Environ Chem Lett (2003) 1:38–44

DOI 10.1007/s10311-002-0017-0

ORIGINAL PAPER

Elodie Guivarch · Stephane Trevin · Claude Lahitte ·
Mehmet A. Oturan

Degradation of azo dyes in water by Electro-Fenton process

Accepted: 9 October 2002 / Published online: 13 February 2003 
Springer-Verlag 2003

Abstract The degradation of the azo dyes azobenzene, pmethyl red and methyl orange in aqueous solution at room
temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potentialcontrolled electrolysis conditions, using a Pt anode and a
carbon felt cathode. The electrochemical production of
Fenton’s reagent (H2O2, Fe2+) allows a controlled in situ
generation of hydroxyl radicals (·OH) by simultaneous
reduction of dioxygen and ferrous ions on the carbon felt
electrode. In turn, hydroxyl radicals react with azo dyes,
thus leading to their mineralization into CO2 and H2O.
The chemical composition of the azo dyes and their
degradation products during electrolysis were monitored
by high performance liquid chromatography (HPLC). The
following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol.
Degradation of the initial azo dyes was assessed by the
measurement of the chemical oxygen demand (COD).
Kinetic analysis of these data showed a pseudo-first order
degradation reaction for all azo dyes. A pathway of
degradation of azo dyes is proposed. Specifically, the
degradation of dyes and intermediates proceeds by
oxidation of azo bonds and aromatic ring by hydroxyl
radicals. The results display the efficiency of the ElectroFenton process to degrade organic matter.
Keywords Azo dye · Fenton’s reagent · Electro-Fenton
process · Hydroxyl radicals · Water treatment ·
Mineralization · COD
E. Guivarch · M. A. Oturan ())
Laboratoire des Geomateriaux, CNRS FRE 2455,
Universit de Marne La Valle,
5 Boulevard Descartes, Champs sur Marne,
77454 Marne la Valle Cedex 2, France
e-mail: oturan@univ-mlv.fr
Tel.: +33-1-49329065
S. Trevin · C. Lahitte
EDF, Division Recherche et Dveloppement,
Site des Renardires, Route de Sens-Ecuelles,
77818 Moret sur Loing Cedex, France

Introduction
Color is one of the most obvious indicators of wastewater
pollution. The discharges of highly colored dye effluent
can indeed pollute the receiving water bodies. Synthetic
dyes are used extensively by several industries including
textile dyeing (60%), paper (10%) and plastic matter
(10%). The textile industry uses about 10,000 different
dyes. The worldwide annual production of dyestuffs is
over 7105 tons (Poon et al. 1999). It is estimated that 10–
15% of the dye is lost in the effluent during dyeing
processes (Bandara et al. 1996). Furthermore, some azo
dyes, their precursors and a number of their reaction
products are carcinogenic (Brown and De Vito 1993).
Therefore, the treatment of the effluent containing these
compounds is important for the protection of natural
waters.
It is very difficult to successfully treat dye wastewater
using traditional biological processes (Poon et al. 1999).
Dyes are indeed refractory to microbial degradation
because of their substitution groups such as the azo, nitro
or sulpho groups (Nigam et al. 1996). In recent years,
there has been growing interest in finding better ways to
degrade those recalcitrant compounds. Several studies
have shown that oxidation of organic compounds using
Fenton’s reagent (H2O2, Fe2+) is efficient to degrade
organic compounds like azo dyes (Tzedakis et al. 1989;
Oturan and Pinson 1992; Chou et al. 1999; Aaron and
Oturan 2001). Fenton’s reagent is known as a precursor of
the hydroxyl radical .OH, a highly oxidizing agent
(Fenton 1896). The processes based on the production
and the oxidative action of hydroxyl radicals are called
"advanced oxidation processes" (AOPs). They provide a
convenient method for the treatment of undesirable
pollutants. The goal of these processes is to decrease
the strong color of the effluents and their toxicological
effects. This implies the decrease in the dye concentration
below ppm levels.
In this study, we propose the use of an indirect
electrochemical method: the Electro-Fenton process
(EFP) to degrade three azo dyes, azobenzene, methyl

the current is kept constant (60 mA). pore size 0.5 mmol/ L of ferrous iron (Fe2(SO4)3. Electrochemical apparatus and cell Electrolyses were performed with an EG and G Princeton Applied Research 273A potensiostat/galvanostat and were carried out in a cylindrical cell with three electrodes. This potential favors the hydroxyl radicals’ production (Oturan 2000). The counter electrode was a Pt sheet of 5. Oxygen was bubbled through for 10 min prior to the electrolysis to saturate the aqueous solution.8. The working electrode was a carbon felt piece of 60 cm2 (Carbone-Lorraine). and V0 is the volume of the sample. The anodic compartment was filled up with 102 M H2SO4 solution. The degradation was followed by high performance liquid chromatography (HPLC) analyses and chemical oxygen demand (COD) measures. CH3CN/H2O/CH3COOH:27/71/ 2 v/v for methyl orange. 5H2O) was added.5 V/SCE in the cathodic compartment. 10 (30–35). Detection of the intermediates was carried out at the maximal absorption intensity. Solutions were prepared with deionized water (resistivity 18. 80–10 (25–30). This electrode was immersed in a cylindrical anodic compartment separated from the cathodic compartment by a glass frit. Potassium dichromate and ammonium iron(II) sulfate hexahydrate (Mohr salt) Fe(NH4)2(SO4)2·6H2O used for chemical oxygen demand (COD) analysis were purchased from Aldrich. 4-(4-dimethylaminophenylazo)benzoic acid sodium salt (Acros) and p(p-dimethylaminophenylazo)benzosulphonic acid (Merck) and reference compounds for identification of intermediates 4-nitrocatechol and catechol (Acros). The electrical charge consumed was followed by a coulometer. 1. Degradations of 110 mL of aqueous azo dye solutions (pH 2) were monitored by potentialcontrolled electrolysis at 0. is saturated by dioxygen (air) . Runs were performed at isocratic mode. During the Electro-Fenton process. The solution was stirred with a magnetic bar to achieve the transport of electroactive matter toward the cathode. The excess of potassium dichromate was measured out by Mohr salt titration. acetonitrile. Methanol. 0. The volume of samples was 20 mL.cm) from a Millipore Simplicity 185 system. The organic matter was oxidized by potassium dichromate K2Cr2O7 under energetic conditions. The results display the efficiency of the Electro-Fenton process to degrade azo dyes. 5 mm. Under these conditions. around 260–290 nm. Results and discussion Principles of the electrochemically assisted Fenton’s reaction The dye solution.6250 mm column from Merck.5 cm2 area. The temperature was kept constant at 40 C by an L-7350 Merck oven. Experimental Reagents The azo dyes diphenyldiazene (Aldrich). The azobenzene intermediates were separated using the following CH3CN-H2O gradient: vol% CH3CN (min): 10 (0–5).1 M H2SO4. Calibration curves were prepared for the quantitative analysis of azo dyes. COD was calculated from the expression: CODðmg O2 =LÞ ¼ 8000  ðVðMSÞblank VðMSÞsample Þ  NðMSÞ =V0 ð2Þ where V(MS) blank and V(MS) sample are the volumes of standard Mohr salt solution used for the blank and the sample respectively. The temperature of the solution was raised to 170 C over 2 h. the pH is maintained at 2 by addition of 0.4-benzoquinone (Fluka) were used without further purification.5 and 1 mL/ min respectively.2 MW. Chemical oxygen demand Chemical oxygen demand (COD) measurements were carried out using the French AFNOR norm. Flow rate was 0. 10–80 (5–20). Samples were withdrawn from the electrolysis solution at different electrical charge intervals and were microfiltered onto a hydrophilic membrane (Millex-GV Millipore. which already contains a catalytic amount of an iron salt. N(MS) is the normality of the Mohr salt solution.39 orange and p-methyl using hydroxyl radicals produced by Fenton’s reagent according to the following reaction: High performance liquid chromatography Fe2þ þH2 O2 ! Fe3þ þOH þ OH The decay of azo dye concentrations was followed by a reverse-phase high performance liquid chromatography (HPLC) using a Merck Lachrom system equipped with a diode array detector (model L-7455) and fitted with a reverse phase Purospher RP-18. ð1Þ The Fenton’s reagent is generated in situ by electrochemistry. 0. They were studied at their own maximal wavelengths (see first discussion part). Product identification was conducted by comparison of the retention times (tR) with those of authentic standards under the same conditions and by co-injection. 80 (20– 25). hydroquinone (Aldrich). acetic acid and sulfuric acid were purchased at the purest grade (Prolabo). A mineralization reaction pathway was also proposed. A saturated calomel electrode (SCE) from Radiometer was used as reference electrode. 4. The composition of the mobile phase was: MeOH/H2O/CH3COOH:67/21/ 2 v/v for p-methyl red. CH3CN/H2O/CH3COOH:39/59/ 2 v/v for azobenzene.22 mm).

To resolve this issue. Hydroxyl radicals then react on organic compounds by three types of reactions: hydrogen atom abstraction [reaction (5). The production of hydroxyl radicals via electrochemically assisted Fenton’s reaction constitutes a catalytic system. lead finally to the mineral end products (Oturan et al. Figure 2 shows the rapid decay of the azobenzene concentration in the aqueous solution as a . Oturan and Pinson (1995) suggest the formation of H2O2 in several steps: first. The electrochemically assisted Fenton’s reaction was used in the present work for the degradation of the azo dyes azobenzene. l=507 nm. Electrochemical generation of Fenton’s reagent The Fenton’s reagent constitutes an efficient oxidant for a great variety of organic substrates (Tzedakis et al. Hsiao and Nobe 1993). dissolved dioxygen is reduced to superoxide ion. Azobenzene: [diphenyldiazene].000.2. the electrolysis can be realized in an undivided cell where dioxygen is produced in situ by oxidation of water at the Pt anode (Hsiao and Nobe 1993. consequently the hydroxyl radicals. [p-(p-dimethylaminophenylazo) benzosulphonic acid]. Calindo et al. p-methyl red. 1998]: Fig. 2000]. 1 Chemical structure of azo dyes treated by the Electro Fenton process. Reactions are particularly complex and depend on experimental conditions.5 V/SCE) to the working carbon electrode to start the production of the Fenton’s reagent and. Oturan 2000). the first reaction intermediate is a radical species. Colonna et al. the molecular oxygen and ferric ions are simultaneously reduced at the cathode to generate hydrogen peroxide and ferrous ions according to reactions (3) and (4): O2 þ2e þ2Hþ ! H2 O2 ð3Þ Fe3þ þe ! Fe2þ ð4Þ The classical Fenton’s reaction (1) then takes place in solution. 1995. These compounds represent about 60% of azo dye production (Zollinger 1987). 1989. two cathodic reactions take place simultaneously: reduction of dioxygen to hydrogen peroxide (reaction 3) and reduction of ferric ð10Þ Azo dye degradation The Electro-Fenton process has been used to degrade three azo dyes. pKa=3. 1). p-methyl red and methyl orange (Fig.8 ions to ferrous ions (reaction 4). It is sufficient to apply a low cathodic potential (0. molecular oxygen. They are characterized by the presence of an azo bond (–N=N–) attached to two substituents. mainly benzene and naphthalene derivatives. l=465 nm. Do and Chen 1993. e=26. e=22.40 before processing. molecular oxygen. to generate ·OH radicals: Fe2þ þH2 O2 ! Fe3þ þOH þ OH ð1aÞ The ferrous ions produced by reaction (1) are regenerated by reaction (4). l=320 nm.900. At this potential. 2000). methyl orange and p-methyl red. no pollution displacement to another medium and complete degradation of toxic organic pollutants. and electron transfer [reaction (7). The chromatographic survey by HPLC during the entire electrolysis allowed to follow the chemical evolution of the solution as a function of the total electrical charge consumed. The electrochemistry offers the opportunity to produce this reagent in situ in aqueous medium. electrophilic addition on double bond [reaction (6). saturated in oxygen and without any reagent addition except ferric iron as catalyst. containing electron withdrawing and/or donating groups. where they react on the organic compounds present in the medium.300. In all cases. Oturan 2000). e=26. Further reactions. The Fenton’s reagent (H2O2. Thus. the transport of the hazardous oxidant (H2O2) becomes unnecessary. They take place in several steps with hydroxyl radicals. O2· (reaction 8) which react quickly with H+ in acidic medium to produce peroxyl radical HO2· (reaction 9): O2 þe ! O 2 ð8Þ þ  O 2 þH ! HO2 ð9Þ RHþ OH ! H2 O þ R ð5Þ This radical is unstable and finally leads to the formation of hydrogen peroxide: PhXþ OH ! PhXOH ð6Þ 2HO2 ! H2 O2 þO2 RXþ OH ! RXþ þOH ð7Þ However. Brillas et al. 1995. azobenzene. Electrolyses were performed in aqueous acidic medium (pH 2–3). Brillas et al. Fe2+) used in this reaction is generated in situ and in a catalytic way by electrochemistry (Brillas et al. which occur with the participation of hydroxyl radicals. Oturan and Pinson 1995. During the Electro-Fenton process. this approach requires a permanent supply of dioxygen. pKa=5. and the quantity of oxidant can be precisely controlled (Do and Chen 1993. methyl orange. ferrous and /or ferric ions taking part and lead finally to the mineralization of the initial organic compound. 1999]. The hydroxyl radical production takes place in homogeneous solution. Oturan and Pinson 1995). [4-(4-dimethylaminophenylazo) benzoic acid]. ferrous and/or ferric ions. The Electro-Fenton process presents the following major advantages: no addition of chemical reagent except a catalytic quantity of ferrous ions.

245).04 mM) follow an exponential decrease with the electrical charge passed. t1/2 min): azobenzene (0. p-nitrophenol (14. The degradation rate constant kapp and half-life time t1/2 for azo dyes were (kapp min1. the degradation rate constants were higher in both cases (kapp=0. The degradation curves show a pseudo-first order kinetic for the hydroxylation of dye molecules by hydroxyl radicals: d½Dye ¼ k½Dye½ OH ð11Þ dt In the Electro-Fenton process.OH formation rate is controlled by the electrical current developed during  Degradation products The occurrence of new HPLC peaks and a modification in spectral range (260–300 nm) indicate the formation of new structures. the color loss is visually significant for the charge consumed.5 mM.06. Initial concentration C0=0. This kinetic consideration is in agreement with recent works concerning the reaction of hydroxyl radicals with organic compounds (Bandara et al. The p-methyl red and the methyl orange follow a more similar concentration decrease trend than azobenzene. This hypothesis is in agreement with Lagrasta et al.85.OH is a very reactive species. 1. 1. p-methyl red (0. The concentration of these intermediates increases to reach a maximum value and then decreases until disappearance. 275. In order to confirm the azo bond cleavage.29.47.25 min1 for p-methyl red and methyl orange.41 . The cleavage of the azo bond is responsible of the chromophoric characteristic loss and generates the formation of aromatic intermediates. 2000). Eapp=0. (1999). They suggest also that aromatic rings break into fragments.5-trihydroxynitrobenzene (14. This suggests that the removal of the aromatic ring with amino or acetamino substituents is more pronounced. The formation of hydroxylated aromatic derivatives was observed. other authors confirm this tentative assumption (Joseph et al. electrolysis. we tried to identify a large number of compounds which appeared during the electrolysis.5 mM ferric iron concentration because we noted that the current efficiency was optimal with this concentration to promote the electrocatalytic cycle.7). 1996. dye concentrations decrease exponentially and quickly until total disappearance. it not only accumulates in solution. The current being constant (60 mA). 4-nitrocatechol (11. Assuming a firstorder kinetic for the degradation of azo dyes. k being the absolute rate constant (L mol1 s1).45 min. Detection of degradation products such as hydroquinone confirms this hypothesis. Indeed. who have shown that the total organic carbon (TOC) decrease is even more marked during photomineralization for a ring substituted by an amino or actemino group.3. pyrocatechol (6. Both degradation curves of methyl orange (initial concentration=0. Some degradation products formed during the Electro-Fenton process were identified by comparison of their HPLC retention time with those of authentic samples: hydroquinone (tR=3. Joseph et al. 346). d½Dye ¼ kapp ½Dye ð12Þ dt where kapp=k [. 2.75). lmax=290 nm).11. Lin and Lo 1997. Carbon felt cathode. the OH production rate is also kept constant.032 mM.6). The degradation of the initial molecule is complete at 60 coulomb in both cases. than that of the azobenzene (kapp=0. particularly those which contain dialkylamino groups. The electrophilic addition of . 2000). V=110 mL function of the electrical charge passed during the electrolysis and its complete degradation at 60 coulombs. [Fe3+]=0. As . Our results show that the Electro-Fenton process is efficient to degrade azo dyes in aqueous solution and to remove solution color. methyl orange (0. 1. 2 Evolution of aqueous azobenzene solution during the Electro-Fenton treatment. The retention times of all degradation products were . but its concentration takes a steady-state value during the process.OH on the azo double bond leads to its rapid breaking.94.11 min1).1 mM) and p-methyl red (initial concentration=0.OH] is the apparent pseudo-first order rate constant (min1).54). 346). The dye degradation is more efficient in acidic medium due to the better sensibility of the protonated form for oxidation process. using a gradient mode to separate compounds formed. Three electrolyses were carried out with 0. The production and evolution of azobenzene degradation products were followed by liquid chromatography during the electrolysis.5 V/SCE.25.42 and 0. The evolution of chemical composition and the degradation kinetics are similar for the three dye molecules.  Fig.36). respectively). 6. the . 314. For all the compounds.42. Kinetic data show that p-methyl red and methyl orange are easier and faster to degrade by the Electro-Fenton process than azobenzene. time plot in accordance with the equation ln([Dye]/[Dye]0)=kappt. the apparent rate constants were determined analytically from the slope of concentration vs. In all cases.4-benzoquinone (6. The fast bleaching of the solution and the decrease in the absorption band associated with the –N=N– bond corroborate this suggestion.

catechol was also detected by many authors (Hsiao and Nobe 1993. which leads to the formation of the molecules with lower molecular weight in the first step. Oturan et al. we propose a general reaction mechanism for mineralization of azo dye molecules by oxidative action of hydroxyl radicals in the Electro-Fenton process (Fig. organics still in solution are carboxylic acids. The identification of degradation products permits us to prove that the first step of azo dye degradation is the azo bond cleavage and the second step is hydroxyl radical addition on the aromatic ring. 1.4 benzoquinone. quinone. Oturan 2000) in the case of the Electro-Fenton degradation of aromatic compounds. 1995. (2000) and reduction of retention times suggests the formation of derivatives more polar than azobenzene. compounds more polar than azobenzene. . Furthermore. 1998.5 mM. Chemical oxygen demand (COD) decay versus charge during potential controled electrolysis. the azo dye solutions rapidly took a yellowbrown color. though slightly faster at the beginning of the electrolysis. Feng et al.3. The spectral range 260–300 nm was attributed to multisubstituted benzene according to Feng et al. 4-nitrocatechol) suggests that aromatic intermediates are formed by the addition of hydroxyl radicals to azo bond leading to its breaking. 2001). The rate of mineralization is higher at the beginning of electrolysis and diminishes with concentration and changes in structure. It was confirmed by the detection of 1. but complete mineralization remains nevertheless possible. Due to the Fig. For the azobenzene. 4). Thereafter. The decrease in the degradation rate represented by the weakening of the slope (Fig. 3) can be explained by the transformation of the aromatics into aliphatics by ring opening reactions. The COD of the solution decreases regularly with the kinetic rate. Eappl=0. During the electrolysis.5 V/SCE. the mineralization yield is 80% at 5. pnitophenol. which resists to the degradation.42 lower than those of the initial molecule. Chemical oxygen demand Chemical oxygen demand analyses were realized during azobenzene electrolysis to show the mineralization process efficiency of the Electro-Fenton process. the decrease in degradation rate can be influenced by the competition with the reaction (13) when the concentration in organic matter becomes weak.5trihydroxynitrobenzene. Electrolysis of initial azo dye solutions leads to a gradual decrease in chemical oxygen demand (COD) with electrical charge and indicates the mineralization progress. V=110 mL) inactivation of the electrophilic attack centers. The second step is an electrophilic addition of ·OH on the aromatic ring to form hydroxylated derivatives such as 4-nitrocatechol. 2001). pyrocatechol.  OH þ Fe2þ ! Fe3þ þOH ð13Þ The mineralization of azobenzene by oxidative reaction by hydroxyl radicals follows the equation (14): C12 H10 N2 þ68 OH ! 12CO2 þ38H2 O þ 2Hþ þ2NO3 ð14Þ which is equivalent to: C12 H10 N2 þ17O2 ! 12CO2 þ4H2 O þ 2HNO3 ð15Þ The COD abatement suggests that the disappearance of the peaks on HPLC chromatograms is not only due to their transformation into their oxidation intermediates. but is the result of the mineralization process which takes place during the Electro-Fenton process. (2001). Detection of hydroxylated intermediates (p-nitrophenol.5105 M. aliphatic molecules have a lower reactivity toward hydroxyl radicals than aromatic structures. The presence of oxidation products such as phenol. The degradation process seems to occur according to a similar mechanism for all selected dyes. The degradation mechanism was corroborated by other authors (Padjama and Madison 1999. particularly acetic acid. At this electrical charge. 3 Electrolysis of azobenzene. Oturan et al. Detection of a simple substituted aromatic ring such as hydroquinone and decolorization observed in a relatively short time confirm the hypothesis of the azo bond cleavage. Brillas et al. This phenomenon was also reported by different authors (Brillas et al. [Fe3+]= 0.000 coulombs. This hypothesis was also reported by Oturan et al. Mineralization reaction pathway With the results obtained in this work and the examination of intermediary products identified by several authors. the electrophilic addition of hydroxyl radicals to the aromatic ring takes place to form hydroxylated derivatives. which increased in intensity and became colorless again after the passage of 600 coulombs. The brown color was attributed to the formation of benzoquinone by oxidation of hydroquinone in the media. Figure 3 shows the COD decrease as a function of total charge passed during the Electro-Fenton process for azobenzene under conditions described in the experimental part. hydroquinone and pyrocatechol. the overall aromatic compounds are converted to aliphatic derivatives. Initial concentration C0=3. At the end of the bleaching period.

we propose a mechanism reaction pathway for the azobenzene mineralization. Bastide RM. Chen et al. (2000) have also detected some substituted benzene and especially quinones and nitrobenzenes. pyrocatechol. (2001) have shown that the infrared (IR) characteristic peak of the phenyl group disappeared after reaction with ·OH. Morrison C. Indeed. The degradation of the azo dye was not only a break of the azo bond. Savall A (1999) Mechanistic aspects of phenol electrochemical degradation by oxidation on a Ta/PbO2 anode. The chemical oxygen demand measurements indicate an efficient abatement (over 80%) of organic carbon during the Electro-Fenton process. Peral J. Mur E. Pulgarin C.4-benzoquinone. Kiwi J.43 Conclusion Fig. 2000).3. Oturan MA (2001) New photochemical and electrochemical methods for the degradation of pesticides in aqueous media. this novel process can be considered ecologically friendly. References Aaron JJ. as well as CO2 and H2O (Maletzky and Bauer 1998. nitrocatechol. electro-Fenton and photo-Fenton processes. Sanchez L. Tanaka et al. color disappearance and COD decrease in azo dye solutions under study. The degradation of the three azo dyes azobenzene. NO3. methyl orange and p-methyl red were determined under our experimental conditions. Domenech X (1998) Aniline mineralization by AOP’s: anodic oxidation. 4. UV/TiO2 and VIS/TiO2 comparative mechanistic and kinetic investigations. The degradation mechanism begins with the azo bond cleavage and is followed by the hydroxylation of the aromatic ring. (16): Cn Hm Op Nq Sr þ½ðn þ ð5q þ mÞ=4 þð3r  pÞ=2O2 ! nCO2 þqHNO3 þrH2 SO4 þ½ðm  q  2rÞ=2H2 O ð16Þ A proposed mineralization reaction pathway for azobenzene is given in Fig. Sauledad R. but also degradation of the aromatic rings. J Electrochem Soc 142:1733– 1741 Brillas E. photocatalysis. 2000). Joseph et al. According to the experimental results. The evolution of intermediates into their oxidized compounds and decrease in the retention time (HPLC) indicate that the last derivatives before ring opening reactions are more and more polar (hypothesis confirmed by compound identification). Calindo et al. 2000. and SO42 according to the substituent groups included in the initial molecule. The degradation kinetic of azo dyes follows a pseudofirst order reaction in aqueous acid media. Llosa E (1995) Electrochemical destruction of aniline and 4-chloroaniline for wastewater treatment using a carbon-PTFE O2-Fed cathode. Appl Catal A Environ 16:31–42 Brown MA. As hydroxyl radicals are nonselective species. 1. Tr J Chem 25:509–520 Bandara J. p-nitrophenol. De Vito SC (1993) Predicting azo dye toxicity. Jacques P. Kalt A (2000) Photodegradation of the aminoazobenzene acid orange 52 by three advanced oxidation processes: UV/H2O2. J Photochem Photobiol A 99:57–66 Belhadj T. 1. It is also to be mentioned that final degradation products were mineral ions such as NH4+. We have shown that the Electro-Fenton process is efficient for azo dye degradation. the Electro-Fenton process can be generalized for the treatment of wastewater effluents containing toxic organic pollutants. The apparent rate constants for degradation of azobenzene. The general oxidation process for mineralization of azo dyes in the Electro-Fenton process can be summarized by Eq. Some degradation products were identified: hydroquinone. J Electrochem Soc 145:3427–3434 Brillas E. Belhadj and Savall 1999. 4 Proposed reaction pathway for the mineralization of azobenzene by Electro-Fenton process (2000) and Joseph et al. Crit Rev Environ Sci Technol 23:249–324 Calindo C. Acknowledgement This work was supported in part by EDF (Electricit de France). proving that carboxylic intermediates were generated.5-trihydroxynitrobenzene. It is explicitly exhibited by the concentration decrease. simple to handle and economical since catalytic processes are involved and no chemical reagent is needed except molecular oxygen from compressed air. 1998. Peringer P (1996) Degradation/decoloration of concentrated solutions of Orange II. Formic acid and acetic acid are known to be the ultimate organic by-products of aromatic ring opening reactions (Brillas et al. Environmental applications. J Photochem Photobiol A: Chem 130:35–47 . The chemical oxygen demand measurements have shown in this study that the reaction follows an evolution by way of a total mineralization. Kinetics and quantum yield for sunlight induced reactions via Fenton type reagents. methyl orange and p-methyl red by the Electro-Fenton reaction has been studied in aqueous medium.

J Electrochem Soc 140:1632–1637 Feng WD. diazo and reactive dyes.4 D. Nansheng H. Water Res 34:327–333 Tzedakis T. Bonardi M (1999) Photobleaching and photomineralization of azobenzene and substituted azobenzenes in aqueous solution by photocatalytic membranes immobilizing titanium dioxide. Banat I. Huang YH. Caronna T. Savall A.I. Application to the mineralization of an organic micropollutant. synthesis. Process Biochem 31:435–442 Oturan MA (2000) An ecologically effective water treatment technique using electrochemically generated hydroxyl radicals for in-situ destruction of organic pollutants: application to herbicide 2. Chartrin P. reactive red 2 by iron powder reduction and photooxidation in aqueous solution. Bauer R (1998) The photo-Fenton method – degradation of nitrogen containing organic compounds. Hoffman M (2000) The sonochemical degradation of azobenzene and related azo dyes: rates enhancements via Fenton’s reactions. Pinson J (1995) Hydroxylation by electrochemically generated . Clifton MJ (1989) The electrochemical regeneration of Fenton’s reagent in the hydroxylation of aromatic substrates: batch and continuous processes. J Phys Chem 99:13948–13954 Oturan MA. Huang GH.44 Chen F. Nobe K (1993) Hydroxylation of salicylic acid by electrochemically generated ·OH radical. Huang C (1999) Treatment of high strength hexamine-containing wastewater by electro-Fenton method. J Phys Org Chem 12:211–226 Poon CS. Environ Sci Technol 34:3474–3479 Oturan MA. Amsterdam . pentachlorophenol. Madison SA (1999) Hydroxyl radical-induced oxidation of azo dyes: a pulse radiolysis study. Chen CP (1993) In situ oxidative degradation of formaldehyde with electrogenerated hydrogen peroxide. N J Chem 16:705– 710 Joseph J. Lee SN. Chemosphere 41:1233– 1238 Fenton HJH (1896) Oxidation of tartaric acid in presence of iron. Lahitte C. Helin H (2000) Degradation mechanism of azo dye C. Mono -and polyhydroxylation of benzoic acid: products and isomers’ distribution. Lo CL (1997) Fenton process for treatment of desizing wastewater. J Photochem Photobiol 110:201–205 Lin SH. J Chem Soc 65:899–910 Hsiao YL. N J Chem 16:705– 710 Oturan MA. Water Res 33:751–759 Colonna GM. Trevin S (2001) Production of hydroxyl radicals by electrochemically assisted Fenton’s reagent. Xie Y. Chemosphere 38:1005–1014 Tanaka K. Bellobono IR. Hung H. Pinson J (1992) Polyhydroxylation of salicylic acid by electrochemically generated OH· radicals. Peiroten J. Water Res 31:2050–2056 Maletzky P. J Appl Electrochem 19:911–921 Zollinger H (1987) Color chemistry. Fung C (1999) Degradation of cuprophenyl Yellow RL by UV/H2O2/Ultrasonication (US) process in aqueous solution. Marchant R (1996) Microbial process for the decolorization of textile effluent containing azo. Acher AJ (2000) Complete destruction of p-nitrophenol in aqueous medium by electroFenton method. J Photochem Photobiol A: Chem 138:139–146 Chou S. Marcandalli B (1999) Oxidative degradation of dyes by ultraviolet radiation in the presence of hydrogen peroxide. Chemosphere 37:899–909 Nigam P. Singh D.·OH radicals. Zhao J (2001) Photo-Fenton degradation of dye in methanolic solution under both UV and visible irradiation. Destaillats H. Huang QP. J Phys Chem A 104:301–307 Lagrasta C. VCH. J Electroanal Chem 507:96–102 Padjama S. Dyes Pigments 41:211–220 Do JS. Oturan N. Hisanaga T (2000) Photocatalytic degradation of commercial azo dyes. Padermole K. J Appl Electrochem 30:475–482 Oturan MA. properties and applications of organic dyes and pigments.