO45H2O, NiSO47H2O, ZnSO47H2O,
ions as corresponding hydroxides and co-precipitation with MnSO4H2O, were used in the EC setup at different concentrations
hydroxides: (from 50 to 250 mg/L). Experiments were made by using a cylindri-
cal glass cell of 500 mL on a magnetic stirrer (Falc Instruments F60
M nþ þ nOH ! MðOHÞn ðsÞ ð5Þ
model, Italy). Six plates of iron, were installed vertically with a
250 B. Al Aji et al. / Separation and Purification Technology 86 (2012) 248–254

spacer to ensure fixed distance and immersed to a 4 cm depth, 4.1. Effect of current density
were used as electrodes in monopolar mode in the experiments.
The total immersed area of both anode and cathode electrodes In all electrochemical processes, current density is the most
was 100 cm2. The inter-electrode distance was 0.3 cm. The exper- important parameter for controlling the reaction rate within the
imental setup is shown in Fig. 1. The electrode surfaces were rinsed electrochemical reactor. It is well known that the current density
with diluted HNO3 and distilled water and then dried to eliminate determines the production rate of coagulant (amount of Fe2+ ions
the oxides and passivation layers between the experiments. A DC- released by the anode), adjusts also bubble production, its size
power supply (Statron type 3262, Germany) characterized by the and distribution, and hence affects the growth of flocs Fe(OH)2 (s)
ranges 0–5 A for current and 0–80 V for voltage was used to apply or Fe(OH)3 (s) coagulate particles) in the EC reactor with different
different current densities i.e. 2, 5, 8, 15 and 25 mA/cm2. The polar- electrode configurations [54].
ity of the cell was reversed after each experiment to limit the for- Fig. 2 shows the effect of current densities on the removal rate
mation of the passivation layers on the electrodes. To determine of heavy metals, and indicates that the removal rates of all studied
the system performance, samples of 5 mL were taken periodically metals increased, as expected, with increasing current density.
from the reactor at predetermined time intervals (5 or 10 min), Current density studies were accomplished at the original pH val-
and then filtered using Whatman filter paper (Grade 40) to elimi- ues (5.5–5.7) and the final pH values varied between 8.0 and 8.35.
nate sludge formed during electrolysis. The residual heavy metal For the initial Cu concentration of 250 mg/L, the residual concen-
concentrations were determined by ICP-OES (Varian 720 ES model, trations were 7.9, 2.9 and 2.15 mg/L at the current densities of 8,
Australia). 15 and 25 mA/cm2, respectively after 40 min EC treatment as
In the second stage, the effect of initial pH on heavy metal re- shown in Fig. 2(a). Fig. 2(b) shows that the residual Ni concentra-
moval was investigated with initial metal concentrations of tions were 58.5, 17.25 and 11.00 mg/L after 40 min EC treatment
150 mg/L. The procedure in this stage was similar as the first stage. at the current densities of 8, 15 and 25 mA/cm2, respectively, for
pH of the solutions was adjusted by adding either 0.5 N NaOH or the initial Ni concentration of 250 mg/L. As given in Fig. 2(c), initial
0.5 N H2SO4. pH and conductivity of solutions were measured by Zn concentrations of 250 mg/L were reduced to 52.5, 10.55, and
a pH meter (Thermo-Orion 420 A model, USA) and a conductivity 6.4 mg/L after 40 min EC treatment at the current densities of 8,
meter (WTW Cond 720, Germany). All runs were performed at 15 and 25 mA/cm2, respectively. Similarly, initial Mn concentration
the laboratory temperature with a stirring speed of 200 rpm. of 250 mg/L were decreased to 104, 100.5, 82.5 mg/L after 40 min
Removal efficiency was calculated as follows: EC treatment at the current densities of 8, 15 and 25 mA/cm2,
respectively as seen in Fig. 2(d).
ðC 0  C t Þ Variation of removal efficiency values with time for heavy met-
Removal efficiency;% ¼  100 ð6Þ
C0 als and total energy consumption values as a function of current
density are given in Fig. 3. Studies given in Fig. 3(a and b) were
where C0 and Ct are heavy metal concentrations for each heavy me-
realized at the same initial concentration of 250 mg/L with the cur-
tal at times 0 and t.
rent densities of 15 and 25 mA/cm2, respectively. All heavy metals
had similar trend for treatment. However, EC system was more
4. Results and discussions successful in less time periods at the higher current density. For
example, after 10 min EC treatment, removal efficiency values of
The EC process is affected by several operating parameters, such 87.28, 41, 39.4 and 42.2% were obtained at the current density of
as initial concentrations, current density, initial pH and contact 15 mA/cm2, whereas those were 90.8, 59.2, 63.6 and 66.4% at the
time. In this study, all these parameters were explored in order current density of 25 mA/cm2 for Cu, Mn, Zn and Ni, respectively.
to evaluate a treatment technology for Cu, Ni, Zn and Mn removal According to Fig. 3(a and b) the removal rates of Cu were higher
from a model wastewater. than other metals studied. Only after 20 min EC treatment
In the first stage, experimental studies were carried out at the 98.32% Cu removal was achieved at the current density of
different current densities of 2, 5, 8, 15 and 25 mA/cm2, with differ- 25 mA/cm2 as shown in Fig. 3(b). It can be explained by additional
ent initial metal concentrations (50, 100, 150 and 250 mg/L) at the partial removal of Cu by direct electroreduction at the cathode or
original pH (5.5–5.7) of the solutions. by electroless deposition. Additionally, Ni and Zn exhibited very
For the second stage of experiments, studies were carried out at similar trend for all runs (Fig. 3(a and b)). These two metals had
different initial pHs of 3, 5.68 and 8.95 at the current density of more times to reach high removal efficiency values in comparison
25 mA/cm2 and initial metal concentration of 150 mg/L. to Cu. Although Mn removal was lower than the other metals stud-
ied, after 50 min EC treatment, removal efficiency value of 72.6%
was reached at the current densities of 25 mA/cm2.
Electrochemical reactor Besides, energy consumption is directly related with the current
density as also seen in Fig. 3(c). Because model wastewater is a
+ - pH meter mixture of four different heavy metals, energy consumption values
Multimeter
Electrode represent total energy consumed to remove all metals simulta-
connections neously. Total energy consumption was 49 kWh/m3 to gain more
than 96% removal value for Cu, Ni and Zn removals and 72.6% Mn
Sacrificial iron removal at the current density of 25 mA/cm2. Using the current
electrodes average electrical energy price in Turkey of €0.07 kWh1 the cost
of energy consumed per m3 of treated water is €3.43.
+-+-+ - Model solution
4.2. Effect of initial concentration
Power supply

EC treatment for initial concentrations of 50, 100, 150 and

Magnetic stirrer 250 mg/L were tested. Cumulative removals of heavy metals from
solution progress with EC. Initial concentrations from 50 to
Fig. 1. Experimental setup used in the studies. 250 mg/L of Cu, Zn, Ni and Mn did not influence the removal rates,
 B. Al Aji et al. / Separation and Purification Technology 86 (2012) 248–254 251

a b
300 300

Residual Cu conc., mg/L

Residual Ni conc., mg/L

250 8 mA/cm2 250 8 mA/cm2
15 mA/cm2 15 mA/cm2
200 200
25 mA/cm2 25 mA/cm2
150 150

100 100

50 50

0 0
0 1 2 3 4 0 1 2 3 4
Charge, Ah/L Charge, Ah/L

c 300 d 300

Residual Mn conc., mg/L

Residual Zn conc., mg/L

250 8 mA/cm2 250 8 mA/cm2

15 mA/cm2 15 mA/cm2
200 200
25 mA/cm2 25 mA/cm2
150 150

100 100

50 50

0 0
0 1 2 3 4 0 1 2 3 4
Charge, Ah/L Charge, Ah/L

Fig. 2. Effect of current densities on the residual concentrations of heavy metals (C0 = 250 mg/L): (a) Cu, (b) Ni, (c) Zn, and (d) Mn.

a b
100 100
Removal efficiency, %

Removal efficiency, %

80 80

60 60

40 40
Cu Mn Cu Mn
20 20
Zn Ni Zn Ni
0 0
0 10 20 30 40 0 10 20 30 40 50
Time, min Time, min

c
Energy consumption, kWh/m 3

50

i= 15 mA/cm2
40
i= 25 mA/cm2
30

20

10

0
0 10 20 30 40 50
Time, min

Fig. 3. Variation of removal efficiency values with time for heavy metals: (a) C0 = 250 mg/L, i = 15 mA/cm2, (b) C0 = 250 mg/L, i = 25 mA/cm2 and (c) total energy consumption
values as a function of current density.

whereas higher initial concentrations caused higher removal rates studies were realized at the original pH values (5.5–5.7) and the
of heavy metals. Fig. 4 shows the variations of Cu, Ni, Zn and Mn final pH values varied between 8.09 and 8.34. All graphics from
concentrations for different initial concentrations as a function of Fig. 4(a–d) for each metal exhibited a logical trend related with
time at the current density of 8 mA/cm2. Initial concentration time depending on their initial metal concentrations. Certainly,
252 B. Al Aji et al. / Separation and Purification Technology 86 (2012) 248–254

a 1 b 1
50 mg/L 50 mg/L
0.8 0.8 100 mg/L
100 mg/L
150 mg/L 150 mg/L
0.6 0.6
Ct/Co

Ct/Co
250 mg/L 250 mg/L
0.4 0.4

0.2 0.2

0 0
0 10 20 30 40 0 10 20 30 40
Time. min Time. min

c 1 d 1
50 mg/L 50 mg/L
0.8 100 mg/L 0.8 100 mg/L
150 mg/L 150 mg/L
0.6 0.6

Ct/Co
Ct/Co

250 mg/L 250 mg/L

0.4 0.4

0.2 0.2

0 0
0 10 20 30 40 0 10 20 30 40

Time. min Time. min

Fig. 4. Effect of initial concentration on the removal efficiency of heavy metals (i = 8 mA/cm2): (a) Cu, (b) Ni, (c) Zn and (d) Mn.

for higher concentrations longer time for removal is needed, but So, it can be said in general that the removal of metals fits well
higher initial concentrations were reduced significantly in rela- with the first-order kinetic model at high metal concentrations.
tively less time than lower concentrations. For instance, correlation coefficients of Ni were calculated as
According to Fig. 4, no direct correlations exist between each 0.8878, 0.9296, 0.9524 and 0.9765 for initial Ni concentrations of
metal concentration and removal efficiency. The EC treatment is 50, 100, 150 and 250 mg/L, respectively. On the other hand, when
more effective at the beginning of the process when the concentra- the first-order rate constants (k) of different heavy metals for a gi-
tion is higher than at the end of the operation when the concentra- ven concentration are investigated in horizontal order, it can be
tion is relatively lower. Fig. 4 shows that after 40 min EC treatment seen that k values are decreasing from Cu to Mn, also comply with
at the current density of 8 mA/cm2, 1.9, 2.55, 4 and 7.90 mg/L for the removal results. As an example, k values are 0.083, 0.0347,
Cu (Fig. 4(a)), 1.95, 7.53, 10.2 and 58.5 mg/L for Ni (Fig. 4(b)), 2.1, 0.0368 and 0.0308 min1 for Cu, Ni, Zn and Mn, respectively for ini-
5.18, 11.35 and 52.5 mg/L for Zn (Fig. 4(c)) and 13, 24.93, 52 and tial metal concentration of 250 mg/L. These results, at the same
104 mg/L for Mn (Fig. 4(d)) were achieved for the initial metal con- time, mean that Cu can be removed 2.39, 2.25 and 2.69 times faster
centrations of 50, 100, 150 and 250 mg/L, respectively. in comparison to Ni, Zn and Mn, respectively.
Additionally, electrical conductivity of the solution was moni-
tored during the EC treatment in one study performed at the initial 4.3. Effect of initial pH
concentration of 150 mg/L (for each metal), current density
of 25 mA/cm2 and original pH. The initial electrical conductivity It has been established that the influent pH is an important
of 1467 lS/cm decreased to the final electrical conductivity of operating factor influencing the performance of the EC process
520 lS/cm at the end of the experiment (40 min). Reduction in [55]. Generally, the pH of the medium changes during the process
the electrical conductivity value generally complies with the initial as also observed by other investigators and this variation depends
concentration study results. on the type of electrode and initial pH. The final pH was 8.02, 8.30
First order kinetic model was applied to the results obtained. and 11 for the initial pH of 3, 5.68 (original pH) and 8.95, respec-
Cu, Ni and Zn removal kinetic fitted well; however, Mn removal tively. In the current density, initial concentration and initial pH
did not fit with the kinetic model very much as also seen in Table studies, pH was observed to increase during the reactive phase,
1. According to the Table 1, correlation coefficients (R2) for each then to stabilize at pH close to 8–11 depending on the initial pH
metal studied increase with increasing initial metal concentration. value as also referred by Yavuz et al. [49]. This increase in pH

Table 1
First order rate constants for different initial concentration of heavy metals (i = 8 mA/cm2).

Concent. (mg/L) Cu Ni Zn Mn
k (min1) R2 k (min1) R2 k (min1) R2 k (min1) R2
50 0.0943 0.8813 0.0947 0.8878 0.0895 0.9225 0.0408 0.5217
100 0.1028 0.9304 0.0734 0.9296 0.0772 0.9925 0.0423 0.6398
150 0.1024 0.9201 0.0607 0.9524 0.0594 0.9620 0.0281 0.8909
250 0.083 0.9753 0.0347 0.9765 0.0368 0.9821 0.0308 0.9079
 B. Al Aji et al. / Separation and Purification Technology 86 (2012) 248–254 253

can be explained by the occurrence of water electrolysis resulting 120

in hydrogen evolution and production of OH ions. The relative

Removal efficiency, %
stability of pH afterwards could be probably due to the formation 100
of the insoluble Fe(OH)3 flocs and the rest metal hydroxides.
80
To see the effect of initial pH on the removal efficiency, initial
pH of 3, 5.68 and 8.95 was studied. As an example, variations of 60
Cu removal efficiency values with initial pH are given in Fig. 5.
According to this figure, best result was obtained at the original 40
pH. Fig. 5 also shows that 15 min EC treatment is enough to have
20
more than 97% Cu removal value, whereas it takes 25 min to reach
the same removal value for the initial pH of 8.95. On the other 0
hand, 94.7% Cu removal value was obtained after 45 min EC treat- pH= 3 pH= 5,68 pH= 8,95
ment for the initial pH of 3. Therefore, pH adjustment for better Cu
Cu Zn Ni Mn
removal seem does not necessary if solution contain only Cu.
The removal efficiency values for all heavy metals studied as a Fig. 6. Variation of removal efficiency with initial pH (initial concentration for each
function of the initial pH for 45 min EC treatment are demon- metal = 150 mg/L, i = 25 mA/cm2, t = 45 min).
strated in Fig. 6. As shown in this figure, removal efficiencies in-
crease generally at high pH values, because the majority of iron alone and a mixed of these metals and found a linear decrease in
complexes (coagulants) are formed at these values. metal concentrations with time except Cr. They have indicated that
As aforementioned, natural pH of the solutions was initial pH, metal removal from mixed solution is harder than single metal
except studies that the effect of initial pH was investigated. There- solution for all metals studied. They have reached a total metal re-
fore, while initial pH was from 5.5 to 5.7, final pH varied be- moval for Zn, Cu and Ni metals like us. However, we used iron elec-
tween 8.0 and 8.35. For pH value of 4 < pH < 7, iron undergoes trodes different from their study. In another study performed by
hydrolysis and Fe(III) hydroxide begins to precipitate as floc with Hanay and Hasar [5], effect of sulfate and chloride anions on Cu,
yellowish color. For pH 6 < pH < 9, precipitation of Fe(III) hydroxide Zn and Mn removal has been examined. According to their results,
continues, and Fe(II) hydroxide precipitation also occurs present- electrocoagulation using aluminum electrode is more successful
ing a dark green floc. The pH is in the range of 7–8 for minimum for specially Cu and Zn metals, whereas system shows a limited
solubility of Fe(OH)n. EC floc is formed due to the polymerization performance for Mn removal. Similar results for these three metals
of iron oxyhydroxides [47]. In this case, conditions throughout were obtained in the present work. Adhoum et al. [6] have studied
the electrochemical cell are not stable, and concentrations, species a model and real wastewater and also found that Cu and Zn re-
and pH vary as it may be illustrated using Fe-Pourbaix diagram. On moval rate is faster than Cr. They indicated that 5 min is enough
the other hand, when the Pourbaix diagrams are investigated for to reach admissible limit for Cu and Zn, whereas it is 20 min for Cr.
the metals studied (Cu, Ni, Zn and Mn) in this work, followings
can be mentioned: According to the Cu-Pourbaix diagram, cupper
5. Conclusions
is solid in the form of Cu(OH)2 at pH approximately >4.5 until pH
14. Nickel is also solid in Ni(OH)2 form at pH approximately >6
In this work, EC treatment using iron sacrificial electrodes for a
according to its Pourbaix diagram. Zn-Pourbaix diagram shows
model wastewater containing Cu, Ni, Zn and Mn heavy metals
that zinc is solid as ZnO at pH between 7 and 14. And finally,
were investigated. The effects of current density, initial metal con-
manganese is solid as Mn(OH)2 from pH 7.5 to 13 according
centration and initial pH on the removal efficiency were examined
to the Mn-Pourbaix diagram. Consequently, it can be concluded
in a parallel plate electrochemical reactor. An evaluation using
that all chemicals were desirable form for good EC performance
Pourbaix diagrams for working electrode and studied metals were
with respect to pH values measured during the experimental stud-
also realized.
ies and Pourbaix diagrams for working electrode and heavy metals.
In the study, at the current density of 25 mA/cm2 with a total
In some literature studies electrocoagulation of mixed metal
energy consumption of 49 kWh/m3, more than 96% removal effi-
solution [1,5] and electroplating wastewater [6] has been investi-
ciency was obtained for Cu, Ni and Zn, whereas it was 72.6% for
gated using aluminum electrodes. According to Heidmann and Cal-
Mn. This means at the same time that the cost of energy consumed
mano [1], metals are removed by direct reduction at the cathode
per m3 of treated water is €3.43 when the current average electri-
surface, as hydroxides by the hydroxyl ions formed at the cathode
cal energy price in Turkey of €0.07 kWh1 is taken into account.
via water electrolysis and by co-precipitation with aluminium
According to the results, EC using monopolar iron electrodes is a
hydroxides. The authors have studied Zn, Cu, Ni, Ag and Cr metals
convenient route for effective removal of heavy metals from a
model wastewater and achieves faster removal of pollutants in
100 comparison to chemical coagulation, where several hours are
needed and adsorption on activated carbon. Using both the same
Removal efficiency, %

80 model solution and the electrochemical system in bipolar electrode

configuration can be employed to comparison purposes for future
60
studies.
40
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