30320130402003

International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 –
6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME
21
MEMBRANE ASSISTED ELECTRO CHEMICAL DEGRADATION
FOR QUINOLINE YELLOW, EOSIN B AND ROSE BENGAL DYES
DEGRADATION
B. Chirsabesan and M.Vijay*
Department of Chemical Engineering, Annamalai University, Annamalai Nagar,
Chidambaram -608002, India
ABSTRACT
Industrial waste often contains a mixture of organic and inorganic compounds, in
addition to solid or soluble material, and because of this diverse feature no universal
strategy of remediation is feasible. In the present study, Quinoline Yellow, Eosin B and Rose
Bengal model dye were chosen and its characterization was done by measuring pH, EC, TDS,
COD, and Color etc. Degradation studies of Quinoline Yellow, Eosin B and Rose Bengal
model dye was carried out with Membrane assisted electro chemical degradation cell in
specially designed reaction vessel in the electro membrane reactor equipped with poly
electrolyte membranes. Experiments were performed in four poly electrolyte membranes
(PEM) such SPES, SPSf, SPEEK and Nafion at optimized condition. The SPES, SPSf,
SPEEK were prepared with different ion exchange capacity. The dyes degradation were
compared with commercial Nafion commercial PEM membranes.
Key words: Quinoline Yellow, Eosin B, Rose Bengal Quinoline Yellow, Membrane assisted
electro chemical degradation, decolourization of dye.
1. INTRODUCTION
Industrial waste often contains a mixture of organic and inorganic compounds, in
addition to solid or soluble material, and because of this diverse feature no universal
strategy of remediation is feasible. As to the treatment of effluents polluted with organic
compounds, biological oxidation is the cheapest process, but the presence of toxic or bio-
refractory molecules may hinder this approach. It is important to design (or select) an
electrochemical reactor for a specific process, and it is clear that reactors for energy
conversion and electrochemical synthesis will have different drivers to those used in the
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destruction of electrolyte-based contaminants. Adequate attention must be paid to the form of
the electrode, its geometry and motion, together with the need for cell division or a thin
electrolyte gap. However, some limitations are there in electrochemical technology such as
relatively few “showcases” for the technology, shortage of experienced electrochemical
engineers, Chemical reactions, corrosion, adsorption, etc., at electrode surfaces can cause
complications, Damage to electrodes via, e.g., corrosion and fouling, can restrict performance
and longevity. Ion-exchange membranes can play a critical role in electrochemical reactors, it
provides high surface area electrodes, acceptable cost, lifetime, and practicality of electrodes
and membranes, low potential drop over electrodes and membranes, membranes that are
selective to a particular ion and low solvent transport rate through membranes.
Textile Printing and dyeing processes include pretreatment, dyeing / printing, finishing and
other technologies. Pre-treatment includes desizing, scouring, washing, and other processes.
Dyeing mainly aims at dissolving the dye in water, which will be transferred to the fabric to
produce colored fabric under certain conditions. Printing is a branch of dyeing which
generally is defined as ‘localized dyeing’ i.e. dyeing that is confirmed to a certain portion of
the fabric that constitutes the design.
Table 1 The scope for electrochemical technology in environmental treatment
Avoidance of pollution
clean electro
synthesis
Recycling of valuable materials
precious metal deposition
Remediation of polluted sites
soil remediation by electrodialysis
Monitoring and sensors
in the gas and liquid phase
Efficient energy conversion
fuel cells and redox flow cells
Avoidance of corrosion
choice of materials/protective coatings
Removal of contaminants
metal ion, organics, and inorganics removal from water and process
liquors
Disinfection of water
chlorination, peroxy species, or ozone
Effluent from textile mills also contains chromium, which has a cumulative effect,
andhigher possibilities for entering into the food chain. The scope of electrochemical
technology in environmental treatment is shown in Table 1. Due to usage of dyes and
chemicals,effluents are dark in color, which increases the turbidity of water body (Joseph and
Egli, 2007). Adsorption techniques have recently gained a considerable importance due to
their efficiency in the removal of pollutants too stable for conventional methods (Robinson et
al. 2001, Aksu 2005). Most adsorbents are not equally effective towards different types of
dyes (van der Zee 2002). Membrane technology has emerged as a feasible alternative to
conventional treatment processes of dye wastewater and has proven to save operation costs
and water consumptions by water recycling. Usually this technique is applied as a

23
tertiary/final treatment after biological and/or physical-chemical treatments (Ciardelliet al.
2000, Marcucciet al. 2002). Electro oxidation of organic compounds in aqueous solution can
be obtained without electrode fouling by performing electrolysis at high anodic potentials in
the region of water discharge due to the participation of intermediates of oxygen evolution.
This process results in partly conversion or full mineralization of the organics, does not need
to add oxidation catalysts to the solution and does in principle not produce any by-products.
The decontaminated solutions showed no mutagenicity towards Salmonella
typhimurium(Lunn and Sansone, 1991). In literature, it is reported that AOP using Fenton’s
reagent can reduce the eosin concentration of 678 mg/l by 20% in 1hwhen treated with 278
mg/l FeSO4·7H2O and 3400 mg/l hydrogen peroxide. The results showed that anionic
surfactants performed significantly better than a cationic one during the desorption of
anionic dyes Eosin (Purkait et al).Quinoline yellow (QY) is also another food colorant.
Different techniques such as adsorption, oxidation, reduction, electrochemical and membrane
filtration are applied to remove these pollutants from the industrial effluents. Oxidation
processes are widely used both in industrial preparations and in environmental treatments.
Karacakaya and colleagues (2009) investigated the removal capabilities of Synechocystis sp.
And Phormidium sp. The pseudo-second order kinetic model (PSOM) is widely used because
of the simplicity of applying its linear form and the general applicability to adsorption kinetic
data (Ho and McKay 1999). However, the models with simple expressions are more favored
(Levenspiel 2002; Gonzo and Gonzo 2005). Among all the models used in adsorption kinetic
studies, pseudo-first order model (PFOM) and PSOM were frequently applied (Ho and
McKay 1999). However, as yet, there has not been a method employing the electrochemical
oxidation process combined with the membrane filtration process for the treatment and reuse
of textile dyehouse wastewater. The goal of this research is to study the performance of the
arc-shaped transfer-flow membrane module, at the same time, to demonstrate these processes
and to develop a potential dye wastewater treatment system for reuse.
2. MATERIALS AND METHODS
Textile dye Quinoline Yellow, obtained from pollution control division, Central
Electrochemical research Institute, Karaikudi, Tamilnadu.PES (3500) was received from
Udel. Eosin B dye (4´,5´-Dibromo- 2´,7´dinitrofluorescein di sodium salt, colour index:
45400), chloroform, chlorosulfonic acid,methanol, and dimethylformamide (AR grade) were
obtained from S.D fine Chemicals, India, and were used without any further purification. The
Characteristics of organic dyes are shown Table 2. Fungal strain Corialusversicalor ((MTCC-
138)wasobtained from microbiology laboratory, Bharathidasan University, Trichy and used
for the study.
2.1. Dye Effluent Preparation
Dye concentration selected for experiments was 200 mg/L. This value is included in
the range of real dye concentration found in textile effluents. Synthetic Quinoline Yellowand
Eosin B dye bath effluent used in the present study was prepared according to the
composition commonly used in cotton dyeing. In order to dye 0.1kg of fabric, 0.004 kg of
dye is used. It is dissolved in 1 L of double distilled water along with the auxiliary chemicals
such as 0.003 kg Na2CO3, 1 mL of NaOH 38°Bé (441×10-3
kgm-3
NaOH solution)and0.01kg
of NaCl.

24
2.2 Electrochemical process
The electric current induces redox reactions resulting in the transformation and
destruction of the organic compounds and almost complete oxidation to CO2 and H2O.
Table 2: Characteristics of organic dyes
The oxidation of pollutants in an electrolytic cell can occur through the following
processes:
Anodic oxidation: This refers to processes in which an electron transfer reaction of the
desired pollutant occurs at the surface of the anode. The electrode reactions involving the
degradation of organic compounds are given by Equations 2.1 and 2.2. The potential required
for the oxidation of organic compounds is usually high and collateral reactions such as water
electrolysis are inevitable.
M + H2O→M (HO•
) + H+
+ e−
(2.1)
M (HO•
) + R→M + CO2 + H2O + H+
+ e−
(2.2)
where M is the electrode and R is the organic compound.
Cathodic reduction: Electro reduction of textile wastewater with azo dyes was also
reported. The reductive cleavage of the azochromogene leads to a decrease in the specific
absorbance of the dye without the addition of chemicals or formation of sludge.
Indirect oxidation: This process relies on the electrolytic generation of strong
oxidising agents. The action of these oxidizing species leads to total or partial
decontamination, respectively. When NaCl is used, the electrode reactions to indirect
degradation of organic compound proceeds as follows:
2Cl−
−→Cl2 + 2e−
(2.3)
Cl2 + H2O→H+
+ Cl−
+ HOCl (2.4)
HOCl→H+
+ OCl−
(2.5)
R + OCl−
−→CO2 + H2O + Cl−
(2.6)
where: R is the organic compound.
Name of Dyes Class of dye
(ionic type)
Mwt
gm/gmol
Chemical
structure
ߣߣߣߣmax
(nm)
Quinoline Yellow
Colour Index No.:
47005
Quinoline
(anionic)
375.3 C19H11N1Na2O8S2 411
Eosin B
(disodium salt)
CI Number:
45400
Xanthene
(anionic)
580.09 C20H6N2Na2O9Br2 514

25
The main advantages of using these electrochemical methods include that they do not
consume a significant amount of chemicals, nor do they produce sludge. Additionally, the
processes are commonly performed at room temperature and atmospheric pressure, thus
avoiding the undesirable volatilization and discharge of untreated residues.
By means of electrochemical oxidation, pollutants in wastewater can be completely
mineralised by electrolysis using high oxygen over-voltage anodes such as PbO2 and boron-
doped diamond. Polcaro et al. (1999) studied the performance of the Ti/PbO2 anode during
electrolysis of 2-cholorophenol in terms of faradic yield and fraction of toxic intermediates
removed.
2.3. Membrane Separation Process
Membrane-wet oxidation, an integrated process, has been demonstrated by Dhale and
Mahajani (2000) to treat the disperse dye bath waste. On the other hand, these techniques do
not eliminate definitively the dyes but only separate and concentrate them. The destruction of
the concentrated pollutants requires an additional operation as incineration. However,
electrochemical processes that use hydroxyl radicals, a very strong oxidant to destroy
compound that cannot be oxidized by conventional oxidant. An advanced oxidation method
is a result of their high potential. The chain mechanism of oxidation, which involves hydroxyl
and hydroperoxide radicals guarantees efficiency and quick rate of the process. The high
reactivity and low selectivity of the reaction enable the method to be applied to a large
number of organic compounds present in the wastewater. Further advantages include a lack
of by-products, which can produce secondary pollution of the environment and thus risk over
dosage of the oxidizing agents
2.4. Membrane assisted electrochemical oxidation techniques for degradation of dye
effluents
Electrochemical oxidation has a high COD removal efficiency (89.8%) of the textile
wastewater while membrane filtration can almost totally remove TSS (nearly 100%
reduction) and turbidity (98.3% elimination) in it. The traditional single-chamber
electrochemical method used in the wastewater treatment mainly focuses on anodic
oxidation, but hydrogen is produced on the cathode, which also consumes much energy, is
often ignored. The simultaneous production of evolved hydrogen at a cathode as a
byproduct, along with high power requirements is the main disadvantage for electro-
oxidation of organics. In this work, an innovative two-chamber electrolytic cell, connected
with an anion exchange membrane, was developed. In this new reactor, indirect oxidation at
anode, indirect oxidation by hydrogen peroxide and UV/H2O2 at cathode can occur
simultaneously. Therefore “dual electrodes oxidation” in one electrochemical reactor was
achieved successfully. Compared to a traditional one cell reactor, this reactor considerably
reduces the energy cost by 25–40%, and thus the present work becomes significant in
wastewater treatment for dye effluents.
Electrochemical oxidation of dye solution was carried out in electrochemical cell.
Anode and cathode were Fisher platinum electrodes. The volume of solution to be treated
was 400 mL and the effective electrode area was 25 cm2
. The homogeneous nature of the
medium during the electrolysis was maintained using magnetic stirring. The electrolysis cell
used in the present study consists of a glass beaker of 500 ml capacity closed with a PVC lid
having provision to fit a cathode and an anode (surface area of the electrode19.5 cm2
). Anode
was ruthenium coated on titanium metal (RuOx–TiOx) (expanded mesh type) and cathode

International Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976
6995(Print), ISSN 0976 – 7002(Online) Volume 4, Issue 2, May
was stainless steelplate. The current was supplied by multi
source (with ammeter and voltmeter).
Figure 1: Schematic diagram of electrochemical reactor employed for dye degradation
Schematic diagram of electrochemical reactor
in Figure 1. Electrochemical reactor was made of PTFE and divided into an anode
compartment (AC) and cathode compartment (CC) by PEM (8.0×10
pumps were used to move each stream, while an adjustable dc power supply (model L 1285,
Aplab, Mumbai, India) was used to apply constant potential gradient. NaOH concentration in
the CC was also monitored regularly. In all cases, equal v
study the feasibility of the separation process. Build
determined by acid-base titration using phenolphathalein indicator.
were analyzed by UV-Vis spectrometry at m
calibration curve (Figure1) and dyes removal was obtained following equation
Dyes removal (%) = 1-
2.5. Preparation of Polymer Electrolyte Membrane
2.5.1. Preparation of sulfonated poly
Polyethersulfone (Gadone TM 3400 was sulfonated as per the procedure developed
by Chen et al., (1996). Poly ether sulfone 40g was dissolved in 1,2
the solution at a temperature of 85
and 5 ml of chlorosulfonic acid was added drop wise to the solution for about 15 minutes. This
reaction mixture was maintained at 4
sulfone obtained was precipitated
dried in vacuum for 1-2 h at 40°C.
al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976
7002(Online) Volume 4, Issue 2, May - August (2013), © IAEME
26
inless steelplate. The current was supplied by multi-output 2 A and 30 V, DC power
source (with ammeter and voltmeter).
Schematic diagram of electrochemical reactor employed for dye degradation
Schematic diagram of electrochemical reactor employed for dye degradation is depicted
compartment (AC) and cathode compartment (CC) by PEM (8.0×10-3
m2
). Two peristaltic
the CC was also monitored regularly. In all cases, equal volumes of AC and CC were taken to
study the feasibility of the separation process. Build-up of NaOH concentration in CC was
base titration using phenolphathalein indicator. The dye concentrations
Vis spectrometry at maximum wavelength (λmax = 517 nm) using
calibration curve (Figure1) and dyes removal was obtained following equation
(C1/C0) × 100
Preparation of Polymer Electrolyte Membrane
Preparation of sulfonated poly (ether sulfone)
by Chen et al., (1996). Poly ether sulfone 40g was dissolved in 1,2-dichloroethane by heating
the solution at a temperature of 85°C ± 5°C, for 2-3 h. The solution was then cooled to 4
reaction mixture was maintained at 4°C for 2 h. The solid sodium salt of sulfonated poly ether
sulfone obtained was precipitated in ice cold water followed by treatment with methanol and
C.
al Journal of Design and Manufacturing Technology (IJDMT), ISSN 0976 –
August (2013), © IAEME
output 2 A and 30 V, DC power
Schematic diagram of electrochemical reactor employed for dye degradation
employed for dye degradation is depicted
). Two peristaltic
olumes of AC and CC were taken to
up of NaOH concentration in CC was
The dye concentrations
max = 517 nm) using
(4.1)
dichloroethane by heating
solution was then cooled to 4°C
C for 2 h. The solid sodium salt of sulfonated poly ether
in ice cold water followed by treatment with methanol and

27
Figure 2: Sulfonation process sequence
2.6. Membrane Formulations
The polymers of SPSf, SPES and SPEEK were prepared by individually at 17.5 wt% in
presence polar solvent, DMF (82.5 wt%), under constant mechanical stirring in a round bottom
flask for 3 h at 40°C. The homogeneous solution was allowed to stand for 1 h in airtight
condition to get rid off the air bubbles. The compositions and casting conditions of PEM
membranes is displayed in Table 3.
2.6.1.Preparation of Membranes
All membranes were prepared by the “diffusion induced phase separation”
method, namely, casting a thin film of the polymeric solution on a glass plate and, after
allowing the solvent to evaporate for a predetermined period at the desired humidity and
temperature conditions, immersing it into a bath of non-solvent (water, solvent, surfactant)
for final precipitation. Prior to membrane casting, a gelation bath of 2L of distilled water
(non-solvent), containing 2% DMF (Solvent) and 0.2% SLS (Surfactant) was prepared and
cooled to 10°C.
Table 3: Compositions and casting conditions of PEM membranes
Name of Polymer
Polymer
composition (%)
Solvent, DMF
(%)
SPSf 17.5 82.5
SPEEK 17.5 82.5
SPES 17.5 82.5
Nafion® 117 - -
Total weight percentage of polymer = 17.5 wt %. Casting solution temperature = 85 ± 2°C,
Casting temperature = 34 ± 2°C Casting relative humidity = 20 ± 2 %, Solvent evaporation
time = 30 s.
Poly Sulfone +Chloroform
(PSU)
Dissolved + Sulfonating agent
PSU (TMSCS)
Sulfonating
Polysulfone (PSU)
Silylsulfonate PSU
+
Sodium methoxide
[A]
[C]
[B]
[A] = reaction at ambient temperature
[B] = continuous stirring for 24 h
[C] = stir for 1 hour, then added drop wise into methanol bath
(TMSCS) = trimethylsilylchlorosulfonate
Note: The solution were contiuously stirred under N2 atmosphere during the

28
Figure 3. PEM membranes
2.6.2. Membrane properties and stability
The sulfonated sample was characterized for functional group determination by FT-IR
Spectroscopy. FT-IR spectra were recorded on a Perkin-Elmer, model-Spectrum RX1 Fourier
transform spectrometer either with powder samples inside a diamond cell or by using KBr
pellets composed of 50 mg of IR spectroscopic grade KBr and 1mg polymer sample.
2.7. Estimation of water content, ion-exchange capacity (IEC) and counter-ion transport
number
Membrane thickness was measured by a digital micrometer with 0.1 µm accuracy.
The membrane water content was determined by weight of membrane in wet and dry
conditions. Membrane was dried in vacuum oven at 60 °C for 24 h and recorded its weight.
Further the dry membrane was kept in distilled water for same period of time and their wet
weight was recorded. The water content was finally calculated using the following equation:
(4.2)
Where Ww and Wdare the weight of the wet and dry membrane, respectively.
For the estimation of ion exchange capacity (IEC), desired pieces of ion-exchange
membranes were conditioned in 1.0 M HCl solution for 12 h to convert them into H+
form.
The excess HCl was removed by washing with distilled water. The membranes were then
equilibrated in 50 ml of 0.5 M NaCl solution. The amount of H+
ions liberated from SPS
membrane was determined by acid–base titration.
Nafion® 117 SPSf SPEEKSPES

29
Counter-ion transport number across the membranes was estimated by membrane
potential measurement in 0.01 and 0.10 M NaCl solutions, according to equation 4.3 reported
previously using TMS (Teorell, Meyer, and Sievers) approach.
‫ܧ‬௠
ൌ ሺ2‫ݐ‬௜
௠
െ 1ሻ
ோ்
ி
݈݊
௔భ
௔మ
(4.3)
Where a1 and a2 are the activities of electrolyte solutions contacting two surfaces of the
membrane, R is the gas constant, T is the absolute temperature, and F is the Faraday constant.
2.8. Membrane conductivity
The membrane conductivities were recorded in equilibrium with eosin and NaCl
solution of different concentrations. The specific membrane conductivity (κm
) was estimated
by:
‫ܭ‬௠
ൌ
∆௫
஺ோ೘
(4.4)
Where ∆x is the thickness of equilibrated membrane, A is the membrane area.
2.9. Analytical methods
2.9.1. Chemical Oxygen Demand(COD)
In order to determine the extent of degradation of the effluent Chemical Oxygen
Demand (COD) was measured. The COD as the name implies is the oxygen requirement of a
sample for oxidation of organic and inorganic matter. COD is generally considered as the
oxygen equivalent of the amount of organic matter oxidizable by potassium dichromate. The
organic matter of the sample is oxidized with a known excess of potassium dichromate in a
50% sulfuric acid solution. The excess dichromate is titrated with a standard solution of
ferrous ammonium sulfate. COD of all samples were determined by the dichromate closed
reflux method using thermo reactor TR620-Merck.In COD measurement, 3 samples are
subjected to analysis for one COD data. From that, any two same values or the average of any
two nearer values is considered as the measured data.
2.9.2. Spectral analysis using UV-visible spectrophotometer
For UV-Visible spectral analysis, 5 mL of treated and untreated samples were taken and
centrifuged at 12,000 rpm for 10 min. The supernatant of untreated and treated samples were
analyzed by monitoring the changes in its absorption spectrum using UV–visible
spectrophotometer with a cell having 1 cm optical path length.
3. RESULTS AND DISCUSSION
3.1. Characterization of sulfonated poly (ether sulfone)
FTIR spectra were also used to confirm the pendant SO3H group on the polymer
chain. Figure 4 shows the spectra of SPES. The presence of the sulfonic group can be
visualized by the presence of the absorption bands. On the spectra of SPES, the new
absorbance at 1020 cm-1
and 1250 cm-1
are contributed separately by symmetric and
asymmetric O=S=O vibration. The peak at the peak at 1770 cm-1
to the ester cardo group of
sulfonated poly (ether sulfone).It has been known that the asymmetrical stretching vibrations

of sulfonic acid groups appear at
overlapping absorbance. However, it still can getconclusion that the sulfonic acid groups has
been introduced into the polymer chains
Figure
Table 4: Physicochemical and electrochemical properties
Property
Thickness (µm)
Water content (%)
Ion-exchange capacity
(mequiv./g of dry membrane)
Counter ion transport number
Membrane conductivityb
(mScm
a
(tm) was estimated from membrane potential measurements in
solutions of 0.1M and 0.01M concentrations.
b
Membrane conductivity was measured in equilibration with 1.0MNaCl solution
30
of sulfonic acid groups appear at ∼1180 cm−1
, but we could not readily observe it due to near
ntroduced into the polymer chains
Figure 4. The spectra of SPES
Physicochemical and electrochemical properties of the cation exchange membrane
SPSf SPES Nafion® 117
150 150 150
12 23 38
(mequiv./g of dry membrane)
1.40 0.80 0.90
Counter ion transport numbera
(tm) 0.94 0.99 1.05
(mScm−1
) 20.2 41.4 94.6
(tm) was estimated from membrane potential measurements in equilibrium with NaCl
solutions of 0.1M and 0.01M concentrations.
, but we could not readily observe it due to near
of the cation exchange membrane
SPEEK
150
35
1.10
0.98
99.5
equilibrium with NaCl

31
For EMR, knowledge on membrane conductivity in equilibration with actual
operating conditions is an essential parameter. Membrane conductivity data (km) for SPS
membrane inequilibration with eosin B and NaCl solutions of different concentrations (10-
100 ppm) is presented in Figure 5. km values depended on ionic strength of equilibrating
solution, and increased initially with concentration (eosin B and NaCl) before attending
limiting value (beyond 30 ppm). This observation may be attributed to comparatively low
dissociation and ionic strength of eosin B solution. However, comparable membrane
conductivities under both operating conditions (eosin B or NaCl) revealed the membrane
suitability for an EMR.
Figure 5. Membrane potential measurements in equilibrium
3.2. Membrane Morphology
The top face shows non-uniformaggregates that might have formed due to solvent
removal fromthe top as mentioned earlier and the bottom face appears smooth. Dense
membranes with reproducible thickness could beobtained by using a sufficient quantity of
polymer solution.The pore structure of the PEM membranes were sensitively changed for
SPSf, SPES, SPEEK and Nafion membranes (Figure 6). The average pore size of SPES
membrane clearly increased with respective IEC. In this comparison of morphology, dyes
mass transport driving forcesknown for flows of dye molecules through microporous,
diffusion driven by activity gradients, migrationof protons in the electric field, pressure-
driven convective flow, and electro-osmotic flow of uncharged species, dueto forces exerted
on them by the migrating protons. Therefore it is necessary to analyse morphology of
membranes for dyes transport mechanisms
0
1
2
3
4
5
6
Nacl Eosin B Rose bengal
Km(mScm-1)

SPSf Membrane
SPEEK Membrane
Figure 6.
3.3. Chlorine tolerant of SPS, SPES and SPEEK and Nafion® 117 membranes
The chlorine tolerant nature of prepared SPS, SPES and SPEEK membrane was
assessed in comparison with Nafion® 117 membrane in terms of percentage in weight loss
and IEC loss for definite time intervals. Formation of oxy radicals during electrochemical
water splitting in the presence of halide ion occurred AC, which may attack on hydrogen
containing bonds of PEM. Thus, developed PEM should be highly chlorine tolerant in nature.
Resultant image are presented in Figure
It is obvious that prepared membranes
after 24 h treatment when compared with Nafion® 117 membrane. Progressively, loss in IEC
and weight attained limiting values. Furthermore, for SPEEK membrane, weight loss was
slightly higher than Nafion® 117 membra
loss.
32
SPSf Membrane SPES Membrane
SPEEK Membrane Nafion Membrane
6. SEM image of all PEM membranes
hlorine tolerant of SPS, SPES and SPEEK and Nafion® 117 membranes
r splitting in the presence of halide ion occurred AC, which may attack on hydrogen
Resultant image are presented in Figure 7.
It is obvious that prepared membranes (SPS, SPES and SPEEK) lost about 5
slightly higher than Nafion® 117 membrane, while latter showed comparatively high IEC
hlorine tolerant of SPS, SPES and SPEEK and Nafion® 117 membranes
r splitting in the presence of halide ion occurred AC, which may attack on hydrogen
(SPS, SPES and SPEEK) lost about 5-6% IEC
ne, while latter showed comparatively high IEC

33
Figure 7. Comparison of percentage loss in weight for SPS, SPES and SPEEK and
Nafion® 117 membranes
The membrane degradation occurred chemically as a result of oxy-chloride free
radical (•OCl) attack on the polymer chain in the vicinity of hydrophilic domains. IEC is
measure of functional group concentration in the membrane matrix, and high for SPS
membrane (1.40 mequiv./g) in comparison with membrane Table 4. Thus, because of more
hydrophilic nature of SPS membrane than other three membranes, IEC loss was
comparatively high under chlorine stability test (Figure 8). Moreover, chlorine tolerant nature
for all (SPS, SPES and SPEEK and Nafion® 117) was same and these membranes showed
their potential applications under chlorine environment.
Figure 8. Comparison of IEC for SPS, SPES and SPEEK and Nafion® 117 membranes
0
1
2
3
4
5
6
7
8
9
0 10 20 30 40 50 60 70 80 90 100 110
%Weightloss
Time allowed for NaoCl treatment (h)
SPSf
SPES
Nafion
SPEEK
0
1
2
3
4
5
6
7
8
0 10 20 30 40 50 60 70 80 90 100 110
%IECloss
Time allowed for NaoCl treatment (h)
SPSf
SPES
Nafion
SPEEK

This result means that SPEEK membrane is highly chlorine
other PEM membranes. In addition, there is no degradation moiety in this polymerbackbone
which is composed ketone and ether linkage,unlike poly(ether sulfone) backbone structu
which consists of thebenzene ring, ether and sulfone linkage (Figure
theall membranes under5% aq. NaOClsolution, time requirement with the weight loss
increased, whichmeans that the potassium ion was exchanged with sodium ionun
solution.
Figure 9. Comparison of percentage loss in weight for SPS, SPES and SPEEK and
However, for SPEEK membranes the overall values reduced after the chlorine
treatment. On the contrary, commercial Nafionmembrane
5% aq. NaOCl solution at 80◦
C for different time intervalswas lesser when compared with
SPES and SPSf respectively, after exposure to NaOCl solution.
The IEC loss of membraneswas main factor to measure hydrophilicity on t
of membranes. The increase of the IEC loss with time of NaoCl treatment shown in Figure
.The increase of hydrophilicity may correspondto % of IEC loss of membranes, which
indicates that theNafionmembrane is unstable under the chlorine condition at
solution at 80◦
Cas reported in other literatures.However, the % of IEC loss of SPS
membranes exhibit change after the treatment under wild acidic condition. From Figure
data give quite reliable informationon the hydrophobic/hydrophilic separation in the
amorphouspart of the ionomer. The typical dye separation and distributionis read
from % of IEC loss of membranes andits dependenton the water volume fraction
3.4.Investigations on membrane electrochemical properties
3.4.1 Electro-membrane reactor with PEM for separation dye solution
The physicochemical and electrochemical
investigation arepresented in Table
exchange capacity, and counter
specific membraneconductivity. Furthermore,
comparable with the best-known ion
34
This result means that SPEEK membrane is highly chlorine-resistant membrane than
which is composed ketone and ether linkage,unlike poly(ether sulfone) backbone structu
which consists of thebenzene ring, ether and sulfone linkage (Figure 9).After the treatment of
increased, whichmeans that the potassium ion was exchanged with sodium ionun
Comparison of percentage loss in weight for SPS, SPES and SPEEK and
Nafion® 117 membranes
treatment. On the contrary, commercial Nafionmembrane displays the chlorine resistant at
SPES and SPSf respectively, after exposure to NaOCl solution.
The IEC loss of membraneswas main factor to measure hydrophilicity on t
of membranes. The increase of the IEC loss with time of NaoCl treatment shown in Figure
indicates that theNafionmembrane is unstable under the chlorine condition at 5% aq. NaOCl
as reported in other literatures.However, the % of IEC loss of SPS
membranes exhibit change after the treatment under wild acidic condition. From Figure
amorphouspart of the ionomer. The typical dye separation and distributionis read
Investigations on membrane electrochemical properties
membrane reactor with PEM for separation dye solution
The physicochemical and electrochemical properties of PEM prepared and used in the
Table 4. All membranes exhibited good watercontent, ion
exchange capacity, and counter-ion transportnumbers in the membrane phase and high
specific membraneconductivity. Furthermore, all properties of these membranesare
known ion-exchange membranein the world.The chemical (chlorine
resistant membrane than
which is composed ketone and ether linkage,unlike poly(ether sulfone) backbone structure
).After the treatment of
increased, whichmeans that the potassium ion was exchanged with sodium ionunder NaOCl
Comparison of percentage loss in weight for SPS, SPES and SPEEK and
displays the chlorine resistant at
The IEC loss of membraneswas main factor to measure hydrophilicity on the surface
of membranes. The increase of the IEC loss with time of NaoCl treatment shown in Figure 9
5% aq. NaOCl
as reported in other literatures.However, the % of IEC loss of SPSf
membranes exhibit change after the treatment under wild acidic condition. From Figure 9,
amorphouspart of the ionomer. The typical dye separation and distributionis readily obtained
properties of PEM prepared and used in the
. All membranes exhibited good watercontent, ion-
ion transportnumbers in the membrane phase and high
all properties of these membranesare
exchange membranein the world.The chemical (chlorine

35
resistance) stabilities of these membranes are attractive features for theirapplicability in the
electro-membrane processes. For developingelectrochemical membrane reactor, knowledge
on membraneconductivity in equilibration with actual operating conditionsis an essential
parameter.
Most dye contains NaCl as the major constituent, thus electrochemicaldegradation is
easy in absence of supporting electrolytes. Principle of EMR used for dye degradation
wasbased on electro-membrane electrodialysis as presented in Figure 10.Generally, dye
molecule is electrochemically inactive andanode changes occurred because oxidation of
water/Cl−
to O2/Cl2.Chlorine gas is robust oxidizing agent and dissolves in water
(HOCl),which is instable in acidic solution (pKa = 7.4). HOClimmediatelydissociates and
formation of OCl−
is responsible for dye degradation.Thus, basic or neural pH conditions are
more favorable for dyedegradation.
Figure 10. Cyclic voltammetric responses of 0.1M NaCl: Scan rate in all cases was
50mVs−1
The above diagram describes the basic electrochemical principles by which
Electrosep's cell works. As the stream to be treated passes through the anolyte chamber,
sodium (Na+) ions are transferred through the membrane to the catholyte chamber to
combine with available hydroxyl (OH-) ions and produce caustic (sodium hydroxide).
Organics are oxidized or acidified at the anode, allowing them to be removed from the treated
stream. Hydrogen gas (H2) is liberated at the cathode, and may be recovered for fuel.pH of
the solution was monitored by using a digit al desktop,pH Meter (CP901) from Century
Instrument Company and pH was adjusted with the help of 0.1MNaOH and 0.1M HCl batch
mode. Constant stirring of the solution was ensured using magnetic stirrers. In AC, eosin B
degraded in AC by chloride/hypochlorite mediatedoxidation. Degradation was effected by
O2/OCl−
generationat anode, and migration H+
/Na+
from AC through SPS membrane(CEM)
towards cathode. This leads formation of NaOH in CC usingOH−
formed due to reductive
water splitting Moreover,eosin B degradation process depends on the initial eosin B
dyeconcentration and oxidizing strength of anode (active species concentration).Electro-
active species produced at electrodes exhibited peaktyperesponses in cyclic voltammetry
because exchange of electronduring anodic- and cathodic-potential scans.
-20
-17.5
-15
-12.5
-10
-7.5
-5
-2.5
0
2.5
5
7.5
10
12.5
15
-1.5 -1 -0.5 0 0.5 1 1.5
I/A
E/V vs SCE
with addition of dye solution
Without dye solution

36
40
50
60
70
80
90
100
20 40 60 80 100 120 140 160 180
QuinolineYellowdyeremoval
(%)
Time (min)
100 ppm
50 ppm
30 ppm
10 ppm
3.5. Effect of operating conditions on Quinoline Yellowdegradation in EMR
Rate of dye degradation was affected applied potential, dye concentration and feed of
flow rate. Variation of Quinoline Yellow removal under different applied potential are
presented in Figure 11 for 50 ppm Quinoline Yellow in feed at 40 ml/min. Quinoline
Yellowconcentration was monitored by absorbance spectra before and after degradation at
411 nm band. With time and applied potential, dye removal was enhanced during electrolysis.
About 95% Quinoline Yellowdegradation was achieved for it 50 ppm concentration in AC
(40 ml/min flow rate) after 180 min electrochemical treatment at 12.0V applied potential.
Figure 11. Variation of Quinoline Yellow removal under different applied potentials
Figure12. Rate of change of dye concentration was relatively fast at high concentration
under similar experimental conditions
70
75
80
85
90
95
100
25 45 65 85 105 125 145 165 185
QuinolineYellowdyeremoval(%)
Time (min)
12V
10V
8V

37
40
50
60
70
80
90
100
20 40 60 80 100 120 140 160 180
QuinolineYellowdyedyeremoval(%)
Time (min)
100 ppm
50 ppm
30 ppm
10 ppm
Rate ofchange of dye concentration was relatively fast at high concentrationunder
similar experimental conditions. It revealed about95% degradation of eosin B (40 ml/min
flow rate) after 180 min at12.0 V.
From Figure12, It is observed for the minimum dye concentration (100 ppm) when
reduced color in EMR using SPEEK membrane for the maximum time of 180 min. When the
highest dye concentration (100 ppm) was observed SPEEK membrane for time 30 min, only
66.5% of Quinoline Yellowdye removal in the dye concentration was detected in the samples.
The effects of reaction time and dye concentration were significant at the 180 min. The
interaction between the dye concentration and reaction time was significant in the removal
ofQuinoline Yellowdye (Figure 13).These results also showed that removal efficiency
SPEEK membrane at all the concentration levels. Similarly, all the times were also
significantly different from each other at the different concentration.Figure 14 showed
influence of time on concentration of Quinoline Yellowduring oxidative degradation of eosin.
These data revealedthat high applied potential, dye concentration and low feed flowrate are
required for fast and efficient degradation process.
Figure 13. The interaction between the dye concentration and reaction time was
significant in the removal ofQuinoline Yellowdye
Further,these parameters also depended on EMR flow pattern andmembrane as well
as electrode area. Thus complete optimizationof these parameters is essential for an efficient
process.

38
Figure 14. Influence of feed flow rate or turbulence (AC) during oxidative degradation
of eosin
Under optimumconditions about 95–98% degradation was observed during180 min,
which can be further enhanced with increase in appliedpotential or membrane area.The dye
removal percentages when the dye was treated with 25 ml/min was higher than that observed
when 50 ml/min and 75 ml/minusing SPEEK membrane. A maximum dye removal efficiency
of 97% was obtained after 180 min of time.
Figure 15. Effect of operating conditions on Eosin B degradation in EMR
70
75
80
85
90
95
100
25 45 65 85 105 125 145 165 185
QuinolineYellowdyeremoval(%)
Time (min)
25 ml/min
50 ml/min
75 ml/min
65
70
75
80
85
90
95
100
25 45 65 85 105 125 145 165 185
EosinBdyeremoval(%)
Time (min)
12V
10V
8V

39
3.6. Effect of operating conditions on Eosin B degradation in EMR
The result of the Eosin Bdye color removal on time for electro membrane oxidation is
shown in Figure 15. The final color removal ratio at 10V isabout 88 % which is higher than
that at 8V. If the potential was up to 12V, the color was increased 95%,which was about 2
times of that at 8 V.Furtherincrease in the potential leads to increase in the color
removalto95%. The result is consistent with the quasi-steadystatecurves on EMR for the
Eosin B dye solution. It was supposed thatthe functional group on SO3-H underwent some
reactionswhen polarized at a certain potential and could enhance the degradation for electro
membrane.
Figure 16. The influence of concentration of the Eosin Bdye solution
The pollutant concentration is very important parameter in wastewater treatment. The
influence of concentration of the Eosin Bdyesolution has been investigated on the electro
membrane degradation with SPEEK membrane after the optimization of pH. In order to
optimize the % removal the initial dye concentrations was varied during the EMR treatment
from 10 to 100 ppm, at constant pH of 4.0. It has been observed from the graph Figure 16 that
increasing concentration of dye solution from 10 to 100 ppm decreases the percentage Eosin
Bdyeremoval and it was found that at 10 ppm dye concentration, % removal was 43% and at
100 ppm dye concentration, percentage removal was increased to 76%. The reason behind
this behavior may be due to the increase in the extent of pore size, permeation and mass
transfer through membranes at necessary dye concentration which increases the migration of
dye. The increases in the dye concentration also increase the transfer ions form dye solution
in to respective poles.
40
50
60
70
80
90
100
20 40 60 80 100 120 140 160 180
EosinBdyeremoval(%)
Time (min)
100 ppm
50 ppm
30 ppm
10 ppm

40
Figure17. Effect of timefor various concentrations of eosin dye
Experiment carried out at different contact times for various concentrations of eosin
dye showed that the percentage removal increases rapidly with increasing contact time for the
first 60 min (Figure17). With increase in reaction time, the external mass transfer coefficient
increases, resulting in movement of eosin dye molecules through membrane. However, the
membrane morphology was affecting the transfer of eosin dye molecules. At 75ml/min, the
highest % removal of eosin dye was observed, hence an indication of the influence of
molecular weight of eosin dye. The percentage of eosin dye removal influenced the chemistry
of both the eosin dye molecule and dipoles in aqueous solutions. Eosin is a dipolar molecule
and chemical structure at low pH, as shown in Figure 17. PEM contains oxygen donor sites
on its surface, e.g. hydroxyl groups and sulfonic groups.
CONCLUSION
Membrane assisted electro chemical degradation (MAEO) process showed 97%
degradation of eosin B against 92% CEand 4.97 kWh/kg of eosin B removed energy
consumption, with SPES, SPSf, SPEEK membranes. While for Nafion® 117showed 76.6%
CE and 3.94 kWh/kgof eosin B removed energy consumption for same extent of eosin B
degradation (97%) under optimum operating conditions. Depending on polymer stabilities
and properties, SPEEK membrane also can be tailored for specific separation purposes by
electro dialysis, because of its high chlorine tolerance, stabilities, conductivity and counter-
ion transport number. The studies presented using MAEO exhibit that the removal of Rose
Bengal from its aqueous solutions can be efficiently achieved through SPES, SPSf, SPEEK.
It was also found that increase in reaction time, the external mass transfer coefficient
increases, resulting in movement of Rose Bengal dye molecules through membrane.
However, the membrane morphology was affecting the transfer of Rose Bengal dye
molecules. The percentage of Rose Bengal dye removal influenced the chemistry of both the
Rose Bengal dye molecule and dipoles in aqueous solutions.
70
75
80
85
90
95
100
25 45 65 85 105 125 145 165 185
EosinBdyeremoval(%)
Time (min)
25 ml/min
50 ml/min
75 ml/min

41
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