IJSRD - International Journal for Scientific Research & Development| Vol.

1, Issue 10, 2013 | ISSN (online): 2321-0613

Treatment of organic content at high Total Dissolved Solids

By Electrochemical Oxidation
Imranul Islam Laskar1 Deepak Ramachandran O.2
1,2
Dept. of Chemical Engineering, Sathyabama University, Chennai, India

Abstract--- The electrochemical treatment of synthetic

wastewater with salinity of 330 g NaCl/L and organic load

of up to 3200 mg COD/L was investigated. The effects of
important parameters like pH, temperature, potential,
current, reaction time, and initial organic concentration were
studied using graphite electrodes. Tween80 and phenol were
used as organic pollutants for the preparation of the
synthetic wastewater. The best reduction in COD was
observed at pH 6.0 for phenol and 6.4 for tween80,
temperature of 10C, potential of 4.0V(tween80) and
3.0V(phenol), current of 0.2A(tween80) and 0.3A(phenol),
and reaction time of 60 minutes. The variations were
depicted using State-Ease Design Expert software trail
version 8.0.6 and response surface methodology (RSM).
Total current efficiency (TCE), anode efficiency (AE) and
energy consumption (EC) were also most desirable at these
optimum conditions. Reaction kinetics reveal that the
electro-oxidation here follow the pseudo-first-order model.
Negative values of S and H for both phenol and
tween80 indicate that at lower temperatures the reaction is
feasible and spontaneous so as to make G negative. Using
these optimized parameters, significant reduction in COD of
up to 100% was achieved in a real saline wastewater with
COD of up to 1100 mg/L.
Keywords: Electrochemical treatment of synthetic saline
wastewater, Modified method, real saline sample, Response
surface methodology.
I. INTRODUCTION
Saline wastewater is generated from many industrial sectors
like textile, petroleum, petrochemical, leather etc. All these
sectors generate very large amount of saline wastewater,
rich in both salt (NaCl) and organic matter. When this
wastewater is discharged into the environment without prior
treatment, it can cause severe damage to the aquatic life,
water potability and agriculture by contamination of soil,
surface and groundwater [1]. Biological treatment of saline
wastewater results in poor removal of chemical oxygen
demand (COD) due to the inhibition by high salt content
[2]-[5]. Due to high conductivity in saline wastewater with
the presence of anions and cations, electro-oxidation
treatment might be a favorable route [6]. Several studies
have been carried out on the electro-oxidation of different
organic compounds and anode materials [7], [8]. This
method also has been successfully applied for the treatment
of saline wastewater in textile industry, tannery, distillery,
domestic sewage and landfill leachate [9]-[16]. Graphite
electrodes have been widely used recently, for organic
removal because of its low cost. It has large surface area and

high current efficiency compared to other electrodes [10]. In

graphite electrodes, oxidation is dominated mainly by
physisorbed active oxygen hydroxyl radicals. These
hydroxyl radicals cause the complete destruction of organic
matters. However, the relatively poor service life due to
surface corrosion especially when the electro-oxidation is
conducted at high potential is the notable short-coming of
graphite electrode. But here since the potential for the
operation is optimized to 3 - 4V only, the short-coming can
be neglected.
In the electrochemical oxidation, organic pollutants are
removed by electro-generated oxidizing agents like chlorine
and hypochlorite [17]. In general, the following reaction
takes place during electro-oxidation using graphite
electrodes in the presence of sodium chloride, magnesium
chloride, calcium chloride and ammonium chloride.
At the anode:
2Cl- Cl2 + 2e-

(1)
-

(2)

2H2O + 2e- H2 + 2OH-

(3)

4OH O2 + 2H2O + 4e
At the cathode:

In the undivided cell, chlorine formed at the anode and

hydroxides formed at the cathode react to form chloride and
hypo chlorites. Both the hypochlorite and free chlorine are
chemically reactive and oxidize the organic pollutants in the
effluent to carbon dioxide and water [14].
HOCl is then formed.
Cl2 + H2O H+ + Cl- + HOCl

(4)

The HOCl dissociates into OCl and H ions.

HOCl H+ + OCl-

(5)

These hypochlorite ions act as the main oxidizing agent in

the organic degradation.
The overall desired reaction of electrolysis is:
Organic matter + OCl- Intermediates
-

Intermediates CO2 + Cl + H2O

(6)
(7)

The other important products of electrolysis include Cl2,

ClO2, O3, OH., O., ClOH., H2O2, O2, H2 and CO2. Due to the
high oxidation potential of the radicals, they may undergo
decomposition to produce other oxidants which may oxidize
the organic compounds. This process is called direct
oxidation. The primary (Cl2 and O2) and secondary (ClO2,
O3 and H2O2) oxidants have long life. They are capable of
diffusing into the areas away from the electrodes and
continue to oxidize the pollutants [18].

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Treatment of organic content at high Total Dissolved Solids By Electrochemical Oxidation

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In the classical method of optimization one parameter is

varied at a time while the other being constant. However,
the classical method is unable to understand the complex
interactions between the variables and the response.
Response surface methodology (RSM) is an effective
statistical tool for collection of mathematical and statistical
information useful for developing, improving and
optimizing processes and can be used to evaluate the relative
significance of several parameters in complex interactions
[19]. Here, after the parameters have been optimized, RSM
was used for graphical representation and generation of
mathematical relation of the parameters with the response.
Present work investigates the effectiveness of the critical
parameters such as pH, current, potential, temperature and
reaction time in chemical oxygen demand (COD) reduction
by electro-oxidation of synthetic saline wastewater using
graphite electrodes and the variations in total current
efficiency (TCE), anode efficiency (AE) and energy
consumption (EC). Scope of this work also includes
optimization of the process using RSM; finding a modified
method suitable for COD analysis of sample with salt
content of 330g NaCl/L and COD of up to 3200 mg/L; study
of reaction kinetics and thermodynamic parameters of the
process; and electro-oxidation of a real saline reject water
using the optimized conditions.
II. MATERIALS AND METHODS
A. Electro-oxidation cell
A cylindrical vessel of 100 mL working volume
(Length=5cm, Breadth=3.5cm, Height=8cm) was used as
the electro-oxidation cell as in Fig. 1. Graphite electrode
with a diameter of 1 cm was used as an anode and stainless
steel (SS304) of same diameter as the cathode. The
electrodes were arranged parallel to each other with a
constant electrode gap of 1 cm. The electric power supply
was provided by laboratory A.C. to D.C. convertor power
source equipped with currentvoltage monitoring. For
temperature studies, a separate electro-oxidation cell was
used with a provision for jacketed water flow at varying
temperature.
B. Synthetic wastewater

Fig. 1: Schematic diagram of electro-oxidation cell.

The synthetic wastewater prepared here was a prototype of
reverse osmosis (RO) reject in leather industry with COD in
the range of 2800-3200 mg/L and inorganic composition as
follows: NaCl: 330 g/L, CaCl2: 16.5 g/L, MgCl2: 6.624 g/L,
and NH4Cl: 0.486 g/L. The organic compounds taken in this
study were: phenol and tween80 as both are major organic

pollutant in the RO reject stream. For pH studies, the pH of

the synthetic salt was altered using either NaOH or HCl. The
salts used here were from Hi-Media Laboratories and of
analytical (AR) grade.

Fig. 2: Electro-oxidation cell for temperature studies.

C. Analysis of wastewater
COD is the main pollution parameter and was analyzed
following the standard procedure as reported by American
Public Health Association [20]. Mercuric sulphate is used to
mask the chloride interference in COD estimation. However,
there are limitations when measuring the organic matter in
wastewater samples with chlorides higher than 2000 mg/L
using the standard method. This is due to the oxidation of
chloride ions expressed by the following equation:
(8)
Cr2O72- + 6Cl- + 14H+ 3Cl2 + 2Cr3+ + 7H2O
The standard method suggests the use of a HgSO4: Cl ratio
of 10:1 when the chloride concentration is up to 2000 mg/L
in order to mask the excess of chloride by the formation of
HgCl2. However, many researchers have found that this
ratio (10:1) in samples with chlorides more than 2000 mg/L
contributed to a significant error at low and moderate CODs
[21]-[24]. Here with chlorides higher than 330 g/L, even a
high dilution of the samples does not eliminate the problem
as the organics are diluted accordingly. These existing
methods have substantial errors, mainly in the range of low
organic concentrations with high salinity. A modified
method, which will enable the range of the standard method
to be extended up to 40 g NaCl/L with low COD values
(less than 230 mg COD/L), with error less than 10% in
contrast to an error of about 50-85% with the standard
method, was applied here [25]. However, this only solves
the problem for low organic concentrations with high
salinity. Here the synthetic saline wastewater contains both
the inorganic and organic matter in high amount. We found
that following the modified procedure together with dilution
of the sample and ferrous ammonium sulphate (FAS), error
was minimized to 1%.
D. Experimental Design
Central composite design (CCD) and RSM has been used to
design the experiments. Five factors were used in this study
based on RSM and a total of 50 experiments were
summarized by the trail version of Stat-Ease Design
Expert V8.0.6 Software. Here, we conducted experiments
based on our assumptions, then optimized each parameter
step by step. Later, the software was run and the response
for COD was given in accordance with the experimental
results. Analysis Of Variance (ANOVA) was done for the

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Treatment of organic content at high Total Dissolved Solids By Electrochemical Oxidation

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justification of the model. Five factors: current,

initial organic concentration per liter of the
wastewater, time and pH were selected as
whereas, COD removal efficiency from the
wastewater was the response.

potential,
synthetic
variables,
synthetic

E. Anode efficiency, total current efficiency (TCE), and

energy consumption
Using (9), (10), and (11), we calculated anode efficiency,
TCE, and energy consumption at optimum conditions for
COD removal [26], [27].
(9)
[

(10)

where CODt and CODt+t are chemical oxygen demands at

time t and t+t in gram of O2 per dm3 respectively; F is
Faradays constant (96,487 Cmol-1); V is the volume of
electrolyte in liters and I is the current in Ampere and 8 is
the oxygen equivalent mass (g/equiv.-1).
(11)
where t is the time of electrolysis in hours, V is the average
cell voltage, I is the current in Ampere, Sv is sample volume
in litres and COD is the difference in COD in time t in
mg/L.
F. Reaction kinetics
In order to investigate the electrochemical oxidation of the
prepared synthetic wastewater, pseudo-first-order and
pseudo-second-order integral equations were used [28].
The integral pseudo-first-order equation is given as:
(12)
where rt is the COD reduction capacity at time t (mg/L), re is
the COD reduction capacity at equilibrium (mg/L), kf is the
pseudo-first-order rate constant (min-1), and t is the
electrolysis time (min).
The pseudo-second-order model is represented as:
(13)
where ks is
(L/mg.min).

the

pseudo-second-order

rate

constant

G. Estimation of thermodynamic parameters

The Gibbs free energy change of the electrochemical
process is related to the equilibrium constant by the classic
Vant Hoffs equation:
(14)
According to thermodynamics, the Gibbs free energy
change of the electrochemical process is also related to the
entropy change and heat of reaction at constant temperature
by the following equation:
(15)
Combining the above two equations, we get

(16)
where G is the free energy change (kJ/mol), H is the
change in enthalpy (kJ/mol), S is the entropy change
(kJ/mol K), T is the absolute temperature (K) and R is the
universal gas constant (8.314 J/mol.K). The above equation
can be plotted using lnK as y-axis and 1/T as x-axis; hence
H and S are then calculated.
III. RESULTS AND DISCUSSION
A. Model fitting and ANOVA
The response(y) of COD by electro-oxidation experimental
data were fitted to quadratic model to obtain the
regression equations, sequential model sum of
squares, model summary statistics and subsequent
ANOVA were tested and it was found that the
quadratic model most suitably described the COD
values obtained from the experiments. The quadratic
equation obtained in terms of coded factors is given
below:
For phenol synthetic saline solution:
y = 916.75 + 717.74X1 + 38.25X2 656.37X3 76.89X4
64.18X5 + 99.38X1X2 70.63X1X3 44.38X1X4
43.12X1X5 + 104.38X2X3 21.87X2X4 +
6.88X2X5 11.87X3X4 75.62X3X5 84.37X4X5
+ 274.11X12 + 109.71X22 + 231.69X32 + 54.91X42
+ 61.98X52.
(17)
For tween80 synthetic saline solution:
y = 806.5608164 + 261.0501133X1 163.259299X2
335.9547309X3 + 192.3746207X4 116.6477117X5
83.75X1X2 127.5X1X3 30.625X1X4
93.125X1X5 +
47.5X2X3 + 75.625X2X4
24.375X2X5 5.625X3X4
5.625X3X5 +
22.5X4X6 + 41.25829025X12 29.45238787X22 +
233.9448881X32
+
48.32935806X42
+
1.483533804X52.
(18)
The ANOVA of COD values with respect to various
parameters after electro chemical oxidation showed model
F value of 13.21(phenol) and 14.28(tween80) for the
quadratic model, implying that the model is significant as
shown in Table I and II. A prob>F lower than 0.0500 for
the quadratic model indicates that the model terms are
significant. The ANOVA table for phenol saline solution
obtained from the response surface quadratic model shows
that the parameters concentration, time, (concentration)2
and (time)2 are the significant terms and for tween80,
concentration, time, pH,voltage,current,concentration*pH,
concentration*current, concentration*time and (time)2 are
the significant terms. Adequate Precision measures the
signal to noise ratio. A ratio more than 4 is desirable. For the
present study signal to noise ratio was found to be 14.578
for phenol and 17.530 for tween80 indicating adequate
signal. Therefore quadratic model can be used to navigate
the design space to optimize the operational parameters.
According to normal probability, studentized residuals and
outer-t residual plots which are not shown here, the
quadratic model well satisfied the ANOVA. R2 is a
statistical measure of how well the regression line
approximates the real data points. An R2 of 1.0 indicates that

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Treatment of organic content at high Total Dissolved Solids By Electrochemical Oxidation

(IJSRD/Vol. 1/Issue 10/2013/0041)

the regression line perfectly fits the data. The R2 value

obtained here is 0.9011 for phenol and 0.9078 for tween80
which indicates that there is a good co-relation between the
observed and predicted values of COD.
Source

Sum of
squares

D
F

Mean
square

F value

Model

493422
00.4

2
0

246711
0.02

13.2132
575

X1
concentra
tion

pvalue
Prob
>F
<0.00
01

initial phenol concentration of 0.5ml/L. It follows the same

trend for tween80. As time increases, more OCl- and other
radicals are formed for oxidation, thereby reducing COD.
These variations were noted by keeping the other parameters
like current, potential, temperature and pH at their optimized
values. However, the reaction time was optimized at 1 hour
so as to reduce power consumption since beyond that period
COD reduction was found to be minimal.

Signifi
cant

pvalue

Source

Sum of
squares

D
F

Mean
square

F value

Model

158662
04

20

793310
.2

14.284
49

<0.000
1

Significa
nt

X1

concentrati
on

295170
6

295170
6

53.148
97

<0.000
1

Significa
nt

X2 pH

115446
6

115446
6

20.787
53

<0.000
1

Significa
nt

X3 time

488862
7

488862
7

88.025
52

<0.000
1

Significa
nt

X4

potential

160295
3

160295
3

28.863
08

<0.000
1

Significa
nt

589356.
1

589356
.1

10.612
06

0.0029

Significa
nt

X1X2

224450

224450

4.0414
88

0.0538

X1X3

520200

520200

9.3668
18

0.0047

X1X4

30012.5

30012.
5

0.5404
11

0.4682

X1X5

277512.
5

277512
.5

4.9969
42

0.0333

X2X3

72200

72200

1.3000
47

0.2635

X2X4

183012.
5

183012
.5

3.2953
57

0.0798

X2X5

19012.5

19012.
5

0.3423
43

0.5630

X3X4

1012.5

1012.5

0.0182
31

0.8935

X3X5

1012.5

1012.5

0.0182
31

0.8935

X4X5

16200

16200

0.2917

0.5933

X12

94591.9
9

94591.
99

1.7032
41

0.2021

X22

48202.8
7

48202.
87

0.8679
5

0.3592

Table 1: ANOVA for Response Surface Quadratic Model

(Phenol)

X32

304129
8

304129
8

54.762
18

<0.000
1

B. Effect of various parameters

The effects of various parameters on COD removal were
analyzed using 3-D graphs with contour plot. Fig. 3 shows
the effect of time(X3) and concentration(X1) on COD
reduction for phenol. At higher concentrations of phenol,
COD increased expectedly from 2800mg/L for 1.5ml/L to
1200mg/L for 0.5ml/L after 5 min. reaction time. From Fig.
3 it can be noted that there is a drastic reduction in COD
until 60 min., no appreciable removal of COD happens after
that period. With 2 hour electrolysis time, COD reaches only
up to 320mg/L where after an hour it is 380mg/L for an

X42

129793.
8

129793
.8

2.3370
91

0.1372

X52

122.300
1

122.30
01

0.0022
02

0.9629

Residual

161055
8

29

55536.
47

Lack of fit

161055
8

22

73207.
17

Pure error

X2 pH
X3 time
X4
potential
X5
current
X1X2
X1X3

223133
93.4
63370.6
259
186604
98.8
256055.
636
178428.
499
316012.
5
159612.
5

1
1
1
1
1
1
1

223133
93.4

119.505
255

<0.00
01

63370.6
259
186604
98.8
256055.
636
178428.
499
316012.
5
159612.
5

0.33939
808
99.9412
162
1.37137
34
0.95562
083
1.69248
818
0.85484
679
0.33748
004
0.31873
487
1.86708
607
0.08201
013
0.00810
059
0.02416
788
0.98017
165
1.22010
985
22.3618
63
3.58211
591
15.9753
245
0.89728
779
1.14327
251

0.564
7
<0.00
01
0.251
1
0.336
4
0.203
5
0.362
8
0.565
8
0.576
7
0.182
3
0.776
6
0.928
9
0.877
5
0.330
3
0.278
4
<0.00
01
0.068
4
0.000
4
0.351
3
0.293
8

X1X4

63012.5

63012.5

X1X5

59512.5

59512.5

X2X3

348612.
5

348612.
5

X2X4

15312.5

15312.5

X2X5

1512.5

1512.5

X3X4
X3X5
X4X5
X12
2

X2

X3

X42
X52
Residual
Lack of
fit
Pure
error

4512.5
183012.
5
227812.
5
417528
9.56
668833.
86
298282
8.64
167536.
861
213465.
836
541472
7.62
540192
7.62
12800

1
1
1
1
1
1
1
1
2
9
2
2
7

4512.5
183012.
5
227812.
5
417528
9.56
668833.
86
298282
8.64
167536.
861
213465.
836
186714.
745
245542.
165
1828.57
143

134.280
871

<0.00
01

Signifi
cant

Signifi
cant

X5
current

Signifi
cant

Signifi
cant

Signifi
cant

Prob>
F

Significa
nt

Significa
nt

Significa
nt

Table 2: ANOVA for Response Surface Quadratic Model

(Tween80)

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Treatment of organic content at high Total Dissolved Solids By Electrochemical Oxidation

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From Fig. 5, it can be noted that higher pH favors COD

Removal. This is due to the release of more OCl- ions at
alkaline medium and also increased rate in (5) in the
forward direction. Same variation was also observed in [29].
Increase in current also led to an increase in COD reduction
due to the release of chlorine gas at the anode and
subsequent formation of hydroxides at the cathode. Both
react to form hypo chlorites which oxidize the organic
pollutants to CO2 and H2O. Other oxidizing agents formed
here are: ClOH., ClO2. Native pH of 6.0 for phenol and 6.4
for tween80 in the synthetic saline wastewater was
optimized here since it gave a favorable COD reduction.
From an economic point of view, current optimization at
0.3A for phenol was done.
Fig. 3: COD removal response plot between time and
concentration (phenol).

Fig. 4: COD removal response plot between potential and

concentration (phenol).
Fig. 4 shows the effect of potential(X4) and
concentration(X1) on COD removal for phenol. The
concentration variations is similar to Fig. 3. Effect of
potential in COD removal is negligible for 1ml phenol/L.
Current and potential was optimized at 3V and 0.3A for
phenol since the power consumption would be less and also
desirable COD level was attained. For tween80, optimized
potential and current were 4V and 0.2A respectively.

Fig. 6: COD removal response plot between current and

time (tween80).
Fig. 6 depicts a similar response for tween80 with COD
reduction being negligible at reaction time more than 60
minutes and current being directly proportional with COD
removal due to increased rate of hypo chlorites at higher
current, therefore better reduction but was optimized at 0.2A
for the process to be economically viable.
C. Thermodynamic studies
The thermodynamic parameters S and H were found to
be -26.1891kJ/mol.K (phenol), -15.71kJ/mol.K (tween80)
and -7045.2836kJ/mol (phenol), -3926.536kJ/mol (tween80)
from the graphs intercept and slope as shown in Fig. 7 and
8. Since both the parameters are negative, therefore for the
system and the electro-oxidation to be spontaneous, lower
temperature is favorable as higher temperature results in
non-spontaneity.

Fig. 5: COD removal response plot between current and

concentration (tween80).

These can be noted from (12) and (13) where the TS term
must be greater than the H term for G to be negative. A
negative G indicates the feasibility and spontaneity of the
process. Also, according to Le Chateliers principle, since
the process here is exothermic (H negative), lower
temperature is favorable.

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Treatment of organic content at high Total Dissolved Solids By Electrochemical Oxidation

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Fig. 9: Effect of temperature on COD reduction (phenol).

1/T (K )
-1

Fig. 7: Thermodynamic analysis of degradation of phenol.

Fig. 10: Effect of temperature on COD reduction (tween80).

1/T (K-1)

Fig. 8: Thermodynamic analysis of degradation of tween80.

A. Effect of temperature
For temperature studies, all the other parameters were kept
constant at their optimized values, current: 0.3A (phenol)
and 0.2A (tween80), voltage: 3V (phenol) and 4V
(tween80), pH: 6(phenol) and 6.4(tween80), concentration:
1ml/L (phenol) and 2.1ml/L (tween80), and reaction time:
60 min. Electrochemical treatment was carried out at
varying temperatures ranging from 10C to 70C as shown
in Fig. 9 and 10 for phenol and tween80 respectively. It can
be noted that at 10C COD reduction was maximum for both
phenol and tween80 after 60 minutes of electrolysis. Thus,
the thermodynamic results can be verified here as according
to Le Chateliers principle and thermodynamic stability, a
lower temperature was suggested for spontaneity of the
electrochemical process. For phenol, at 10C and 20C,
93.33% and 80% of COD reduction was achieved
respectively. In case of tween80, we achieved 81.25% and
75% COD reduction at 10C and 20C respectively.

Fig. 11: Effect of temperature on anode efficiency

Temperature (C)
Fig. 12: Effect of temperature on energy consumption.

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A. Real sample analysis

Electroly
Initial
Final
sis
COD
COD
time
(mg/L)
(mg/L)
(min.)
3
60
400
Nil
3.1
90
1110
Nil
3.1
30
768
16
3.1
30
203
Nil
Table 4: COD Analysis in a Real Saline Sample

Current
(A)
0.2
0.2
0.2
0.2
Temperature (C)
Fig. 13: Effect of temperature on total current efficiency.
At 10C, anode efficiency (AE), energy consumption (EC)
and total current efficiency (TCE) were also the most
desired for both phenol and tween80 as shown in Fig. 11, 12
and 13 respectively. This is due to the better performance in
COD reduction at that temperature. At 10C, AE was the
highest for both phenol and tween80 at 0.743
KgCOD/A.m2.h and 0.6897 KgCOD/A.m2.h respectively.
Similarly, TCE peaked at 4.69% (phenol) and 4.35%
(tween80) at the same temperature as shown in Fig. 13.
Energy consumption was the lowest at 10C measuring
2.857 kWh/KgCOD for phenol and 3.08 kWh/KgCOD for
tween80.
A. Kinetics studies
The regression coefficient (R-squared) values were found
to be closer to unity at most temperatures for pseudo-firstorder kinetics than that for the pseudo-second-order kinetics
model. Therefore, the electro-oxidation of the synthetic
phenol/tween80 saline solution can be approximated more
appropriately by the pseudo-first-order kinetic model than
the second order kinetic model.
RK2
squared
(10-6
st
(1
L/mg.min)
order)
10
0.034
0.9973
10.123
20
0.0414 0.9834
16.075
30
0.0426
0.969
17.075
40
0.0428 0.9857
29.8
50
0.058
0.9513
23.8
60
0.052
0.9578
41.35
70
0.05
0.9887
17.17
Table 3: Reaction Kinetics Data (Phenol)

Temperature
(C)

K1
(min-1)

Rsquared
(2nd
order)
0.9522
0.9556
0.9375
0.9857
0.9857
0.9822
0.996

RRsquare
K2
Temperature K1
squared
-6
d
(10
(C)
(min-1)
(2nd
st
.
(1
L/mg min)
order)
order)
10
0.0327 0.9883 8.6
0.9511
20
0.0405 0.9867 11.13
0.9
30
0.0394 0.9966 15.36
0.9866
40
0.0283 0.9944 6.35
0.765
50
0.0329 0.9632 13.23
0.323
60
0.0355 0.9872 13.23
0.982
70
0.0385 0.9902 30.46
0.901
Table 4: Reaction Kinetics Data (Tween80)

Volta
ge
(V)

A real saline wastewater from petrochemical industry was

electrochemically treated using the optimized current 0.2A.
We achieved a COD reduction of up to 100% with the pH
being native, since the sample was alkaline and therefore
favored (5) in the forward direction and subsequent release
of hypo chlorites for oxidizing the organic matter.
IV. CONCLUSION
Electro oxidation of organic content under high saline
condition (330 g NaCl/L) was studied using phenol and
tween80 as model system and graphite as the anode. The
standard method for COD analysis was modified for better
precision and the parameters such as current of
0.2A(tween80) and 0.3A(phenol), potential of 4V(tween80)
and 3V(phenol), pH of 6.4(tween80) and 6.0(phenol),
temperature of 10C and reaction time of 60 minutes were
optimized with respect to pollution reduction and energy
consumption. RSM has been successfully employed for the
electrochemical treatment of phenol and tween80. The
reaction kinetics of this process was found to follow pseudofirst-order rate expression. It gave about a positive value for
G which indicates non-spontaneity. S and H values
from the thermo dynamical analysis were found to be
negative for both phenol and tween80. Therefore for
spontaneity, lower temperature was preferred and COD
removal of up to 93.33 % was achieved.
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