DOI: 10.

18311/jsst/2019/22232
ISSN (Online) : 0976-9420
J. Surface Sci. Technol, Vol 35(3–4), pp. 120–127, December 2019 ISSN (Print) : 0970-1893

Evaluation of E-Fenton Process in Decolourization

of Azo Dye (Congo Red) using Response
Surface Methodology
S. Sathish1*, J. Aravind Kumar1, D. Prabu1 and G. Narendrakumar2
1
Department of Chemical Engineering, Sathyabama Institute of Science and Technology, Chennai – 600119,
Tamil Nadu, India; sathish.chemical@sathyabama.ac.in
2
Department of Biotechnology, Sathyabama Institute of Science and Technology, Chennai – 600119,
Tamil Nadu, India

Abstract
Today there is a great focus on reusing the effluent water in the dyeing process. The objective of this research work is
to effectively remove colour from textile wastewater using Electro Fenton (E-Fenton) process. E-Fenton process is the
combination of Fenton and electrochemical processes. In this study decolorization of Congo red dye was investigated
by E-Fenton process in a continuous reactor equipped with iron electrodes. Experiments were carried out in a reactor
of working volume of 1L. The degree of decolourisation varies with the operating parameters. The optimal working
conditions were maintained with an electrode potential difference of 2V, 40°C, pH 4. For Electro Fenton’s process the
parameters giving the highest efficiency were decolourisation percentage of 97%. The process parameters were optimized
by using response surface methodology to understand the effectiveness of the interactions of variables when the maximum
decolourization can be achieved. The experimental results proved that the combination of Fenton and Electrochemical
process was an excellent method for treatment of textile wastewater.

Keywords: Congo Red, Decolourisation, Electrode Potential, Electro Fenton

1. Introduction material coloring and paper. It is assessed that 10–15%

Water is the most essential component of life and is
vital for nourishment. Water pollution is a major global
issue which needs evaluation and prevention. Industrial
effluents are one of the significant wellsprings of water
contamination. Wastewater from textile industries cause
hazard to the environment [1]. The dyes utilized in the
material coloring and printing ventures, not exclusively,
can confer shading to water sources yet in addition can
make ecological harm to oceanic living beings by blocking
daylight, in this manner aggravating the regular growth
activity. A portion of the dyes are likewise harmful and
cancer-causing in nature. A small amount of dyes in water
is exceptionally unmistakable and unwanted. Synthetic
dyes are utilized broadly by a few enterprises including
of the color is lost in the emanating amid coloring forms
[2]. The greater part of the dyes utilized in the material
business are exceedingly steady and non biodegradable;
moreover, the utilization of non-controlled oxidative
responses can create harmful by-products [3]. Among
these, some of the dyes are prominent, utilized in textile
dying, because of their chemical stability and versatility.
Azo dyes are having one or more Azo linkages with phenyl,
naphthyl rings that are substituted with functional groups
such as amine, chloro, hydroxyl, methyl and nitro. The
Congo red was used as model of an Azo dye. Congo red
is a benzidine based anionic diazo dye. These colors have
been known to cause an unfavorably susceptible response
and to be used to benzidine, a human cancer-causing
agent. On reduction of Azo groups aromatic amines are

*Author for correspondence

 S. Sathish, J. Aravind Kumar, D. Prabu and G. Narendrakumar

produced which are more toxic compare to the original were set up by dissolving imperative amount of dye in
compounds. The Sulfo groups and Azo groups of the Azo demineralised water.
dyes make the dyes as resistant to oxidative biodegrada-
tion. Congo red is very difficult to expel because of their 2.2  Electro Fenton Treatments
complex aromatic structure [3]. Advanced Oxidation
The experiments were carried out in a partitioned twofold
Process (AOP’s) considered as non-waste generating
electrochemical cell which comprises of 1L glass utensil
technology and an alternative wastewater treatment for
and is furnished with vertical electrodes with an electrode
dye effluent [4]. AOP are utilized to oxidize complex
gap of 5 cm. The cathode and anode were pieces of steel,
organic compounds in wastewaters which are hard to
which were plunged in to the cell. Sigma 30 V, 5A, direct
degrade [5]. AOPs have been used as pretreatment ven-
current RPS was used for providing reasonable voltage
ture proceeding to biological treatment. Fenton process
was connected to the electrodes. The H2O2 concentration
was widely used and has been applicable for textile efflu-
was 5 to 7 mM and was added externally. Based on the
ents [6]. To conquer the hindrances of Fenton process
previous study the reaction was carried out at the pH
an Electro Fenton Process has been developed. Electro
3.0±0.5. The arrangements were blended with a magnetic
Fenton method was used for various kinds of pollutants
stirrer seamlessly at a reasonable speed so the vortex was
such as Pentachlorophenol [7], reactive dyes [8, 9], wash
not made to keep the homogeneity of the electrolyte.
water [10], phenol removal [11], p-nitrophenol [12, 13].
Test samples from the reactor were taken at occasional
The E-Fenton method has favorable position of permit-
interims to examine the remaining dye concentration.
ting a superior control of hydroxyl generation [14]. In the
Tests were centrifuged at 5000 rpm for 10 minutes
E-Fenton process the hydroxyl radical was delivered by
and investigated in an UV/Visible spectrophotometer
reduction on the cathode, then the addition of Fe2+ into
(Varian Cary 100). The shade of dye in the response
the system accelerates the hydroxyl radical similar to
blend was gotten by the proportion of the absorbance
the Fenton reaction. In this study hydrogen peroxide is
at the maximum wavelength (530 nm) and the rate of
externally added while a sacrificial iron anode is used as
decolorization was determined from the underlying
ferrous ion source [15]. The point of this examination is
and last absorbance esteems. The sludge acquired from
to look at the plausibility of utilizing the E-Fenton proce-
the procedures was investigated by Energy-Dispersive
dure to expel Congo red from wastewaters. The impact of
X-beam spectroscopy (EDAX) for elemental composition
parameters, for example, concentration, time, and poten-
determination [16,  17]. Further the examination was
tial difference were analyzed so as to decide the optimized
upgraded utilizing Response surface methodology. Table 1
conditions for decolourization. The present work likewise
demonstrates the structure rundown that with coded
centers on streamlining of procedure parameters utilizing
and genuine estimation of parameters, for example,
Response Surface Methodology (RSM). In these exami-
convergence of color, time and H2O2 concentration. The
nations, the essentials like test setups, primary responses,
plan utilized in RSM was Central Composite Design
and the dynamic parameters that influence these proce-
(CCD) and the structure of trial (DoE) is 20 run. The
dures are talked about in detail.
outcomes from the presentation test were fitted to a
polynomial model, as appeared in Equation (1)
2.  Materials and Methods Y = β0 + β1A + β2 B + β3C + β4 A2 + β5 B2
+β6 C 2 + β7 AB + β8 BC + β9 AC (1)
2.1  Dye and Chemical Reagent
Where, Y is the percentage decolourisation. A, B, and
The Congo red (Azo dye) and the chemicals NaOH, H2O2, C are the coded independent input variables, βo is the
FeSO4.7H2O were of reagent grade. The chemicals and intercept term, β1, β2 and β3are the coefficients showing
reagents used were of AR grade and of high purity which the linear effects, β4, β5, and β6 are the quadratic coeffi-
were purchased from Sigma Aldrich. All the reagents cients and β7, β8 and β9 are the cross product coefficients.

121 Vol 35 (3–4) | 2019 | .J Surface Sci. Technol.

Evaluation of E-Fenton Process in Decolourization of Azo Dye C
( ongo Red) using Response Surface Methodology
Table 1.  Design summary
Study Type Response Surface
Initial Design Central Composite
Factor Name Units High Coded
A Concentration of dye mg/l 1.0
B Time min 1.0
C H2O2 concentration mM 1.0
3.  Results and Discussion
3.1  Effect of Concentration
In E-Fenton process there is significant decolorization.
Figure 1 shows the changes of color removal efficiency
in the synthetic effluent. The effectiveness of color
removal was increased rapidly upto 65% within the first
30 minutes. After that, color removal efficiency gradu-
ally increased and then saturated within 120 minutes.
The 90% color removal was achieved for various con-
centration of dye. As the concentration increased from
100 mg/l to 700 mg/l the percentage decolorization
increased, by further increase in concentration the colour
removal efficiency remained more or less same after 60
min. The increase in dye concentration does not affect the
rate of decolourisation because hydroxyl radicals attack
organic pollutants which produce carbon-centered radi-
cals. With O2, these carbon-centered radicals might be
changed to peroxyl radicals. Every one of these radicals
further respond with the development of increasingly
receptive species prompting synthetic corruption of these
natural mixes. So the ideal focus was taken 500 mg/l for
further investigations.
Figure 1.  Effect of concentration on decolorization of dye.
Vol 35 (3–4) | 2019 |
Runs 20
High Actual Low Coded Low Actual
700 -1 100
60 -1 10
7 -1 5
3.2  Effect of Time
The effect of time on the decolourisation of the syn-
thetic waste water was shown in Figure 2. The maximum
decolourisation efficiency was obtained when the treat-
ment time was 60 minute. The percentage decolorization
increases with increase in the time from 10 min to 60
min which show maximum colour removal. The percent
decolorization becomes constant and represents that all
the hydrogen peroxide has been converted into hydroxyl
radical and their concentration does not change through
the reaction. Thereby the degradation reaction will com-
plete at 60 min [18].
3.3  Effect of Potential Difference
Figure 2 also shows the effect of temperature on the rate
of decolourisation in the E-Fenton process. The optimum
removal efficiency (88%) at temperature of 40°C, poten-
tial difference of 1 volt, a treatment time of 60 minutes,
for initial dye concentration of 500 mg/l was observed.
For the experiment with a temperature value higher than
40°C, the removal efficiency decreases. The other critical
parameter in E-Fenton process is the applied voltage, in
fact that the hydrogen peroxide generation in this pro-
cedure is straight forwardly identified with the applied
voltage. The impact of different voltage esteems on
decolourisation was considered in this study. Figure 2,
demonstrates the proficiency of decolourisation for
electrical potential qualities. As shown in Figure 2, the
greatest expulsion proficiency was equivalent to 88% and
was accomplished at voltage of 2 V, 60°C after 25 min. As
per the outcomes, the potential difference increases, the
removal efficiency increases. At higher voltage the elec-
tro-regeneration of ferrous particles from ferric particle
is overwhelming accordingly the Fenton chain response
increases. Besides, by expanding the connected voltage, a
J. Surface Sci. Technol. 122
 S. Sathish, J. Aravind Kumar, D. Prabu and G. Narendrakumar

higher rate of hydroxyl radicals are created by the degra- peroxide focus will be advantageous for the decolourisa-
dation of hydrogen peroxide; the expansion in hydrogen tion of dye [19, 20].

Figure 2.  Effect of potential difference on decolorization of Congo red dye.

Table 2.  Design of experiment with actual and predicted values

Factor 3 Decolorization
Factor 1 Factor 2
Run C:H2O2
A:Concentration B:Time Actual Predicted
concentration

1 400 35 7.68 38.5 50.4

2 100 60 7 70.5 55.9
3 -104.5 35 6 44.8 47.5
4 700 10 5 32.8 55.8
5 400 35 6 63.7 65.2
6 700 60 5 44.8 52.5
7 400 35 6 61.8 65.2
8 100 60 5 54.6 64.8
9 400 77.04 6 68.4 69.0
10 904.5 35 6 30.2 15.6
11 400 35 6 64.8 65.2
12 700 10 7 37.3 35.5
13 100 10 7 60.3 61.0
14 700 60 7 35.8 38.3
15 400 35 4.31 98.7 75.0
16 400 -7.04 6 88.4 76.0
17 400 35 6 66.2 65.2
18 100 10 5 70.2 76.1
19 400 35 6 066.9 65.2
20 400 35 6 65.8 65.2

123 Vol 35 (3–4) | 2019 | J. Surface Sci. Technol.

Evaluation of E-Fenton Process in Decolourization of Azo Dye C
( ongo Red) using Response Surface Methodology

Table 3.  ANOVA Table

Sum of Mean F p-value
Source Df
Squares Square Value Prob > F
Model 4322.442 9 480.2714 2.347717 0.0244 significant
A-Concentration 1227.104 1 1227.104 5.99847 0.0343
B-Time 59.62538 1 59.62538 0.291468 0.6011
C-H2O2 concentration 728.4878 1 728.4878 3.561077 0.0885
AB 31.60125 1 31.60125 0.154477 0.7025
AC 13.78125 1 13.78125 0.067367 0.8005
BC 18.91125 1 18.91125 0.092444 0.7673
A 2
2038.409 1 2038.409 9.964383 0.0102
B 2
94.98202 1 94.98202 0.464302 0.5111
C2 11.61011 1 11.61011 0.056754 0.8165
Residual 2045.695 10 204.5695
Lack of Fit 2028.142 5 405.6284 115.5417 0.1254 not significant
Pure Error 17.55333 5 3.510667
Cor Total 6368.138 19
Std. Dev. 14.30278 R2 0.978761
Mean 58.225 Adj R 2
0.989646
C.V. % 24.56467 Pred R 2
0.946835
PRESS 15718.77 Adeq Precision 5.97629

3.4  Response Surface Methodology with increase of time the effectiveness of the decoloriza-
tion increases. In the Figure 3(b) the interaction between
The regression equation contain three linear term (A, B, C),
H2O2 concentration and time show there is not much
three square term (A2, B2, C2), and three cross-interactions
variation in the colorization and the Figure 3(c) shows as
(AB, AC, BC) terms plus 1 block term. The empirical
the concentration increase the decolorization decreases.
mathematical model was tested with the ANOVA with
This concludes that the effect of H2O2 will be effective in
5% level of significance. From the interaction the major
lower concentration of dye. Multiple regression analysis
variable were identified as the concentration of dye and
was carried out on the responses to evaluate the adequacy
H2O2 and time (Table 2). The interaction of (a) time
of fit. The coefficients of determination (R2 values) for
and Concentration of dye (b) H2O2 concentration and
the model equation were reported in Table 3. The Model
Concentration of dye and (c) H2O2 concentration and
F-value of 2.347717 implies the model is significant. The
time (Figure 3). The interaction show a better response
coefficient of determination (R2) for the decolourisation
when the concentration of dye is moderate and with
is 97.8% and the adjusted R2 is 98.9% hence the results
respect to the time and H2O2 concentration.
are justified. The linear correlation between the adjusted
Percentage Decolorization = 65.2 − 9.479 A − 2.09 B R2 and predicted R2 indicate that the experimental values
−7.35C + 1.98 AB − 1.312 AC are in good agreement with predicted values. Therefore,
+1.5375BC − 11.89 A2 the models were found to be adequate in representing the
response data of percentage degradation, the dye can be
+2.567 B 2 − 0.897C 2 .
further used for analysis and prediction purposes.
Figure 3(a) represents the interaction of concentra-
tion with respect to time, as the concentration decrease

Vol 35 (3–4) | 2019 | J. Surface Sci. Technol. 124

 S. Sathish, J. Aravind Kumar, D. Prabu and G. Narendrakumar

Design-Expert® Software
is from 6.76 to 3.9%. The increase in the concentration
Decolorization
98.7
of oxygen from 9.07% to 28.07% and iron content from 0
30.2 99
to 41.43% are due to addition of hydrogen peroxide and
X1 = B: Time
X2 = C: H2O2 conc
82
the oxidation of iron electrode. Results confirm that the
Decolorization oxidation process was carried out and the chromophore
Actual Factor 65

A: Concentration = 400.00

of the dye is broken down thereby decolorization of dye

48

was observed.
31

5.00

5.50

6.00
C: H2O2 conc
6.50 10.00
22.50
35.00
47.50
7.00 60.00

B: Time

(a)

Design-Expert® Software

Decolorization
98.7

30.2
99

X1 = A: Concentration
X2 = C: H2O2 conc 81.75

Actual Factor
Decolorization

B: Time = 35.00 64.5

47.25

30

5.00
100.00
Figure 4.  EDAX report of the dye.
5.50
250.00
6.00
400.00
C: H2O2 conc 6.50 550.00
7.00 700.00 A: Concentration

(b)

Design-Expert® Software

Decolorization
98.7

30.2
89

X1 = A: Concentration
X2 = B: Time 74.25

Actual Factor
Decolorization

C: H2O2 conc = 6.00 59.5

44.75

30

100.00
60.00
250.00
47.50

Figure 5.  EDAX report of the sludge obtained by E-Fenton

400.00
35.00
A: Concentration 550.00 22.50
B: Time
process.
700.00 10.00

(c) The sample containing mineralized items was taken

Figure 3.  Effect of process parameters on decolorization after oxidation process, centrifuged and the supernatant
of dye. was exposed to GC examination. The segment utilized
was VF-5 MS 30 m, 0.25 mm measurement with the
3.5 Characterization of Treated Effluent and film thickness of 0.25 micrometer and the section oven
the Sludge was programmed in the range of 70 and 300°C at the
rate of 10°C every moment with the infusion tempera-
The dye and sludge obtained from the Electro Fenton pro- ture of 240°C [21]. The degradation products naphthol,
cess was analyzed by EDAX for elemental composition p-amino benzene sulfonate, ethanol, aniline, formed dur-
determination (Figure 4, 5). The carbon content of the ing the oxidation were affirmed by GC-MS examination
dye was decreased from 63.08% to 20.18% and nitrogen (Figure 6).

125 Vol 35 (3–4) | 2019 | J. Surface Sci. Technol.

avE luation of E-Fenton rP ocess in Decolourization of Azo Dye (Congo Red) using Response Surface Methodology
Figure 6.  GC Analysis of the sample. (a) Before oxidation. (b) After oxidation.
4. Conclusion
Azo dyes are prominently used in textile dying because of
their chemical stability and versatility. On cleavage of Azo
groups, the carcinogenic aromatic amines are produced.
The Azo dye present in the water bodies leads to aesthetic
problem and also public health. In this work the decol-
orization and degradation of Azo dye was analyzed by
E-Fenton process. From the outcomes we reason that by
the E-Fenton treatment of the chosen dye, decolorization
was complete within 40 minutes with the breakdown of
chromophore. EDAX report confirms that the E-Fenton
treatment decolorized the dye solutions as well as miner-
alizes the Azo dye. Validation of the statistical model was
done by running the experiment with the initial concen-
tration of 500 mg/l, at 40°C for 40 minutes which gives
maximum decolorization experimentally. The linear cor-
relation plot between the adjusted R2 and predicted R2
demonstrate that the trial esteems are in great concur-
rence with anticipated quantities as appeared. In this way,
the models were observed to be sufficient in explaining
the degradation rate of the dye.
oV l 35 (3–4) | 2019 |
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