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(1)
Cathode : 6H
2
O 6e
! 3H
2
6OH
(2)
Net reaction:
2Al 6H
2
O ! 2AlOH
3
3H
2
basic condition (3)
2Al 6H
2
O ! 2AlOH
3
6H
, Al(OH)
n
(3n)
,
Al
2
(OH)
2
4+
, Al
7
(OH)
17
4+
, Al
13
(OH)
34
5+
, Al
3
(OH)
4
5+
, Al(OH)
6
3
with
different charge. In addition to anodic dissolution, Al
3+
ions are
released from the surface due to corrosion and pH of the aqueous
solution (chemical dissolution). At high pH values, preferential
dissolution of the protective oxide layer (boehmite) was suggested
as per the following reaction [16].
AlOOH OH
! AlO
2
H
2
O (5)
The dissolved metal ions and metal oxy-hydroxides aid the
coagulation of suspended solids. It is generally accepted that
coagulation of suspended solids is brought about primarily by
reduction of net surface charge to a point where they hold together
by inter molecular Vander Waals forces. The resistivity of the
electrodes was measured before and after electrocoagulation. The
resistivity of original aluminum cylindrical rod and hexagonal rod
before using them for electrocoagulation was measured to be
0.3774 mV and 0.3385 mV, respectively. After 9 h of electro-
coagulation, the resistivity of these electrodes was found to
increase at higher applied current of above 400 mA. This behavior
could be explained due to the formation of Al
2
O
3
lm at the
electrode surface which is non-conductive [17]. Despite the
resistivity is less than the original sample at low current densities,
the coating of white substance on the electrodes was observed. The
decrease in resistivity may be explained due to formation of
conductive lm on the electrode surface. The photograph revealing
the scaling of electrodes is shown in Fig. 3. The coated material was
scrapped from the surface and analyzed for its chemical assay. The
results revealed that CaCl
2
is the major compound. The coating of
CaCl
2
is obvious when the wastewater contain 17.6 g of Ca
2+
and
34 g of Cl
34,083 ppm
17 Sulphur as SO
4
2
11.54 ppm
18 Total iron 1.59 ppm
19 Silica (reactive) as SiO
2
68.6 ppm
20 Carbonate hardness 1020 ppm
21 Non-carbonate hardness 43,461 ppm
22 Free residual chlorine <0.2 ppm
23 TOC 194 ppm
24 COD 1280 ppm
25 BOD at 27 8C for 3 days 284 ppm
Table 2
Effect of electrode material and geometry on TOC removal (sample: as received,
duration of experiment: 9 h, ow rate: 1.0 L/h.
Cathode Anode Current
density
(mA/cm
2
)
TOC
removal
(%)
Resistivity (mV)
Cathode Anode
Al rod Al rod 31.98 54.65 0.3572 0.4402
Al rod Al rod 12.79 49.89 0.2697 0.2964
Al rod Al rod 6.40 38.43 0.2647 0.2834
Al rod
(hexagonal)
Al rod
(hexagonal)
12.79 50.72 0.3409 0.3425
SS rod Al rod 12.79 68.37
Fig. 3. Scaling of aluminum electrodes of different geometries after 6 h of
electrolysis.
N. Lakshmi Kruthika et al. / Journal of Environmental Chemical Engineering 1 (2013) 183188 185
words, the rate of Al
3+
dissolution is less than the rate of diffusion
of dissolved Ca
2+
and Cl
! Cl
2
2e
(7)
Since the experiments were conducted around neutral pH,
entire chlorine is expected to be in the form of HOCl and OCl
).
Cl
2
aq H
2
O ! HOCl H
Cl
(8)
It is known that the oxidation of organics in the presence of
active and dimensionally stable anodes like IrO
2
/TaO
2
/RuO
2
coated titanium was attributed to the formation of higher oxides
[19] via adsorption of hydroxyl/oxy chloride radical which can be
represented as
MO
x
OH
! MO
x
OH
! MO
x1
H
(9)
MO
x
OCl
! MO
x
OCl
Cl
! MO
x1
Cl
2
e
(10)
In the presence of oxidizable organics, the chemisorbed active
oxygen will participate in the formation of selective oxidation
products where as physisorbed active oxygen leads to complete
degradation to CO
2
and H
2
O [20]. Serikawa et al. [21] have
observed strong catalytic effect while converting organic pollu-
tants to innocuous CO
2
and H
2
O in the presence of chloride ion. It
is also apparent that the indirect electrooxidation involving
various forms of chlorine was a predominant process in removing
organic pollutants. Consequently, the oxidation of efuent is poor
under Ti/IrO
2
Ta
2
O
5
electrode. Better oxidation by TiO
2
NT
electrode may be attributed to the difference in band gap and
specic surface area. It is evident that the TiO
2
nanotues grown on
Ti-surface are intact and active even after prolonged usage for
several hours. The SEMEDAX analysis of the electrode surface
indicates the presence of minor amounts of Ca
2+
, Cl
and N. The
possibility of passive lmon the anode surface can be discounted
because of continuous generation of hypochlorite ions in aqueous
solution.
Effect of current density
The degradation of organics using TiO
2
nanotubes as anode and
at different current densities was studied and the results are
presented in Fig. 7a. From the results it is apparent that the TOC
removal was found to increase with current density that too only at
the initial stage. Also, it was observed that the TOC removal beyond
25 mA cm
2
is very marginal. In general, if the applied current is
more than the limiting current, the oxidation will be invariably
under mass transport control and the oxygen evolution dominates
the Cl