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Journal of Electroanalytical Chemistry 731 (2014) 145152

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Journal of Electroanalytical Chemistry


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

Active chlorine species electrogenerated on Ti/Ru0.3Ti0.7O2 surface:


Electrochemical behavior, concentration determination and their
application
Dayanne Chianca de Moura a, Cynthia Krzia Costa de Arajo a, Carmem L.P.S. Zanta b, Ricardo Salazar c,
Carlos Alberto Martnez-Huitle a,
a
Federal University of Rio Grande do Norte, Institute of Chemistry, Lagoa Nova CEP 59.072-970, RN, Brazil
b
Institute of Chemistry and Biotechnology, Federal University of Alagoas, CEP 57072-970, Macei-Al, Brazil
c
Universidad de Santiago de Chile, Departamento de Ciencias del Ambiente, Facultad de Qumica y Biologa, Av. Libertador B. OHiggins 3363, Santiago, Chile

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

Article history: In the present work, the evolution of chlorine-related species was investigated by cyclic voltammetric,
Received 17 June 2014 polarization and electrolytic analyses in order to establish whether their formation and consumption
Received in revised form 5 August 2014 related to either chemical or electrochemical reactions. This study was performed at Ti/Ru0.3Ti0.7O2 anode
Accepted 6 August 2014
by adding known concentrations of Cl in solution by applying different current densities. The results
Available online 23 August 2014
demonstrated that dissolved Cl2, HClO, ClO, chlorite, chlorine dioxide and chlorate can be electrochem-
ically formed. The concentration trends of dissolved Cl2 and chlorite indicated that the electrochemical
Keywords:
route was responsible for their presence in the bulk solution, and these active species are responsible
Active chlorine
DSA anode
of the formation of the other chlorine species. By using Ti/Ru0.3Ti0.7O2 as anode, the efcient treatment
Water treatment of real efuent was favored by applying 25, 50 and 75 mA cm2 in presence of NaCl (1.25 g L1), achieving
Oxidants determination higher elimination of organic matter, ranging from 80% to 86%. Results clearly have demonstrated that
Electrochemical behavior the oxygen evolution inhibition depends predominantly on the specic electrochemical species formed
in association with pH, nature of electrode and applied current.
2014 Elsevier B.V. All rights reserved.

1. Introduction technologies such as electro-Fenton and photoassisted systems like


photoelectro-Fenton and photoelectrocatalysis has also received
As environmental regulations become stringent, new and novel great attention [3].
processes for efcient treatment of various kinds of wastewater at The electrochemical treatment by direct or indirect approaches,
relatively low operating cost are needed. The decontamination and is based on the elimination of pollutants directly on the anode sur-
disinfection of waters by means of direct or integrated electro- face, via production of dOH [911] or/and other oxidants, such as
chemical processes are being considered as a very promising alter- chlorine, (per)bromate, persulfate, ozone, hydrogen peroxide, per-
native due to the signicant improvement of the electrode carbonate, and others, directly on-site using only water, salt, and
materials and the coupling with low-cost renewable energy energy. In the case of active chlorine, the interest in this oxidant
sources [1]. is based on the ubiquitous presence of chloride ions in a certain
The application of electrochemical technologies to environmen- number of efuents and natural waters, making possible the
tal pollution abatement has been the topic of several books and involvement of active chlorine during electrochemical treatment;
authoritative reviews [29]. The main electrochemical procedures and the chemistry and electrochemistry of higher oxidation states
utilized for the remediation of wastewaters are electrocoagulation, for chlorine close to neutral pH [6,7]. However, the addition of
electroreduction, electrootation, electrochemical oxidation and electrolyte is inevitable if the wastewater sample is not sufciently
indirect electro-oxidation with active oxidants, so-called mediated conducting. In many cases, the electrolyte is deliberately added to
electrochemical oxidation. Recently, the treatment by emerging enhance the degradation process and several studies have
employed NaCl as the salt to increase the conductivity [6,7,9].
Several mixed metal oxide electrodes have been used in the
Corresponding author. electrochemical wastewater treatment by indirect electrochemical
E-mail address: carlosmh@quimica.ufrn.br (C.A. Martnez-Huitle).

http://dx.doi.org/10.1016/j.jelechem.2014.08.008
1572-6657/ 2014 Elsevier B.V. All rights reserved.
146 D.C. de Moura et al. / Journal of Electroanalytical Chemistry 731 (2014) 145152

approach [3,4,6]. The most used types of electrode for this method 2. Experimental
are the metal oxide electrodes that, generally, are the derivatives of
four metal oxides, SnO2, PbO2, RuO2, and IrO2 [6,12]. 2.1. Reagents
RuO2- and IrO2-based anodes are active anodes, known for their
electrocatalytic activity for oxygen and chlorine evolution [1214]. Ultrapure water was obtained using a water purication system
It is difcult to realize the direct oxidation of variety of organics on (MilliQ). The chemical reagents used were of the highest quality
these anodes because the oxygen evolution reaction is preferen- available on the market, without additional purication. Na2SO4
tially favored or the decrease on the electrocatalytic activity has and NaCl were obtained from Fluka.
been conrmed [12]. However, several researchers have success-
fully degraded the organic pollutants using these anodes by the 2.2. Surface analysis
production of active chlorine species [12,1519]. Although there
is not enough comparative data in the literature to establish the The surface morphology of Ti/Ru0.3Ti0.7O2 anode was investi-
best kind of anode for this technique, DSA-type electrodes are usu- gated by scanning electron microscopy (SEM). SEM images were
ally preferred due to their high stability and large production of performed with SEM PHILLIPS XL-30 ESEM with Sputter Coater
oxidant ClO that can reach current efciencies as high as 81 BAL-TEC Model SCD-005. And the composition of electrode was
93% and higher removal efciencies of pollutants (see Table 1, with determined by electron probe microanalyzer (EPMA).
the some kind of anodes using chloride solutions).
Based on existing literature [3,12,1519], the effect of operat- 2.3. Electrochemical measurements
ing parameters such as Cl concentration, current density, stir-
ring or ow rate, pH and temperature on the organic matter Potentiodynamic measurements (i.e. linear polarizations curves
decay of synthetic or real efuents has been extensively studied (PC) and cyclic voltammetries (CV)) were carried out in room tem-
using DSA electrodes. However, few works have reported the perature by using AutoLab 302 N. Ti/Ru0.3Ti0.7O2 was used as work-
time evolution of chlorine-related species (i.e., active chlorine ing electrode (1 cm2 of exposed area), Ag/AgCl (3 M) and Pt wire
(dissolved Cl2, HClO, OCl), chlorite, chlorine dioxide, chlorate were used as reference and counter electrode, respectively.
and perchlorate) at the operating conditions used for wastewater Quasi-steady polarization curves were carried out at a scan rate
treatment [13,14]. It is important to remark that, while the iden- of 10 mV s1 and with a 0.45 mV step potential, in solutions of
tication of active chlorine species, as a function of time, has NaCl at different concentrations (1.5; 2.5 and 3.5 g L1), using
been extensively studied and reported for electrochemical disin- 0.01 M of Na2SO4 to further increase the electrolyte conductivity.
fection of water [5,7]; a brief investigation about this behavior
has been explored for the application of electrochemical treat- 2.4. Active chlorine species
ment of efuents.
Predominantly, when Cl-mediated oxidation is employed as To determine the active chlorine species concentration pro-
treatment, an explanation has been assumed by several authors duced (chlorite, chlorine dioxide and chlorate) at Ti/Ru0.3Ti0.7O2
about the role of halide, which is related to the anodic shift of during 120 of electrolysis by applying 25, 50 and 75 mA cm2 in
the oxygen evolution in concomitance with the participation of presence of NaCl (1.25 g L1); a sequence of iodometric titration
active chlorine species in the electrochemical incineration were performed, where aliquots of 5 mL were sampled and chem-
[2029]. ically analyzed, as indicated by Neodo et al. [14] and Caffaro [30].
For this reason, the aim of this work is to investigate the speci- The different species were discriminated on the basis of their reac-
ation of electrochemically generated chlorine-related species at Ti/ tivity, which was emphasized by either changing the pH or adding
Ru0.3Ti0.7O2 anode by applying different current densities to under- specic reagents, as schematized by Eqs. (1)(6).
stand the Cl-mediated oxidation of a real efuent generated at the 
Federal University of Rio Grande do Norte (UFRN). 2ClO2 2I ! I2 2ClO2 1

Table 1
Percentage of color and COD decays and energy consumption for the indirect electro-oxidation with active chlorine of organic pollutants in chloride solutions using undivided
cells with DSA-type anodes.

Anode organic pollutant C0 (mg dm3) Experimental conditions ja (mA cm2) Color removal (%) COD decay (%) Ref.
Ti/RuO2 anode
Basic Blue 9 80 1.2 g dm3 Cl, natural pH, for 95 min 20 100 94 [13]
Reactive Black 5B 1624b 3.61 g dm3 Cl, pH = 10.6, residence time 27 min 25 100 74 [14]
Acid Blue 113 160 1.74 g dm3 NaCl, pH = 9.0, for 90 min 10 c 80 [15]
Ti/TiO2RuO2 anode
Acid Brown 14 330 0.58 g dm3 NaCl, pH = 7.0, for 2.5 h 30 100 67 [16]
Ti/TiO2RuO2PbO2 anode
Acid Brown 14 330 0.58 g dm3 NaCl, pH = 7.0, for 2.5 h 30 100 42 [16]
Ti/TiO2RuO2IrO2 anode
Reactive Black 5 100 1.5 g dm3 NaCl, pH = 6.26.5, for 2 h 36 100 53, 26d [17]
Reactive Blue 19 100 53, 22 d
Reactive Red 141 100 82, 44 d
a
Applied current density.
b
Initial COD.
c
Not determined.
d
Percentage of TOC decay.
D.C. de Moura et al. / Journal of Electroanalytical Chemistry 731 (2014) 145152 147

 
ClO2 4H 4I ! 2I2 Cl H2 O 2 2.6. Characteristics of the wastewater efuent generated by UFRN


Cl2 2I ! I2 2Cl 3 The efuent of the biological stage was collected from biologi-
cal-physical chemical treatment station at Federal University of

ClO3 6KBr 6HCl ! 3Br2 6KCl 3H2 O Cl

4 Rio Grande do Norte (UFRN), located in Natal (Northeast of Brazil).
The efuent contained a concentration of 83.6 mg L1 of TOC. Its
electric conductivity was around 500 lS cm1, while the pH was
3Br2 6I ! 3I2 6Br 5
around 6.3. Through analysis by ion-chromatography (IC), it was
possible to determine the concentration of some important ions
I2 2S2 O2  2
3 ! 2I S4 O6 6 present in the wastewater, such as Cl (208.5 mg L1), NO 3

The overall duration of each test was 120 min; the pH value and (85.8 mg L1), Ca2+ (11.1 mg L1), Na+ (126.1 mg L1), Mg2+
cell potential were checked during the electrolysis because both (6.5 mg L1) and SO2
4 (21.5 mg L
1
).
parameters help to understand the formation of active chlorine
species electrogenerated (pH) and the associated costs to the pro- 3. Results and discussion
cess (V).
3.1. Surface morphology
2.5. Electro-oxidation experiments
SEM pictures for Ti/Ru0.3Ti0.7O2 electrode are shown in Fig. 2.
Bulk oxidations were carried out in an undivided electrochem- These images show an irregular surface without relevant altera-
ical cell, the reaction compartment having a capacity of 0.5 L tions (Fig. 2a). On the other hand, a cracked-mud texture (well-
(Fig. 1). Ti/Ru0.3Ti0.7O2 was used as the anode, and titanium as known denition for this kind of morphology [31]) was observed
the cathode. Both electrodes were square, each of them with at Ti/Ru0.3Ti0.7O2 surface (Fig. 2b), and no other signicant features
50 cm2 of geometrical area. The production of active chorine spe- were recognized by SEM images. Alternatively, as can be observed
cies and oxidation experiments of real efuent were conducted in Fig. 2c, EPMA spectrum shows that the composition of electrode
under galvanostatic conditions using a power supply MINIPA corresponds with the nomenclature used (Ti/Ru0.3Ti0.7O2). Also, the
MPL-3305. Ti/Ru0.3Ti0.7O2 anode was supplied by Industrie De Nora EDS analysis of surface indicates that the dispersion/distribution of
S.p.A. (So Paulo, Brazil). While for production of active chlorine each one of the components of the Ti/Ru0.3Ti0.7O2 electrode on the
species, the solution was vigorously stirred and steadily main- surface, is in accordance with the composition of electrocatalytic
tained at the desired temperature (25 C) by applying 25, 50 or material (Fig. 3) with a higher level of homogeneity.
75 mA cm2 for determine their concentration, as a function of
time; the Cl-mediated oxidations of real efuent were performed
3.2. Electrochemical measurements
at room temperature for studying the role of applied current den-
sity (25, 50 and 75 mA cm2) by adding a known amount of NaCl.
As indicated by other authors [25,31], important information on
Total organic carbon (TOC) values were determined in TOC - VCPH,
the electroactivity of Cl at anode surface material can be obtained
Shimadzu equipment. Proles of all these parameters were
prior to anodic oxygen evolution (o.e.r.) by CV and PC studies. Fig. 4
obtained by sampling solutions at predetermined time intervals
shows the voltammograms for background electrolyte and for
during the degradation process.
solution containing different concentrations of NaCl (1.5; 2.5 and
3.5 g L1). CV curves obtained with a Ti/Ru0.3Ti0.7O2 in 0.01 M Na2-
SO4 (black line), presented the typical behavior of thermally pre-
pared oxide layer. The shape in the CV with not well-dened
peaks can be understood in terms of a large heterogeneity in the
surface site and superposition of the redox processes for the tran-
sition lower metal oxide/higher metal oxide [31,32]. During the
rst cycle, in the solution containing with 1.5 g L1 of NaCl (blue1
curve, in inset of Fig. 4) a broad anodic peak at approxi-
mately +1.02 V vs. Ag/AgCl (3 M) was observed, suggesting the
involvement of reactions of Cl ? Cl2, ClO M ClO 
2 and ClO M ClO2
[14,32]. Alternatively, an increase in the current intensity at a given
potential in the region of supporting electrolyte decomposition was
observed. This behavior suggests an inhibition of o.e.r. due to the
promotion of chlorine evolution reaction, as already stated by other
authors [20,23,25]. Conversely, a pronounced shape was observed
when cathodic scan was performed (+0.67 V), thus providing a clear
indication of the involvement of adsorbed species. These voltammet-
ric signals have showed correspondences with the anodic and catho-
dic responses obtained by Tomcsanyi and co-workers [32], where
they have associated with a series of adsorption reactions.
Then, from the results recorded, the peak, about +0.67 V, would
be due to the reduction of hypochlorite species to chloride, possi-
bly through the formation of adsorbed atomic chlorine, as
described by Hine and Yasuda [33] and Harrison and Khan [34],
according to the follow reactions:
Fig. 1. Diagram of the one-compartment electrochemical cell used for studying
active chlorine production as well as Cl-mediated oxidation of real efuent: C,
1
counter, R, reference, and W, working electrode, respectively; pH electrode; S, For interpretation of color in Fig. 4, the reader is referred to the web version of
sample holder; and m, magnetic stirrer. this article.
148 D.C. de Moura et al. / Journal of Electroanalytical Chemistry 731 (2014) 145152

Fig. 2. Micrographs (a and b, SEM images) and composition of electrocatalytic material used (c, EPMA spectrum), as anode, for studying active chlorine production as well as
Cl-mediated oxidation of real efuent.

Fig. 3. EDS layered image as evidence of the dispersion/distribution of each one of the components of anode used.

This behavior acquires particular importance when an undi-


vided electrochemical cell is used, justifying the no existence of
higher concentration of hypochlorite in the bulk of solution when
RuO2-based electrodes are used, as supported by other authors
[14].
On the other hand, the whole voltammetric curves are shifted to
less positive potentials (Fig. 4, red and green curves), while increas-
ing the chloride concentration is attained due to the increase of the
importance of the Cl2/H2O system [25]. Also, the anodic peak reg-
istered at +1.02 V is shifted to +0.78 V, while the cathodic signal is
shifted from +0.67 V to +0.72 V and +0.76 V when 2.5 and 3.5 g L1
were added in solution. According to Vazquez-Gomez et al. [31],
Cl-mediated oxidation of water involves a quite complex set of
reactions, at the electrode surface as well as in the bulk of the solu-
tion, which are mostly related with the electrochemical reactivity
of Cl and the chemical/electrochemical reactivity of some of its
Fig. 4. Cyclic voltammetric curves obtained at Ti/Ru0.3Ti0.7O2 electrode in absence
(0.01 M Na2SO4) and in the presence of NaCl (1.5; 2.5; 3.5 g L1) recorded at oxidation products. Following the rich literature available on the
10 mV s1. subject, the anodic oxidation of Cl can be represented, in princi-
 ple, by two relatively simple mechanisms, both involving a dis-
ClO H2 O e ! Clads 2OH 7 charge as a rst step, with adsorbed radical formation, and
 differing in the successive radical desorption step: chemical or
Clads e ! Cl 8
electrochemical, conrming the peaks observed in Fig. 4. In partic-
D.C. de Moura et al. / Journal of Electroanalytical Chemistry 731 (2014) 145152 149

ular, the increase on the pronounced shape observed at reaction. These outcomes are in agreement with the gures
about +0.67 V vs. Ag/AgCl (3 M) proposes that some active chlorine obtained at CV measurements.
species are reduced, suggesting that the chemical depletion might From the above results, the understanding of the course of elec-
prevail over the electrochemical. For example, chlorine dioxide is trolytic process by involving the electrochemical production of
converted to chlorate and chlorite due to its instability in alkaline active chlorine species is necessary via determination of these spe-
media. Also, the mechanism of chlorite reduction may be attained, cies at Ti/Ru0.3Ti0.7O2 anode.
being signicantly affected by the surface state of the electrode,
which occurs by the establishment of adsorptive interactions
between the anode surface and ClO 2 species. In fact, an oxide 3.3. Electrolysis of chloride solutions
can be often in the form of a hydrated oxide in aqueous solution
or the formation of a determine concentration of hydroxyl radicals Fig. 6 shows the trends of active chlorine species synthesized at
can be also attained. The mechanism for redox transitions of the Ti/Ru0.3Ti0.7O2 electrode, at current densities, i.e., (a) 25, (b) 50 and
surface oxycations has been proposed as [13,35]: (c) 75 mA cm2, as a function of time of electrolysis, at 25 C. Con-
sidering the electrolysis carried out at the lower current density

MOa OHb  xH2 O dH e $ MOad OHbd  xH2 O 9

where surface oxycations exchange H (or OH) with the electrolyte


solution when electron transfer occurs. The symbol, M, indicates a
transition metal such as Ru, Ir, Ni, Co, etc.
Then, the interaction of hydrated oxide suggests that cathodic
peak can be attributed to the reduction process of ClO2 to ClO 2
[36]. The production of chlorite may be favors that hypochlorite
to be synthesized from chlorite during the reductive scan (ClO 2 +
H++ e ? ClO + OHads) resulting in an enrichment of ClO within
the Nernst layer [14]. Then, overall process generated the pro-
nounced shape in the CV curves. After that, the oxidation of ClO
may proceed to higher electron-state species, such as ClO 3 and
ClO 4 , during anodic scan direction.
In order to extend the voltammetric behavior and on the basis
of the introductory considerations on the possible effect of halide
on the oxygen evolution reaction (o.e.r.); quasi-steady polarization
curves were recorded in background solution of 0.01 M Na2SO4 and
in the presence of different concentrations of Cl (1.53.5 g L1).
The results obtained in the presence of chloride ions are shown
in Fig. 5. At Ti/Ru0.3Ti0.7O2 anode, the whole polarization curve is
shifted to less positive potentials (Fig. 5), while increasing the chlo-
ride concentration, up to 3.5 g L1 due to the increase of the impor-
tance of the Cl2/H2O system as a potentiostatic buffer, as already
indicated in a previous work [25]. As a direct consequence of this
occurrence, the anode potential in the region of J values applied
for electrochemical incineration of organics reaches values of the
order of 2.0 V (vs Ag/AgCl). At these polarization levels, the number
and reactivity of hydroxyl radicals, adsorbed at the electrode sur-
face, may lead to fast incineration of a number of organic sub-
strates [1525] due to the coexistence of active chlorine species,
often assumed as intermediates also in the chlorine evolution

Fig. 5. Linear polarization curves recorded at Ti/Ru0.3Ti0.7O2 electrode in absence Fig. 6. Active chlorine concentrations assessed in the course of the electrolysis of a
(0.01 M Na2SO4) and in the presence of NaCl (1.5; 2.5; 3.5 g L1), scan rate solution containing with 2.5 g L1 of NaCl by applying 25, 50 and 75 mA cm2 at
10 mV s1. 25 C.
150 D.C. de Moura et al. / Journal of Electroanalytical Chemistry 731 (2014) 145152

(25 mA cm2), an increase of the relative active chlorine species 3.4. Electrochemical treatment of actual efuent
concentration, as a function of time, can be appreciated. The active
chlorine species determined by a sequence of iodometric titration The effect of the applied current density on TOC removal during
were Cl2, ClO 
2 , ClO3 and ClO2. It is worth noting the evident pro- electrochemical treatment of an actual efuent, containing with
duction of Cl2 and ClO 2 species when comparing with the concen- 1.5 g L1 of NaCl at 25 C, using Ti/Ru0.3Ti0.7O2 electrode, was inves-
tration of ClO2. This behavior can be correlated to the observation tigated. In all cases, efcient elimination of organic matter was
appointed about the instability of chlorine dioxide in alkaline achieved after 40 min of electrolysis. This treatment time was cho-
media, where the formation of ClO 
2 and ClO3 can be attained by sen because higher concentrations of active chlorine species were
a chemical reaction [14,37,38]. However, chlorate was not detected achieved around 40 and 50 min, as showed in Fig. 6. Nevertheless,
at 25 mA cm2, indicating that it is not formed because a great according to the prole of TOC removal, as a function of time, at
amount of ClO2 suffers preferentially a disproportionation to pro- different current densities (25; 50 and 75 mA cm2), the organic
duce ClO2 via the reaction [39]: matter load was predominantly eliminated after 10 min of electro-
chemical treatment, remaining TOC decays invariable up to com-
  plete 40 min. Results clearly showed that good performances
ClO2aq e $ ClO2 E 0:95 V 10
were attained after 10 min of treatment applying 25 and
75 mA cm2, see Fig. 7. This behavior indicates that the organic
being disfavored a production of signicant concentrations of ClO
3 load decreases by action of electrogenerated active chlorine species
from reaction [40]: produced at Ti/Ru0.3Ti0.7O2 surface. However, these ndings sug-
gest that initial treatment stages exhibit mechanisms involving
  organic matter oxidation to more simple organic compounds by
2ClO2aq 2OH $ ClO2 ClO3 H2 O 11
active chlorine species, and these are dependent on the pH reached
It is important to remark that, the tendency of ClO2 to dispro- at anode surface or in the bulk of the solution.
portionate into ClO 
2 and ClO3 preferably occur at higher pH values. In indirect electro-oxidation, chloride salts of sodium or potas-
Interestingly, the active chlorine concentration trends reach a sium are added to the wastewater for better conductivity and spe-
maximum, which is located at around 40 min for Cl2 and ClO2 con- cic electrochemical reactions at anode surface are attained
centrations when 25 mA cm2 was applied; after that, the concen- (depending on the pH [7,9]) to form active chlorine species such
tration of these species decreased slightly. In the case of ClO 2 , it as Cl2, HOCl, OCl, and ClO2. These are widely recognized as key
achieves a maximum production at 80 min, decaying due to the oxidants responsible for inactivating cells or depletion of organic
behavior explained above. matter by electro-chlorination [7]. These species can be produced
Increasing the current density to 50 mA cm2 and then to at the anode surface by the reactions in Eqs. (12)(14) [7].
75 mA cm2 (Fig. 3), a sort of levelling for the trends at the differ- 
ent experimental conditions is observed, being less evident to 2Cl ! Cl2 2e 12
75 mA cm2, after 50 min of electrolysis. Again, a maximum of con-
 
centration of active chlorine species is attained at 40 min. Never- Cl2 2OH ! H2 O ClO Cl 13
theless, at 50 mA cm2, chlorite is the predominant active specie
formed when comparing with 25 mA cm2 where the Cl2 is prefer-
Cl2 4H2 O ! 2ClO2 8H 8e 14
entially produced. As stated by Neodo et al. [14], the mechanisms

of chlorite reduction occur with the establishment of adsorptive Also, ClO can form HClO in the intermediate region at the elec-
interactions between the electrodes and the ClO 2 species. Then, trode surface, as a consequence of the large acidity (pH is slightly
considering the fact that overall process takes place in an undi- acidic) due to the concomitant oxygen evolution, as indicated pre-
vided cell, the increase of ClO 2 concentration can be attributed to viously by other authors [25,27,29] and further dissociated to give
the reduction process of ClO2 to ClO 
2 (ClO2(aq) + e M ClO2

hypochlorite ion can be attained again:

(E = + 0.95 V)), [14,36,39], while the oxidation of ClO may pro-

ceed to higher electron-state species, such as ClO 3 . These insights
HClO $ H ClO 15
are conrmed by the increase of ClO 
2 and ClO3 species, when an
increase on the applied current density is attained. and the hypochlorite ions act as main oxidizing agent in the pollu-
The bulk concentrations of ClO tant degradation.
3 and ClO2 assessed during in the
course of the electrolytic processes were signicantly lower that
the ClO 2 and Cl2. Possible reasons for that can be found due to their
reactivity at the anode and cathode surfaces and their bulk reactiv-
ity as well as their dependence on pH [13].
Concerning the active chlorine species formed at Ti/Ru0.3Ti0.7O2
electrode and signicant chemical/electrochemical behaviors, we
can infer that these effects can be expected during electrochemical
treatment of an actual efuent. For this reason, an urban wastewa-
ter generated at the UFRN has been considered as a model solution.
Since 1979, at UFRN, chemical chlorination is the advanced oxida-
tion treatment to decrease the organic load of the efuents. Then, a
second objective could be achieved with this work, proposing as an
alternative method the production in situ of the active chlorine
species for depollution of water. As the formation of ClO 3 and ClO4 -

species is undesired reaction and their formation depends on the
applied current density as well as Cl present in solution (as con-
rmed by CV analysis [14]), the concentration of 1.5 g L1 of NaCl Fig. 7. TOC removal efciency as a function of applied current density (25; 50 and
was chosen to be used in the set of experiments to treat a real 75 mA cm2) after 10 min of electrochemical treatment of real efuent by Cl-
efuent. mediated oxidation.
D.C. de Moura et al. / Journal of Electroanalytical Chemistry 731 (2014) 145152 151

In the case of active anodes, when Cl may react with physi- Table 2
sorbed hydroxyl radical (MOx(dOH)) to form adsorbed OCl radicals Operating potential (E), energy consumption and cost for the electrochemical
treatment by Cl-mediated oxidation.
according to the Eq. (16):
Sampling Current Potential Energy Electrical cost
 time (min) density (V) consumption
MOx  OH Cl ! MOx  OCl H 2e 16 (mA cm2) (kWh m3)
Reala Dollarb

Further, in presence of Cl, the adsorbed hypochlorite radicals 40 25 15.4 23.1 6.9 3.1
may interact with the oxygen already present in the oxide anode 40 50 22.1 66.3 19.9 8.9
40 75 27.4 123.5 37.1 16.6
with possible transition of oxygen from the adsorbed hypochlorite
a
radical to the oxide forming the higher oxide MOx+1 according to Brazilian currency (real).
b
the Eq. (17) and also MOx(OCl) simultaneously react with chloride US currency (dollar).

ion to generate active oxygen (dioxygen) and chlorine according to


the Eq. (18):
3.5. Energy consumption and cost

MOx  OCl Cl ! MOx1 Cl2 e 17
An important factor in any treatment system is the energy
expenditure associated with each process. Thus, the energy con-
MOx  OCl Cl ! MOx 1=2O2 1=2Cl2 e 18 sumption (kWh m3) associated with the oxidation tests per-
formed in this study was estimated by Eq. (19):
On the other hand, it should be noted that, OH produced on the
d

surface at Ti/Ru0.3Ti0.7O2 could also participate in the oxidation of Energy consumption V  I  t=1000  V s 19
organic matter.
Restricting now our analysis to solution pH, originally around where t is the electrolysis time (h), V and I depict the average poten-
6.8, it increases during the rst 15 min of electrolysis to values of tial and current of the cell during electrolysis, respectively, and Vs is
9.310, after that, pH around 9.5 is maintained during the overall the volume of the sample (m3).
process (Fig. 8). Based on these results, we can assume that the Results clearly showed that, lower current densities must be
electrochemical/chemical reactions regarding the active produc- preferentially used (25 mA cm2) because a signicant reduction
tion are preferentially favored than the o.e.r or production of of organic matter (83%) is achieved in short electrolysis times
d
OH. Thus, it is possible to infer that, Cl2, ClO 
2 , ClO3 and ClO2 requiring only 23.1 kWh m3, and as a consequence, lower treat-
species can be electrochemically generated under these experi- ment prices can be expected. In fact, taking into consideration an
mental conditions. However, while ClO2 is reduced to ClO 2 due electrical energy cost of about R$ 0.3 (Brazilian price, taxes
to its reaction with organic matter (R) in solution (2ClO2(aq) + excluded) per kWh (Agncia Nacional de Energia Eltrica, Brazil),
+
R + H2O M R + ClO 2 + HClO + H [41]) and its instability in alkaline the process expenditure was estimated and reported in Table 2
media; the occurrence of HClO can be considered as a product of in order to show the viability of this process as a green alternative
the reaction of R with ClO2 or only within the Nernst layer as a con- for the treatment of wastewaters. This price was also converted to
sequence of a slight acidic condition at anode surface by the dollar and reported in the same table.
production of oxygen. The rate of removal of total organic carbon
(TOC) demonstrates that the treatment of the efuent by indirect
oxidation by species generated in situ, i.e., active chlorine is partic- 4. Conclusions
ularly effective in the mineralization process, resulting in up to 82%
to 86% of the TOC removed in just 10 min oxidation at densities of Cyclic voltammetric analysis carried out in chloride-containing
25 and 75 mA cm2, respectively (Fig. 7). However, it is important solutions at Ti/Ru0.3Ti0.7O2 electrode have demonstrated that
to indicate that, the lower efciency attained at 50 mA cm2 after depending on the Cl concentration in solution, the high reactivity
10 min may be due to the chemical/electrochemical reactivity of of active chlorine species is attributed to the specic oxidant specie
some of active chlorine species, especially Cl2 and ClO electrochemically produced. Also, both anodically and cathodically
2 , as observed
at Fig. 6. However, we only was advanced it as supposition, since we polarised surfaces contribute to change the electrochemical reac-
was not corroborated it. tivity of some active chlorine species, such as ClO 
2 , ClO and HClO
and it is a consequence of the importance of the use of an undi-
vided electrochemical cell. Also, CV experiments indicated that at
Ti/Ru0.3Ti0.7O2 anode, Cl and ClO can be easily oxidized to Cl2,
ClO   
2 , ClO2 and ClO3 but also reduced to Cl and ClO2 , thus avoid-

ing the higher production of ClO3 .
On the other hand, potentiodynamic curves have indicated that
the oxygen evolution reaction is greatly inhibited by the produc-
tion of active chlorine species, when the concentration of Cl was
increased in solution, in agreement with the assumptions reported
by several authors [1425]. However, based on the results
obtained, during the determination of active chlorine species in
the course of the electrolysis at different applied current densities,
it was evident that the oxygen evolution inhibition depends pre-
dominantly on the specic electrochemical species formed in asso-
ciation with pH, nature of electrode and potential applied.
Finally, the electrochemical disinfection of real efuent was ef-
ciently performed, conrming that the main effect is due to the
Fig. 8. Prole of pH behavior, as a function of time at different current densities
action of active chlorine species. The present work has recently
(25; 50 and 75 mA cm2), during electrochemical treatment of real efuent allowed to start the design and implementation of a pilot electro-
collected from biological-physical chemical treatment station at UFRN. chemical cell in the treatment station at the UFRN. These
152 D.C. de Moura et al. / Journal of Electroanalytical Chemistry 731 (2014) 145152

experiments are in progress and their results will be reported in [16] S. Raghu, C. Ahmed Basha, J. Hazard. Mater. B139 (2007) 381390.
[17] N. Mohan, N. Balasubramanian, V. Subramanian, Chem. Eng. Technol. 24
detail in a near future.
(2001) 749753.
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Conict of interest 644651.
[19] D. Rajkumar, J.G. Kim, J. Hazard. Mater. B136 (2006) 203212.
[20] S. Ferro, F. Lavezzo, G. Lodi, A. De Battisti, C. Comninellis, Proc. Electrochem.
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[21] Ch. Comninellis, C. Pulgarin, J. Appl. Electrochem. 23 (1993) 108.
[22] F. Bonfatti, S. Ferro, F. Lavezzo, M. Malacarne, G. Lodi, A. De Battisti, J.
Acknowledgement Electrochem. Soc. 147 (2000) 592.
[23] F. Bonfatti, A. De Battisti, S. Ferro, G. Lodi, S. Osti, Electrochim. Acta 46 (2000)
The authors thank the nancial support provided by UFRN, 305.
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