Desalination 264 (2010) 143–150

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Decolorization and degradation of Ponceau S azo-dye in aqueous solutions by the

electrochemical advanced Fenton oxidation
Hanaa S. El-Desoky ⁎, Mohamed M. Ghoneim, Naglaa M. Zidan
Analytical and Electrochemistry Research Unit, Chemistry Department, Faculty of Science, Tanta University, 31527-Tanta, Egypt

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

Article history: Oxidation (decolorization/degradation) of Ponceau S azo-dye in aqueous solutions by electro-generated

Received 8 May 2010 Fenton's reagent (Fe2+/H2O2) was optimized. This was carried out in a reactor containing 0.05 M Na2SO4
Received in revised form 2 July 2010 solution of pH 2.5 and a catalytic quantity of 0.1 mM FeSO4 while a cathode potential of − 1.0 V (vs. SCE) was
Accepted 7 July 2010
applied. The reactor was an undivided glass electrochemical cell with a reticulated vitreous carbon (RVC)
Available online 7 August 2010
cathode and a platinum gauze anode. Progress of oxidation of various concentrations of Ponceau S with time
Keywords:
of electro-Fenton reaction was monitored by UV–visible absorption measurements. Mineralization of the dye
Ponceau S azo-dye solutions was examined by estimation of the chemical oxygen demand removal and HPLC analysis at various
Decolorization times of electro-Fenton oxidation. The complete color removal of 0.05, 0.1 and 0.3 mM Ponceau S was
Degradation achieved by electro-Fenton oxidation for 30, 60 and 90 min, respectively. However, approximately 98%
Mineralization mineralization of 0.05, 0.1 and 0.3 mM Ponceau S was achieved due to electro-Fenton oxidation for 40, 60
Electro-generated Fenton's reagent and 120 min, respectively. HPLC analyses showed also that almost no aromatic compounds were remaining
in the treated solutions indicating the efficiency of the electro-generated Fenton's reagent for complete
decolorization and significant mineralization of the Ponceau S azo-dye in aqueous solutions.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction ously generated by reduction of the dissolved molecular O2 in mildly

acidic aqueous medium (Eq. (1)) using different cathodes (e.g.
Synthetic azo-dyes are widely used in textile, printing, cosmetic, reticulated vitreous carbon [14], mercury pool [15], carbon-felt [16]
food colorants and pharmaceutical industries. Some azo-dyes are also and O2-diffusion [17,18]):
used in laboratories as either biological stains or pH indicators. The
strong electron withdrawing character of the azo-group stabilizes the þ − o
O2 þ 2H þ 2e →H2 O2 ðE ¼ 0:69V=NHEÞ ð1Þ
aromatic substances against conversion by oxygenases. The durability
of azo-dyes, however, causes pollution of surface water and conse- The oxidizing power of H2O2 is enhanced in presence of Fe2+
quently the soil and groundwater once the dye discharged into the ions (as catalyst) in mildly acidic solution. Hydroxyl radical (OH•)
environment as effluent. Most of the synthetic azo-dyes and their and Fe3+ ions are then generated from the classical Fenton's
biodegradation products, sulfonated and unsulfonated aromatic reaction between Fe2+ ions and H2O2 [14–19,26,27]:
amines, are toxic against aquatic organisms and suspicious of being
carcinogenic and mutagenic for humans [1–8]. Therefore, these dyes
þ H2 O þ OH•ðFenton s reactionÞ
2þ þ 3þ 0
Fe þ H2 O2 þ H →Fe ð2Þ
necessitate proper treatment before discharge into the environment.
Various methods for removal of synthetic azo-dyes from waste-
Fe2+ ions consumed by Fenton's reaction in the homogeneous
waters have been reported in the literature. These include adsorption
medium (Eq. (2)) are regenerated at the cathode by reduction of Fe3+
on inorganic or organic matrices, biological activation, coagulation,
ions (Eq. (3)) which would induce the Fenton chain reaction
chemical oxidation and electrochemical oxidation methods [1–3,7–
efficiently [16].
9]. Nevertheless, some of these methods are usually non-destructive,
inefficient, costly, and resulted in production of secondary waste 3þ − 2þ o
products such as sludge which may need further disposal. Electro- Fe þ e ⇌Fe E ¼ 0:77V=NHE ð3Þ
Fenton oxidation method as an indirect electrochemical advanced
oxidation process was developed and widely applied for oxidation of On the other hand, molecular oxygen necessary for production of
various organic pollutants [9–25]. In this method, H2O2 is continu- H2O2 (Eq. (1)) is also regenerated at the anode by oxidation of water
in the reactor (Eq. (4)):
⁎ Corresponding author. Tel.: +20 40 2241143; fax: +20 40 3350804. þ − o
E-mail address: hseldesoky@hotmail.com (H.S. El-Desoky). H2 O⇌1=2 O2 þ 2H þ 2e E ¼ 1:23V=NHE ð4Þ

0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.07.018
144 H.S. El-Desoky et al. / Desalination 264 (2010) 143–150
The sum of the above cathodic and anodic processes gives the
overall reaction:
1=2 O2 þ H2 O → 2OH•
The indirect electro-Fenton oxidation method is environmentally
friendly since it does not involve the use of harmful chemical reagents
due to the fact that Fe2+ ions, H2O2 and the produced hydroxyl radicals
(OH•) are non-toxic, besides the method is easy to handle and its reactor
is simple. Besides, the indirect electro-Fenton oxidation method is very
promising since it achieves high reaction yields with low treatment cost
and has been efficiently applied to degrade many organic compounds
[9–25]. Moreover, there is no production of iron sludge in the reactor
and consequently no subsequent disposal problems were found. On
other side, the hydroxyl radicals (OH•) are non-selective very powerful
oxidizing agent that react with organics yielding dehydrogentated or
hydroxylated derivatives until their overall mineralization (conversion
into CO2 and H2O).
Ponceau S (3-Hydroxy-4-(2-sulfo-4-[4-sulfophenylazo] phenylazo)
-2,7-naphthalenedisulfonic acid sodium salt), Scheme 1, has been used
in the present study as a model of sulfonated azo-dye. Ponceau S azo-
dye (also known as Acid Red 112) is used in dying industry of textile,
leather and paper [28–30] and also used in clinical laboratories as a
protein-binding dye for staining of blood serum proteins [31]. However,
its biotransformation products have toxic effects against aquatic
organisms and suspicious of being carcinogenic for humans [3,29].
To our knowledge there is no information reported in the
literature to date concerning decolorization/degradation of Ponceau
S azo-dye by electro-generated Fenton's reagent. However, its
complete decolorization was achieved using a developed methylene
blue immobilized resin dower-11 photocatalyst [28] for 3 h treatment
in solutions of pH 9. Besides, two biological methods were reported
[32,33] for decolorization of Ponceau S azo-dye in aqueous solutions.
The bacterium, Kerstersia sp. strain VKY1 could only decolorize
Ponceau S azo-dye under aerobic condition with 100% decolorization
efficiency at varying initial dye concentrations of 200, 400, 600 and
800 mg L− 1 during 9, 12, 15, and 18 h incubation [32]. On other hand,
the aerobic reduction of 0.2 mM Ponceau S azo-dye by Gram-positive
bacterium Enterococcus faecalis strain ATCC 19433 to about 4.1% was
achieved after 20 h cultivation in brain heart infusion medium [33].
Therefore, there is a need to optimize the optimal conditions for
degradation of Ponceau S azo-dye, either to less harmful products or,
more desirable, to complete mineralization by an effective and
environmentally friendly method.
The present study was designed to optimize the oxidation
(decolorization/degradation) of Ponceau S azo-dye in aqueous
solutions by electro-generated Fenton's reagent (Fe2+/H2O2) in an
undivided glass electrochemical cell using a reticulated vitreous
carbon (RVC) cathode and a platinum gauze anode.
2. Experimental
2.1. Materials and reagents
A commercial Ponceau S azo-dye (Aldrich Chemical Co. Inc, St.
Louis, MO, USA) was used in the present study without further
Scheme 1. Chemical structure of Ponceau S azo-dye molecule.
purification. Solutions of H2SO4 (1 M), anhydrous Na2SO4 (1 M),
NaCl (1 M), KCl (1 M), FeSO4·7H2O (5 mM), K2Cr2O7 (0.025 N) and
FeSO4(NH4)2SO4·6H2O (0.025 N) (all are analytical-grade reagents)
ð5Þ were prepared in deionized water. Desired lower concentrations
were obtained by the accurate dilution of the standard solutions by
deionized water. Ferrion indicator solution (which was used in
analysis of chemical oxygen demand, COD, by the standard open
reflux method [34]) was prepared by dissolving 1.485 g of 1,10-
phenanthroline monohydrate and 695 mg FeSO4·7H2O in 100 mL
deionized water.
2.2. Electrochemical apparatus
A Potentiostat Model 362-PAR (Princeton Applied Research, Oka
Ridge, TN, USA) was used in the present study. An undivided glass
electrochemical cell (reactor) of 600-mL volume with a three electrode
system was used. The cathode was a reticulated vitreous carbon (RVC)
sheet (60 PPI) of the dimensions 5 cm, 7 cm and thickness of 0.9 cm
(ARG Materials and Aerospace Corporation, Oakland, CA, USA). The
anode was a platinum gauze of an area of 3.8 cm2 placed at the center of
the electrochemical cell. A reference saturated calomel electrode (SCE)
was placed in a glass-luggin capillary at a position of 3 mm from the
cathode surface. RVC was used as a cathode in the present electrochem-
ical cell based on the fact that it is chemically and electrochemically inert
over a wide range of potentials and with a broad variety of chemicals. It
has a high specific surface area within the porous structure that is
accessible to electrochemically active species. RVC has also a high fluid
permeability, and it is easily shaped as required by cell design consid-
erations. Furthermore, RVC has a good selectivity for H2O2 electro-
synthesis. This is because it exhibits a range of electrochemical activities
towards oxygen reduction, high overpotential for hydrogen evolution
and low catalytic activity for decomposition of hydrogen peroxide.
2.3. Procedure
Oxidation of Ponceau S azo-dye by electro-generated Fenton's
reagent was carried out in 450 mL of 0.05 M Na2SO4 solution of pH 2.5
(the pH of solution was adjusted by addition of H2SO4 solution) in the
presence of a catalytic quantity of 0.1 mM FeSO4 at a RVC cathode
applied potential of −1.0 V vs. SCE using the described undivided glass
electrochemical cell (reactor). Pure oxygen gas was bubbled (before
starting the electro-Fenton oxidation) into the supporting electrolyte for
30 min to saturate the aqueous solution. The investigated solution was
stirred magnetically in a rate of 400 rpm and the solution pH remained
practically constant (2.5 ± 0.1). For monitoring the decolorization/
degradation of the examined azo-dye in aqueous solution by electro-
Fenton oxidation, 1.5 mL of the examined solutions were withdrawn
from the reactor at regular time intervals (0, 10, 20, 30, 45, 60, 90, 120,
150, 180, 240, 300, 360, 420, 480, 540 and 570 min) then analyzed.
2.4. Monitoring of oxidation reaction
Progress of oxidation (decolorization/degradation) of Ponceau S
azo-dye by electro-generated Fenton's reagent was monitored in the
present study by:
2.4.1. UV–visible absorption measurements
The UV–visible electronic absorption spectra of Ponceau S azo-
dye in aqueous solutions were recorded at ambient temperature
(25 ± 2 °C) within the wavelength range of 200–800 nm using a
Shimadzu UV–visible spectrophotometer Model 160A (Kyto, Japan)
with a spectrometric quartz cell (1 cm path length). Quantitative
analysis of Ponceau S azo-dye in aqueous solution was monitored
spectrophotometrically by measuring its absorbance at λmax. = 515 nm
at different time intervals of electro-Fenton oxidation and then
computing the corresponding concentration Ct of the dye from a
 H.S. El-Desoky et al. / Desalination 264 (2010) 143–150
constructed calibration curve. The extent of color removal of the
investigated solution can be expressed as:
% Color removal ¼ ð1−Ct =C0 Þ  100 ð6Þ
where C0 is the initial concentration of the Ponceau S azo-dye and Ct is its
concentration at reaction time t (min).
2.4.2. COD analysis
To quantitatively characterize the extent of oxidation of Ponceau S
azo-dye in aqueous solutions, 3 mL of the examined solutions were
withdrawn from the reactor at regular time intervals (0, 10, 20, 30, 45,
60, — min) then the chemical oxygen demand (COD) was determined
by means of the standard open reflux method [34] and then the % COD
removed ratio was estimated:
% COD removal ¼ ð1−CODt =COD0 Þ  100 ð7Þ
where COD0 and CODt are the measure of oxygen equivalent to the
organic matter of a sample that is susceptible to oxidation by a strong
chemical oxidant at reaction time 0 and t of electro-Fenton treatment
of Ponseau azo-dye aqueous solutions, respectively.
2.4.3. HPLC analysis
Reversed-phase HPLC was also utilized for monitoring the
progress of degradation of Ponceau S azo-dye in aqueous solutions,
formation and/or destruction of reaction aromatic products during the
oxidation of Ponceau azo-dye. Liquid chromatograms of solutions of
Ponceau S azo-dye during its oxidation by electro-Fenton's reagent
were recorded using a high-pressure liquid chromatographic pump
(Bischoff, Switzerland) equipped with a UV-detector (Bischoff,
Lambda 1000). Data acquisition and peak integration was done with
the Bischoff McDAcq integrator software v1.5. A reversed-phase
column (Prontosil C18, 250 × 4.0 mm, 5 μm) was used in the present
investigation at ambient temperature (25 ± 2 °C). A mixture of
acetonitrile:water:acetate buffer of pH 5 (50:10:40 v/v/v) was used
as a mobile liquid phase at a flow rate of 0.5 mL/min. The injection
volume was 20 μL with a Rheodyne 7125 injector valve. The detection
was performed by UV absorption at λmax = 349 nm. The % removed
ratio of aromatic rings was calculated as:
% Ar rings removal ¼ ð1−At =A0 Þ  100 ð8Þ
where A0 and At are the peak area at reaction time 0 and t of electro-
Fenton's oxidation of the investigated azo-dye solutions, respectively.
All experiments were performed in triplicate under ambient
temperature. Reproducible results of % Color removal calculated
from spectrophotometric measurements, % COD and % Aromatic ring
removal were obtained under all the tested experimental conditions.
3. Results and discussion
3.1. UV–visible absorption spectral measurements
The absorption spectra of various concentrations of Ponceau S azo-
dye in acidic 0.05 M Na2SO4 aqueous solution displayed a main band
in the visible region with a maximum absorption (λmax) at 515 nm in
addition to three smaller bands in the ultraviolet region of λmax at 349,
311 and 270 nm. The band in the visible region (λmax = 515 nm)
accounts for color of the azo-dye was attributed to the absorption of
the n → π⁎ transition related to the –N = N– group [35]. While the
bands at 311 and 349 nm were ascribed to the absorption of the π–π⁎
transition related to the naphthalene rings bonded to the –N = N–
group of the azo-dye molecule [35]. The band at 270 nm was
attributed to the adsorption of the π–π⁎ transition within the
benzenoid system [35]. Plot of absorbance (at λmax = 515 nm) vs.
concentration of Ponceau S azo-dye in aqueous solution was
145
constructed (r = 0.999) and was used as a calibration curve for
monitoring concentration of the dye in aqueous solution at different
time intervals during its electro-Fenton oxidation.
Preliminary study of decolorization/degradation of 0.1 mM Pon-
ceau S azo-dye in aqueous solution of 0.05 M Na2SO4 regulated with
H2SO4 at pH 2.5 in presence of 0.05 mM FeSO4 was carried out by
electro-Fenton oxidation while controlling the cathode bias potential
at −0.5 V (vs. SCE) using the described reactor. The UV–visible
absorption spectra of a treated solution of Ponceau S withdrawn from
the reactor at different time intervals were recorded and depicted in
Fig. 1. It was clearly observed that the intensity of characteristic band
at 515 nm of Ponceau S azo-dye diminished gradually during the
experiment until it disappeared totally due to electro-Fenton
oxidation for 570 min. The ultraviolet bands (at 349, 311 and
270 nm) were also observed to gradually diminish but with a lower
rate than that of the visible band. This behavior indicated the effective
destruction of the chromophore and breaking down of the aromatic
rings of the dye molecules due to their attack with OH• radicals.
However, decolorization process of Ponceau S azo-dye was faster than
that of destruction of the aromatic rings. This is because OH▪ radicals
attack first the –N = N– group of the lowest energy [35] leading to the
opening of the –N = N– double bonds, then destructing the long
conjugated π systems, and consequently causing decolorization of the
investigated solution.
For optimizing the operational conditions for efficient oxidation of
Ponceau S azo-dye in aqueous solutions by electro-generated Fenton's
reagent, the effect of each of the cathode applied potential, pH of the
medium, nature of supporting electrolyte, and initial concentration of
Fe2+ ions as a catalyst were studied spectrophotometrically.
3.2. Effect of the cathode applied potential
Effect of the RVC cathode applied potential upon the oxidation of
0.1 mM Ponceau S azo-dye by electro-generated Fenton's reagent was
examined at each of −0.5, −0.7, and −1.0 V vs. SCE in 0.05 M Na2SO4
aqueous solution of pH 2.5 containing 0.05 mM FeSO4. Absorbance of
Ponceau S azo-dye solution at λmax = 515, 349, 311 and 270 nm was
found to decrease with the increase of the cathode applied potential
from −0.5 V to −1.0 V. The efficiency of color removal of Ponceau S azo-
dye has found to reach approximately 100% by electro-Fenton oxidation
for 180, 330, and 570 min at the cathode applied potential of −1.0,
Fig. 1. UV–visible absorption spectra of 0.1 mM Ponceau S azo-dye aqueous solution
(diluted 2-folds) at different time t intervals: 0, 10, 20, 30, 45, 60, 90, 120, 150, 180, 240,
300, 360, 420, 480, 540 and 570 min (from up to down) of electro-Fenton oxidation in
0.05 M Na2SO4 aqueous solution of pH 2.5 in the presence of 0.05 mM FeSO4 at a RVC
cathode applied potential of − 0.5 V.
146 H.S. El-Desoky et al. / Desalination 264 (2010) 143–150

−0.7, and −0.5 V, respectively (Fig. 2). This behavior indicated that the
electro-Fenton oxidation (decolorization/degradation) of Ponceau S
azo-dye was much faster under a cathode applied potential of −1.0 V.
However, for a potential more cathodic than −1.2 V vs. SCE the side
reaction of hydrogen evolution commenced [36].

3.3. Effect of pH of the medium

Previous studies [37,38] revealed that the solution pH can

dramatically influence the degradation of synthetic azo-dyes in
water by Fenton oxidation and the optimal solution pH values for
effective Fenton oxidation were achieved over the pH range of 2 to 5.
At lower pH values, the reaction according to Eqs. (1) and (2) could be
slowed down because hydrogen peroxide can stay stable probably by
solvating a proton to form an oxonium ion, H3O+ 2 (Eq. (9)). The
oxonium ion makes hydrogen peroxide electrophilic to enhance its
stability and presumably to reduce substantially the reactivity with
Fe2+ ions [39,40]. In addition, the scavenging effect of the OH• radicals
by H+ is severe (Eq. (10)) [41,42].
þ þ Fig. 3. % Color removal with time (t) of electro-Fenton oxidation of 0.1 mM Ponceau S in
H2 O2 þ H →H3 O2 ð9Þ 0.05 M Na2SO4 aqueous solution of different pH values, containing 0.05 mM FeSO4 at a
cathode applied potential of − 1.0 V.

OH• þ H þ e →H2 O
þ −
ð10Þ
On the other hand, in solutions of pH values higher than 5 the
oxidation efficiency was rapidly decreased, not only by decomposition
of H2O2 leading to lose its oxidation power [43,44] but also by
deactivation of the catalytic action of Fe2+ ions due to the formation of
ferric hydroxide complexes and consequently leading to reduce the
production of OH• radicals [45]. Hence, experiments were conducted
to study the effect of pH on oxidation of 0.1 mM Ponceau S azo-dye by
electro-generated Fenton's reagent in 0.05 M Na2SO4 aqueous
solution of different pH values (2.5–4.5) in the presence of 0.05 mM
FeSO4 at a cathode applied potential of − 1.0 V. The pH of the
examined solution remained almost constant because the protons
consumed at the cathode according to Eq. (1) are continuously
balanced by water oxidation reaction that occurred at the anode
(Eq. (4)). The results (Fig. 3) showed that approximately 100% color
removal of Ponceau S azo-dye was achieved in solutions of pH values
2.5, 3.5 or 4.5 by electro-Fenton oxidation for 180, 390 or 510 min,
respectively (Fig. 3). Since the oxidation reaction was faster in the
solution of pH 2.5, it was used in the rest of the present study.
3.4. Effect of nature of the supporting electrolyte
Electro-Fenton oxidation of 0.1 mM Ponceau S azo-dye was
examined in different supporting electrolytes (0.05 M and 0.1 M of
each of Na2SO4, NaCl, or KCl) of pH 2.5 in the presence of 0.05 mM FeSO4
at a cathode applied potential of −1.0 V vs. SCE. From Fig. 4, it could be
concluded that approximately 100% color removal of the examined azo-
dye was achieved by electro-Fenton oxidation for 270, 330 and 360 min
(for 0.1 M Na2SO4, NaCl and KCl) or 180, 220 and 250 min (for 0.05 M
Na2SO4, NaCl and KCl), respectively. This behavior indicated that the
oxidation of Ponceau S azo-dye by electro-generated Fenton's reagent
was faster in the solutions of Na2SO4 than that in the solutions
containing Cl− ions. In practical applications, Na2SO4 is generally used
as the supporting electrolyte. Such electrolyte improves the solution
conductivity, and accelerates the electron transfer, thus benefits the

Fig. 2. % Color removal with time (t) of electro-Fenton oxidation of 0.1 mM Ponceau S in Fig. 4. % Color removal of 0.1 mM Ponceau S with time (t) of electro-Fenton oxidation in
0.05 M Na2SO4 aqueous solution of pH 2.5 containing 0.05 mM FeSO4 at different RVC different aqueous supporting electrolytes of pH 2.5, containing 0.05 mM FeSO4 at a RVC
cathode applied potentials. cathode applied potential of − 1.0 V.
 H.S. El-Desoky et al. / Desalination 264 (2010) 143–150
electro-Fenton reaction. Furthermore, there are reports available in the
literature [46,47] which shows that in the presence of Cl− ions, the
efficiency of Fenton oxidation is lowered whereas in the presence of
SO−24 ions the effect is marginal. The less efficient degradation of
pollutants in Cl− ions containing solutions may be due to their
interaction with OH• radicals (Eq. (11)).
Cl þ OH•→ClOH•
− −
ð11Þ
where Cl− ions scavenge some of the OH• radicals in a nearly diffusion-
controlled way and the radical anion, ClOH•− may then decay through
reaction (12),
ClOH• þ Fe →Cl þ OH þ Fe
− 2þ − – 3þ
ð12Þ
However, highly negatively charged species SO− 4
2
ions with fully
oxidized sulfur is not expected to interact considerably with the strong
oxidant OH• radicals [48]. On the other hand, it is also advisable to carry
out degradation of dyes in sulfate media (of slower decomposition rate)
instead of chloride-containing media (of much faster decomposition
rate) to avoid the generation of toxic and carcinogenic chlorinated by-
products. Therefore, since the oxidation reaction was faster in solution of
0.05 M Na2SO4, and to avoid generation of toxic and carcinogenic
chlorinated species, a solution of 0.05 M Na2SO4 was chosen as a
supporting electrolyte for the rest of the present study.
3.5. Effect of concentration of catalytic ferrous ions
Oxidation of 0.1 mM Ponceau S azo-dye was carried out by electro-
generated Fenton's reagent in 0.05 M Na2SO4 solution of pH 2.5 at a
cathode applied potential of −1.0 V in the absence as well as in
presence of various concentrations (0.05, 0.1, 0.5 and 1.0 mM) of FeSO4.
The results indicated that decolorization/degradation of Ponceau S azo-
dye was remarkably dependent on concentrations of Fe2+ ions.
Decolorization of Ponceau S azo-dye solution was relatively limited in
the absence of Fe2+ ions. Approximately 30% color removal only of
Ponceau S azo-dye was achieved by its treatment in absence of Fe2+
ions for 210 min under the other optimum conditions (Fig. 5, curve a).
The low oxidative ability of the Ponceau S azo-dye in absence of Fe2+
ions can be related to the poor indirect electro-oxidation reaction of the
dye with the electro-generated H2O2 at the cathode (Eq. (1)) [18],
hydroperoxyl radicals (HO•) that can be produced at the anode
(Eq. (13)) [49] and/or slow reaction of the dye with the adsorbed
Fig. 5. % Color removal of 0.1 mM Ponceau S with time (t) of electro-Fenton oxidation in
0.05 M Na2SO4 aqueous solution of pH 2.5 at a RVC cathode applied potential of − 1.0 V
in the absence and presence of various concentrations of FeSO4.
147
OH• radicals (Eq. (14)) that can be produced from water oxidation at
the surface of Pt anode [17,18].
H2 O2 →HO2 • þ H þ e
þ −
ð13Þ
H2 O→OH•ads þ H þ e
þ −
ð14Þ
However, H2O2 alone is not a powerful enough oxidant and thus
the dye is mainly oxidized via reaction with the adsorbed OH• but
because of its low concentration at anode, there is difficulty of
achieving complete oxidation [17,18], (Fig. 5, curve a).
However, about 100% color removal of Ponceau S was achieved by
electro-Fenton oxidation for 150, 45, 90 or 180 min in presence of
0.05, 0.1, 0.5 or 1.0 mM FeSO4, (Fig. 5, curves b, c, d, e), respectively.
An obvious increase in oxidation extent was observed by increasing
concentration of FeSO4 up to a critical quantity of 0.1 mM (Fig. 5,
curves b, c). This is due to the fast reaction of the examined dye with
enough amounts of OH• radicals generated in the medium from
electro-Fenton's reaction (the main oxidation reaction) according to
Eq. (2) [17,18]. At higher concentrations of Fe2+ ions than the critical
one (0.1 mM), the rate of oxidation decreased (curves d, e) which may
be due to amount of hydroxyl radicals scavenged by the effect of Fe2+
ions [50] as indicated by Eq. (15). The formed Fe3+ ions could react
with H2O2 to produce hydroperoxyl radicals (HO2•) of less oxidation
capability (Eqs. (16) and (17)) resulting in the decrease of rate of
oxidation (decolorization/degradation) of the azo-dye by the electro-
Fenton reaction [15]:
þ OH•→ Fe þ OH
2þ 3þ −
Fe ð15Þ
Fe
3þ
þ H2 O2 → Fe–OOH
2þ
þH
þ
ð16Þ
Fe–OOH → HO2 • þ Fe
2þ 2þ
ð17Þ
This means that the fast oxidation reaction (decolorization/
degradation) of Ponceau S azo-dye was achieved in the presence of
0.1 mM Fe2+ ions. On other words, the oxidation rate enhanced when
the Fe2+ ions content was increased from 0.0 mM to 0.1 mM,
confirming that OH• radicals are mainly produced by the Fe3+/Fe2+
catalytic system (Eq. (2)). Hence, 0.1 mM FeSO4 was considered the
optimum for the cleavage of –N = N– double bonds and break down of
the rest of the investigated dye molecules by electro-Fenton
oxidation.
According to the foregoing results, the optimal operation condi-
tions for oxidation (decolorization/degradation) of Ponceau S azo-dye
in aqueous solution by electro-generated Fenton's reagent were:
0.05 M sodium sulfate solution of pH 2.5 as a supporting electrolyte,
0.1 mM FeSO4 as a catalyst and a cathode applied potential of −1.0 V
(vs. SCE).
3.6. Oxidation of various concentrations of Ponceau S azo-dye under the
optimized operational conditions
Oxidation (decolorization/degradation) of 0.05, 0.1 and 0.3 mM of
Ponceau S azo-dye in aqueous solutions by electro-Fenton's reagent
was performed under the optimized operational conditions. Progress
of oxidation reaction with time was monitored spectrophtometrically.
The recorded UV–visible absorption spectra of the investigated
solutions (e.g. Fig. 6) showed that the absorbance at each of λmax of
515, 349, 311 and 270 nm was decreased which depicted the
oxidation (decolorization/degradation) of the azo-dye by electro-
generated Fenton's reagent. Approximately 100% color removal of
148 H.S. El-Desoky et al. / Desalination 264 (2010) 143–150

Fig. 6. UV–visible absorption spectra of 0.1 mM Ponceau S azo-dye aqueous solution

Fig. 7. Decay of various initial concentrations of Ponceau S azo-dye with time (t) of
(diluted 2-folds) at different time intervals t: 0, 10, 20, 30 and 45 min (from up to
electro-Fenton oxidation under the optimized operational conditions.
down) of electro-Fenton oxidation under the optimized operational conditions.

0.05, 0.1 and 0.3 mM Ponceau S azo-dye solutions has reached by
electro-Fenton oxidation for 30, 45 and 90 min, respectively (e.g.
Table 1). Variation of concentration (C) of Ponceau S azo-dye in aque-
ous solutions (corresponding to the absorbance at λmax = 515 nm)
with time t of the electro-Fenton oxidation of different initial azo-dye
concentrations was exponential indicating a first-order kinetics
behavior, (Fig. 7). The general elementary rate law for reaction of a
target organic compound can be expressed as:
−dCt =dt ¼ kOH •COH •Ct þ ∑i koxi Coxi Ct
where Ct is concentration of the azo-dye during electro-Fenton
oxidation for time interval t and oxi represents oxidants other than
OH• that may be present. Hydroxyl radical is usually regarded as the
sole or most important reactive species. Then:
−dCt =dt ¼ kOH •COH •Ct
Considering that the concentration of reactive species must reach
quickly a stationary-state regimen during the oxidation process, and
provided that COH• can be considered constant, the rate law for the
oxidation process can be treated as being pseudo-first-order. In terms
of consumption of the target organic compound, Eq. (19) can be
written in the form:
where C0 is the initial concentration of the investigated azo-dye.
Linear-fit relationships between ln (C0/Ct) and time t were obtained
for the three investigated azo-dye concentrations which also
indicated that the oxidation reaction of Ponceau S azo-dye followed
pseudo-first-order kinetics (Fig. 8). The apparent first-order constants
(kapp) were found to be 0.1860, 0.1541 and 0.0604 min− 1, for 0.05, 0.1
and 0.3 mM Ponceau S azo-dye, respectively. The decrease in value of
apparent first-order constant with increasing the concentration of the
azo-dye may due to greater extent of reactions between OH• and
ð18Þ oxidation by-products compared to that involving Ponceau S azo-dye,
thus leading to slow down of decay kinetics of the dye.
It is known that reaction intermediates can form during the
oxidation of azo-dyes and some of them could be long-lived and
even more toxic than their parent compounds. Therefore, it is
necessary to evaluate the degradation extent during and at the
end of electro-Fenton oxidation reaction. Mineralization of the
ð19Þ
treated Ponceau S azo-dye in the investigated solutions during
electro-Fenton oxidation was monitored by chemical oxygen

−dCt =dt ¼ kapp Ct ð20Þ

By integration, the following equation was obtained:

lnðC0 =Ct Þ ¼ kapp t ð21Þ

Table 1
Results of oxidation of 0.1 mM Ponceau S azo-dye in aqueous solution by electro-
generated Fenton's reagent for different time intervals under the optimized operational
conditions.

Time Absorbance % Color COD mg % COD % Ar ring

(min) (515 nm) removal O2/L removal removal

0 3.32 0 173.4 0 0
10 0.45 86.5 117.8 32.1 58.75
20 0.17 94.9 74.0 57.3 73.34
30 0.07 98.1 35.0 79.8 88.0
45 0.01 99.9 13.3 92.3 95.0
Fig. 8. Plots of ln (Co/Ct) with time (t) of electro-Fenton oxidation of solutions of various
60 – 100 4.3 97.5 99.0
initial concentrations of Ponceau S azo-dye under the optimized operational conditions.
 H.S. El-Desoky et al. / Desalination 264 (2010) 143–150
demand (COD) measurements. The chemical oxygen demand
removed ratios (% COD removal) for the solutions withdrawn
from the reactor at reaction times 0 and t of electro-Fenton
oxidation were estimated. The results show gradual decrease in
COD with time of electro-Fenton oxidation indicating the miner-
alization of organic matter (dyes molecules) present in aqueous
solution (e.g. Table 1). These results point out also a fast COD
decay, particularly at the beginning of the oxidation reaction, and
consequently a high oxidative ability of electro-Fenton process.
The results showed that approximately 98% destruction of Ponceau
S azo-dye in the investigated solutions (initial concentrations were
0.05, 0.1 and 0.3 mM) was achieved by electro-Fenton oxidation
for 40, 60 and 120 min, respectively.
Also, progress of oxidation of Ponceau S azo-dye in the
investigated solutions by electro-generated Fenton's reagent was
monitored by recording its HPLC chromatograms before and
during the electro-Fenton oxidation. HPLC chromatograms of
Ponceau S azo-dye in the investigated solution before its electro-
Fenton oxidation showed a single well-defined peak (e.g. Fig. 9,
curve a) of a retention time tr = 3 min. While chromatogram of a
treated solution by electro-Fenton oxidation for 10 min (curve b)
showed a diminished peak (t r = 3 min) in addition to the
appearance of two small new overlapped peaks at retention
times tr = 3.25 and 3.60 min. The latter two small peaks may be
related to the degradation products. Also, another three over-
lapped peaks were developed at retention times tr of 4.7 to 5 min
due to electro-Fenton oxidation of Ponceau S azo-dye solution for
20 min (curve c), which may be related to some other degradation
products. The HPLC chromatogram of the treated solution by
electro-Fenton oxidation for 60 min (e.g. Fig. 9, curve d), showed
no peaks corresponding either to the Ponceau S azo-dye itself or
to any of its degradation products indicating that almost no more
aromatic compounds are remaining in the solution. The aromatic
ring removal of about 99% (initial concentrations were 0.05, 0.1
and 0.3 mM) was achieved by electro-Fenton oxidation for 40, 60
and 120 min, respectively.
Plots of % color removal or % Aromatic (Ar) ring removal vs. % COD
removal (Fig. 10) of 0.1 mM Ponceau S azo-dye solution revealed that
approximately 87% color removal and 60% Ar ring removal were
achieved which corresponding to approximately 32% COD removal
by electro-Fenton oxidation for 10 min under the optimal opera-
tional conditions. However, approximately 100% color removal and
Fig. 9. HPLC chromatograms of 0.1 mM Ponceau S azo-dye aqueous solution before
oxidation (a) and during electro-Fenton oxidation for different time intervals: (b) 10 min,
(c) 20 min and (d) 60 min under the optimized operational conditions.
149
Fig. 10. Plots of % Color removal (a) and % Ar ring removal (b) of 0.1 mM Ponceau S azo-
dye aqueous solution vs. % COD removal by electro-Fenton oxidation for 0 to 60 min
under the optimized operational conditions.
99% Aromatic ring removal of the azo-dye solution was achieved
which corresponding to approximately 98% COD removal by electro-
Fenton oxidation for 60 min. This behavior indicated the effective
destruction of the chromophore and breaking down of the aromatic
rings with electro-generated Fenton's reagent, leading to mineral-
ization of the dye molecules. However, Fig. 10 indicated also a faster
color removal (curve a) than the aromatic ring removal (curve b) by
the electro-Fenton oxidation for 10 min. This is may be due to that
the OH• radicals attack first the –N = N– double bonds, which are of
lowest energy absorption band assigned to the n → π* transition [35],
leading to opening of the –N = N– double bonds, then destructing the
long conjugated π systems, and the formation of aliphatic fragments
intermediate products (e.g. carboxylic acids formed by oxidative ring
opening reactions) which are more difficult to be mineralized. On the
other side, the rate of decolorization/mineralization is relatively
rapid at the early stages of electro-Fenton oxidation for ≤ 10 min.
However slower rate of decolorization / mineralization was observed
at longer oxidation time (Fig. 10 and Table 1) because carboxylic
acids formed by oxidative ring opening reactions are less reactive
toward hydroxyl radicals compared to the aromatics [51,52]. When
oxidizeable impurities are present in the treated real azo-dye
containing-wastewater, they may cause slow down, to some extent,
of the rate of decolorization/mineralization of the examined azo-dye
by electro-Fenton oxidation compared to that in the absence of these
impurities. The results of this work demonstrate the efficiency of the
electro-generated Fenton's reagent for treatments of waters polluted
by persistent organic compounds.
4. Conclusion
Oxidation (decolorization/degradation) of Ponceau S azo-dye in
aqueous solutions by electro-generated Fenton's reagent has been
optimized using an undivided electrochemical cell with a reticulated
vitreous carbon (RVC) cathode and a platinum gauze anode. The
obtained results of % COD removal and the disappearance of the UV–
visible absorption spectral bands and those of high performance liquid
chromatograms of various concentrations of treated Ponceau S azo-
dye aqueous solutions clearly indicated the complete decolorization
and significant mineralization of the azo-dye by electro-generated
Fenton's reagent. The results demonstrate the efficiency of the
optimized electro-Fenton's reaction for treatment of waters polluted
by persistent organic compounds
150 H.S. El-Desoky et al. / Desalination 264 (2010) 143–150
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