Dyes and Pigments 61 (2004) 287–296

www.elsevier.com/locate/dyepig

Electrochemical degradation of C. I. Acid Orange 7

A. Fernandes, A. Morão, M. Magrinho, A. Lopes*, I. Gonçalves
Department of Chemistry, University of Beira Interior, 6201 001 Covilhã, Portugal

Received 15 September 2003; received in revised form 14 November 2003; accepted 16 November 2003

Abstract
The electrochemical oxidation of C. I. Acid Orange 7 (AO7) was performed on a boron doped diamond electrode
(BDD). Bulk electrolysis was studied using two different supporting electrolytes—KCl and Na2SO4. The influence of
electrolyte concentration, initial dye concentration and current density on the degradation rates was investigated.
Samples were collected at pre-selected intervals and absorbance measurements and chemical oxygen demand (COD)
tests were performed, to compare the rates of colour and COD removal in each case. From the COD measurements
over the time of electrolysis mass transfer coefficients were determined, and the current efficiency was estimated using a
theoretical model. Results have shown an almost complete colour removal and COD removal, higher than 90%. A
preliminary electro degradation study of an effluent from an UASB reactor, used on the biodegradation of a textile
wastewater containing AO7, was also performed with colour and COD removals of 98% and 77%, respectively.
# 2003 Published by Elsevier Ltd.
Keywords: Acid Orange 7; Electrochemical degradation; Diamond electrodes; Wastewater treatment; Dyeing house effluent

1. Introduction Although the biological degradation for organic

pollutants is the most economic process, the
Azo dyes form the largest group among the response of the various types of dyes towards bio-
synthetic colorants (60–70%) [1]. Their chromo- degradation is not consistent. Depending on its
phoric system consists of azo groups (–N¼N–) in solubility and bio elimination characteristics, dyes
association with aromatic systems and auxo- may be precipitated in the clarifier (coagulation/
chromes (–OH, –SO3, etc.). It was estimated that flocculation tank), biodegraded, retained in the
about 50,000 tons of dye are discharged from biomass or overcome to all these processes, giving
dyeing and colouration industries every year [2]. an unwanted colour to the final effluent. In such
Currently, the textile dyeing industry is under cases, colour has to be removed by tertiary treat-
considerable pressure to reduce the colour in ments. Furthermore, even when decolourisation
effluents discharged to municipal wastewater occurs by azo dye reduction in anaerobic environ-
treatment plants or, in case of on-site treatment ments, the resulting aromatic amines, that could
plants, directly to water courses. be mutagenic and carcinogenic, should be miner-
alised in a post-treatment unit [3,4]. Several
* Corresponding author. Fax: +351-275-319-730. wastewater treatment technologies have been
E-mail address: [email protected] (A. Lopes). applied to colour removal, including physical,
0143-7208/$ - see front matter # 2003 Published by Elsevier Ltd.
doi:10.1016/j.dyepig.2003.11.008
288 A. Fernandes et al. / Dyes and Pigments 61 (2004) 287–296

chemical and biological. All of them have (BDD-DiaChem1) as the anode. AO7 was chosen
advantages and drawbacks and a combination of because, being a simple molecule, it is very useful
different technologies is generally required. as test and it is widely used in paperboard
The application of electrochemical techniques as industries, for coloration, and in wool textile dye-
a tertiary treatment to eliminate colour has ing. The effect of the operating conditions, namely
received great attention in the last years [5–8]. the time of electrolysis, the current density and
These techniques use the electron as the main especially the type of supporting electrolyte
reagent, but also require the presence of support- used were investigated, to maximize the rates of
ing electrolytes. In general, the latter exist in the colour and COD (chemical oxygen demand)
wastewaters to be treated, but not always in suffi- removal.
cient concentrations. These processes can operate The electrochemical oxidation of an effluent
at ambient temperature, without the need of arisen from an Upflow Anaerobic Sludge Blanket
temperature control. (UASB) reactor feeding with a basal medium, in
Decolourisation can be achieved either by elec- which glucose was used as carbon source, and
tro-oxidation with non-soluble anodes or by supplemented with AO7 (60 mg/L) was also
electrocoagulation using consumable materials. performed in order to investigate if the result-
The degradation products in the oxidation of azo ing anaerobic dye metabolites could eventually
dyes are typically carbon dioxide, nitrate and sul- be degraded in a sequential electrochemical
phate, with the possible formation of aromatic pos-treatment.
esters, phenols, aromatic carboxilic acids, cyclic A theoretical model developed by Panizza et al.
and aliphatic hydrocarbons, etc., as intermediates. [17], and already tested with several organic pol-
Usually, the oxidation of the azo group occurs, lutants, was used to estimate the current efficiency
followed by the oxidation of the decomposition during the time of electrolysis, using a BDD
products [7]. anode. Efficiency is a very important issue in this
The oxidation rate depends, among other vari- kind of treatment, due to the relatively high costs
ables, on the material of the anode. Different of the electric power. In BDD electrodes the
anodes have been successfully used in the electro- current efficiency is mainly determined by the
degradation of hazardous compounds [9–15]. For occurrence of mass transport limitations of the
industrial applications, materials like noble metals components from the bulk of the solution to the
or dimensionally stable anodes are required to electrode surface; these are expected to be present
obtain suitable oxidation rates. Diamond is in the case of large molecules being processed (due
another choice, specially since it is possible to to their low diffusivities) or chemical species in low
prepare anodes with a relatively large area [16]. concentrations. The latter is usually the case of
Boron doped diamond (BDD) electrodes have dyes, that are generally found in very low con-
demonstrated very good chemical, mechanical and centrations in industrial effluents (i.e., concentra-
thermal resistance, wide electrochemical potential tions of ppm). According to the previously cited
window in aqueous solutions, very low voltam- model, under mass transport control, organic
metric background current, high resistance to compounds are completely mineralised, but sec-
deactivation via fouling, extreme electrochemical ondary reactions (oxygen evolution, electrolyte
stability and no significant corrosion even under decomposition, etc.) can take place, resulting in a
high current densities. These properties of the loss of current efficiency and leading to a decreas-
BDD electrodes meet the requirements for their ing of the removal yield. In this case, the rate of
use as anodes in the electrochemical degradation oxidation of the organic species can be followed
of organic pollutants [16]. by the decrease of the COD, that can be given by
The aim of this work is the study of the electro- the following equation:
chemical degradation as a polishing technology
of a monoazo dye (AO7), using a commercially @COD A km COD
¼ ð1Þ
available boron doped diamond electrode @t V
 A. Fernandes et al. / Dyes and Pigments 61 (2004) 287–296 289

where COD is the chemical oxygen demand

(mgO2/L), t is the time (s), A is the electrode area
(m2), V is the volume of the solution (m3) and km
is the mass transfer coefficient (m s1). Integration
of this equation from t=0 and initial COD (CODi)
to t and COD leads to the following equation:
 
A km Fig. 1. C. I. Acid Orange 7 structure.
COD ¼ CODi exp  t ð2Þ
V
If the applied current density is higher than a
certain limit current density, jlim, defined as [17]: is usually present in the dyeing baths, and the
jlim ¼ ð1=8Þ F km COD ð3Þ later due to its ability of producing chlorine and
hypochlorite during electrolysis.
the electrochemical process is controlled by mass The electro-oxidation of AO7 was investigated
transport, F being the Faraday constant. In this for each electrolyte type and concentration
case, the Instantaneous Current Efficiency (ICE) (Na2SO4 with concentrations ranging from 0.01 to
will be given by [17]: 0.035 M and KCl in concentrations of 0.07 and 0.1
jlim M), for several initial dye concentrations (20–360
ICE ¼ ð4Þ mg L1) and for different current densities (1.25–
jexp
10 mA cm2). Because the electrochemical
where jexp is the applied current density. Other- degradation should also be considered as an alter-
wise, i.e., if the applied current density is lower native treatment of partial residual dyebath
than the limit one, ICE will be 1. streams, all the essays were conducted in duplicate
in the pH range of 3.5–5, analogous to the pH of
dyeing baths. Furthermore, preliminary tests had
2. Experimental shown little influence of the pH on the electro-
chemical degradation rate.
Electrochemical experiments were conducted at During the degradation tests, dye concentration
25  C in a conventional three-electrode cell, with a was determined by spectrophotometry at 482 nm,
working volume of 0.25 L, equipped with an according to Lambert–Beer law, using a Perkin-
external water-jacket to keep constant temper- Elmer Lambda 6 UV/VIS spectrophotometer. A
ature. The bulk electrolysis were performed in dye free cell was used as control.
galvanostatic mode, using a computer controlled Chemical Oxygen Demand tests were also made,
Potentiostat-Galvanostat Tacussel, model PJT according to Standard Methods [18].
35-2.
A boron doped diamond electrode (BDD-Dia-
Chem1), with an immersed area of 10 cm2, was 3. Results and discussion
used as anode and a copper foil (40 cm2) as
cathode. 3.1. Study of the possible degradation of the
The reagent C. I. Acid Orange 7 (Fig. 1), P.A., supporting electrolytes
+85%, from Aldrich, was used without further
purification. A stock aqueous solution of 800 mg The possibility of electrolyte degradation was
AO7/L was prepared, being all the other solutions first investigated, performing the electrolysis of
obtained by an appropriate dilution with the elec- solutions of KCl without the addition of the dye.
trolyte solution. Two different electrolytes were The expected KCl degradation during electrolysis
tested: sodium sulphate (Merck, PA, +99.5%), was confirmed following the OCl presence by
and potassium chloride (Merck, PA, +99.5%). UV-Visible spectrophotometry as shown in Fig. 2.
The former was selected to be studied because it As it can be seen, there is a maximum, at 292 nm,
290 A. Fernandes et al. / Dyes and Pigments 61 (2004) 287–296

Fig. 3. Influence of the electrolyte concentration on the rate of

Fig. 2. UV–visible spectra of a 0.1 M KCl solution submitted degradation of AO7 at a current density of 5 mA cm2, using
to a current density of 5 mA cm2 at t=0 and t=30 min. Na2SO4 as electrolyte and an initial dye concentration of 60
mg L1.
that corresponds to OCl [17]. According to these
authors the electrolysis mechanism is as follows: In the case of KCl, two different concentrations
were also used (0.07 and 0.1 M), for an initial dye
Anode: 2 Cl ! Cl2+2 e concentration of 20 mg L1 and a current density
Cathode: 2 e+2 H2O ! 2 HO+H2 of 5 mA cm2. The results obtained are presented
Overall: 2 HO+Cl2 ! Cl+OCl+2 H2O in Fig. 4. When KCl was used, the electrolyte
concentration seems not to alter the rate of dye
Accordingly, when the electrolyte was KCl, all degradation, in the range of concentration tested.
the UV–visible measurements were made against a So it may be concluded that, for KCl, the con-
KCl degraded solution, instead of deionised water. centrations to be used in practice can probably be
The same procedure was followed for Na2SO4 decreased.
solutions, but no degradation was observed. In Fig. 5, results obtained with both electrolytes,
at an initial dye concentration of 20 mg L1 and a
3.2. Effect of the electrolyte type and current density of 5 mA cm2, are presented. It
concentration may be concluded that, in general, the AO7
degradation is faster when KCl is used as electro-
The influence of sodium sulphate concentration lyte. However, the use of KCl involves the possi-
on the AO7 degradation rate was tested for three bility of the formation of organochloride
different solutions (0.01, 0.02 and 0.035 M), with compounds, mainly due to the OCl presence, as a
an initial dye concentration of 60 mg L1 and a possible side reaction. In that case, the formation
current density of 5 mA cm2 (see Fig. 3). Using of those unwanted compounds can only be pre-
Na2SO4 as electrolyte, it seems that for con- vented if the complete mineralization of the
centrations higher than 0.02 M, there is no influ- organic compounds is assured, i.e., for high
ence of the electrolyte concentration on the rate of enough times of electrolysis. UV–visible spectra
colour removal. For lower concentrations, there is from samples gathered throughout the reaction
a decrease of that rate, probably because there are time seem to indicate an almost complete degra-
not enough ions to conduct the current. Thus it dation of dye molecule (Fig. 6), for an initial dye
may be concluded that the increasing of the elec- concentration of 40 mg L1.
tric resistance of the solution affects negatively the The KCl concentrations were higher than those
efficiency of the process. of Na2SO4 for two main reasons: first, KCl is a 1:1
 A. Fernandes et al. / Dyes and Pigments 61 (2004) 287–296 291

Fig. 4. Influence of the electrolyte concentration on the rate of Fig. 5. Influence of the electrolyte, Na2SO4 and KCl, on the
degradation of AO7 at a current density of 5 mA cm2, using rate of degradation of AO7: initial dye concentration 20 mg L1,
KCl as electrolyte and an initial dye concentration of 20 mg L1. current density 5 mA cm2.

electrolyte and needs higher concentration for Once again, the charge needed for the electro-
same number of charges in solution; and second, chemical degradation of a certain amount of dye is
the purpose of testing KCl was a different one, lower when KCl is the electrolyte.
because the main idea was to use it as electrolyte The electrochemical degradation of AO7, in
and, simultaneously, verify the ability of hypo- Na2SO4 0.035 M, was also studied for initial dye
chlorite to oxidize the organic compounds, helping concentrations in the range from 150 to 360 mg
the electrochemical degradation, even at very low L1 and a current density of 10 mA cm2. The
dye concentrations. results obtained are presented in Fig. 8 and con-
clusions are similar to those obtained for a lower
3.3. Effect of AO7 initial concentration dye concentration, although, for 360 mg L1, the
beginning of the electrochemical reaction is under
The influence of the initial dye concentration kinetic control, since the applied current density is
was studied, for concentrations ranging from 20 to lower than the limit density current for the initial
100 mg L1, in solutions containing as electrolyte COD (jlim ffi 13 mA cm2).
Na2SO4 (0.035 M) or KCl (0.1 M). These electro-
lyte concentrations were chosen because it was 3.4. Effect of current density
made clear in previous discussion that they were
high enough to guarantee no influence on the The effect of current density for an AO7 initial
degradation rate. Results are presented in Fig. 7 concentration of 20 mg L1 was studied using
and it may be concluded that the colour removal Na2SO4 (0.035 M) as electrolyte (Fig. 9). For
yield increases with initial dye concentration. This the studied current densities, it can be seen that the
fact strongly suggests that, under these conditions, charge needed for an equivalent decrease in
the rate of degradation of the dye is controlled by concentration increases with current density and
mass transfer limitations; in that situation, the the rate of colour removal is almost independent
AO7 concentration at the interface becomes zero of the current density. This is probably because the
because the electrochemical reaction rate is higher oxidation rate is being controlled by the diffusion
than the diffusion rate, thus making the degrad- of AO7 molecules from the bulk to the interface
ation rate proportional to the bulk concentration. anode/solution and not by the electrons flow rate.
292 A. Fernandes et al. / Dyes and Pigments 61 (2004) 287–296

Fig. 6. UV–visible spectra of a 40 mg AO7/L solution in Na2SO4 0.035 M, submitted to a current density of 5 mA cm2, at different
times.

Fig. 7. Influence of the initial dye concentration on the degradation rate of AO7, at a current density of 5 mA cm2
, with two different
electrolytes: (a) 0.035 M Na2SO4; (b) 0.1 M KCl.

3.5. Rate of COD removal and mass transfer Spectrophotometry, was also analyzed by COD
coefficients tests.
Adjusting Eq. (2) to the experimental values of
For initial dye concentrations ranging from 150 COD versus time, for the various essays, an aver-
to 360 mg L1 degradation tests were conducted at age mass transfer coefficient of 1.46105 m s1,
10 mA cm2 current density and using a 0.035 M with a standard error of 3107 m s1, was
Na2SO4 solution as supporting electrolyte. The obtained. Experimental results, as well as the
rate of the electrochemical degradation of AO7, fitting curves, are presented in Fig. 10a. In Fig. 10b,
besides being followed by Ultraviolet-Visible the Instantaneous Current Efficiency (ICE),
 A. Fernandes et al. / Dyes and Pigments 61 (2004) 287–296 293

calculated as the ratio jlim/jexp [Eq. (4)], is made, as in Fig. 11, it can be clearly seen that the
presented as a function of time. Except for the rate of COD removal is lower than that of colour,
beginning of the test with 360 mg L1 initial dye suggesting that the cleavage of the azo bond is the
concentration, all the experiments were run under first step of the electrochemical degradation
diffusion control conditions. For that particular mechanism. Only after that, the aromatic rings are
essay, and during a certain initial period of time, prone to be degraded, thus contributing to the
the electrochemical degradation is under kinetic continuation of the COD removal. A similar
control, thus allowing efficiency to be maximum. degradation mechanism is known that occurs in
If a comparison between percentage of COD the biological anaerobic treatment of this type of
removal and percentage of colour removal is dye, although, in this case, the cleavage of the azo
bond is obtained by a reduction reaction, giving
sulphonated aromatic amines, which are very
resistant to the biological treatments [3,19].

3.6. COD and colour removal of an effluent from

an UASB reactor

Preliminary tests on the electrochemical degra-

dation of an effluent arisen from an Upflow
Anaerobic Sludge Blanket (UASB) reactor feeding
with a basal medium in which glucose was used as
carbon source and supplemented with AO7 (60
mg/L) were also carried out. A BDD anode with
an immersed area of 15 cm2 was used in the elec-
trochemical degradation of 275 mL of this efflu-
ent, with an applied current density of 6.7 mA
Fig. 8. Influence of the initial dye concentration on the rate of cm2 for 10 h. The effluent was previously filtered
degradation of AO7: 0.035 M Na2SO4 as electrolyte; current in glass micro filters (GF/C) for suspended solids
density 10 mA cm2. removal and no electrolyte was added. Results

Fig. 9. Variation of AO7 concentration with the charge passed (a) and time of electrolysis (b) during the degradation essay, using
0.035 M Na2SO4 as electrolyte and initial dye concentration of 20 mg L1.
294 A. Fernandes et al. / Dyes and Pigments 61 (2004) 287–296

Fig. 10. Variation of COD (a) and ICE (b) with time for three different initial concentration of AO7, using as electrolyte 0.035 M
Na2SO4 and 10 mA cm2 current density: (a) symbols: experimental; lines: fitting assuming diffusion control.

Fig. 11. Comparison between percentage of colour and COD removal for the degradation essays performed with different initial dye
concentration, at 10 mA cm2 in a 0.035 M Na2SO4 electrolyte solution.

indicate (Fig. 12) significant alterations on UV– 4. Conclusions

visible spectra, suggesting that aromatic amines
resulting from dye reduction in anaerobic condi- The electrochemical method, using a BDD
tions were almost mineralised, along with degra- anode, has been employed in the present study to
dation of residual glucose and biomolecules (cell mineralize a monoazo dye, AO7. Degradation of
metabolic compounds) that also contribute to the the dye was followed by UV–visible spectro-
total COD. A COD and a color removal rates of photometry and COD determinations. An almost
77% and 98% were achieved, respectively. In complete colour removal and very high COD
these essays a dye free run was also studied and removal are obtained using this technique. Several
used as blank to the spectrophotometry analysis. aspects, such as type and concentration of the
 A. Fernandes et al. / Dyes and Pigments 61 (2004) 287–296 295

Suisse d’Electronique et de Microtechnique SA

(CSEM), are gratefully acknowledged.

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