CHAPTER 1

INTRODUCTION
Wastewater, also written as waste water, is any water that has been adversely affected in
quality by anthropogenic influence. Wastewater can originate from a combination of domestic,
industrial, commercial or agricultural activities, surface runoff or storm water, and
from sewer inflow or infiltration.
Municipal

wastewater

(also

called sewage)

is

usually

conveyed

in

a combined

sewer or sanitary sewer, and treated at a wastewater treatment plant. Treated wastewater is
discharged into receiving water via an effluent pipe. Wastewaters generated in areas without
access to centralized sewer systems rely on on-site wastewater systems. These typically
comprise a septic tank, drain field, and optionally an on-site treatment unit. The management
of wastewater belongs to the overarching term sanitation, just like the management of human
excreta, solid waste and storm water (drainage).
Sewage is a type of wastewater that comprises domestic wastewater and is therefore
contaminated with feces or urine from people's toilets, but the term sewage is also used to
mean any type of wastewater. Sewerage is the physical infrastructure, including pipes,pumps,
screens, channels etc. used to convey sewage from its origin to the point of eventual treatment
or disposal.

Origin
Wastewater can come from these sources:

Human waste (feces, used toilet paper or wipes, urine, or other bodily fluids), also
known as blackwater, usually from lavatories;

Cesspit leakage;

Septic tank discharge;

Sewage treatment plant discharge;

Washing

water

(personal,

clothes,

floors,

dishes,

etc.),

also

known

as greywater or sullage;

Rainfall collected on roofs, yards, hard-standings, etc. (generally clean with traces
of oils and fuel);

Groundwater infiltrated into sewage;

Surplus

manufactured

liquids

from

domestic

sources

(drinks,

cooking

oil, pesticides, lubricating oil, paint, cleaning liquids, etc.);

Urban rainfall runoff from roads, carparks, roofs, sidewalks/pavements (contains oils,
animal feces, litter, gasoline/petrol, diesel orrubber residues, metals from vehicle exhausts,
etc.);

Seawater ingress (high volumes of salt and microbes);

Direct ingress of river water (high volumes of micro-biota);

Direct ingress of manmade liquids (illegal disposal of pesticides, used oils, etc.);

Highway drainage (oil, de-icing agents, rubber residues);

Storm drains (almost anything, including cars, shopping trolleys, trees, cattle, etc.);

Blackwater (contains feces, urine and flushwater from flush toilets);

Industrial waste

Industrial site drainage (silt, sand, alkali, oil, chemical residues);

Industrial cooling waters (biocides, heat, slimes, silt);

Industrial process waters;

Organic or biodegradable waste, including waste from abattoirs, creameries,

and ice cream manufacture;

Extreme pH waste (from acid/alkali manufacturing, metal plating);

Toxic waste (metal plating, cyanide production, pesticide manufacturing, etc.);

Agricultural drainage, direct and diffuse.

Constituents
The composition of wastewater varies widely. This is a partial list of what it may contain:

Water (more than 95 percent), which is often added during flushing to carry waste
down a drain;

Pathogens such as bacteria, viruses, prions and parasitic worms;

Non-pathogenic bacteria;

Organic particles such as feces, hairs, food, vomit, paper fibers, plant material, humus,
etc.;

Soluble organic

materials

as urea,

fruit

sugars,

soluble proteins, drugs, pharmaceuticals, etc.

Inorganic particles such as sand, grit, metal particles, ceramics, etc.;

Soluble inorganic material such as ammonia, road-salt, sea-salt, cyanide, hydrogen

sulfide, thiocyanates, thiosulfates, etc.;

Animals such as protozoa, insects, arthropods, small fish, etc.;

Macro-solids such as sanitary napkins, nappies/diapers, condoms, needles, children's

toys, dead animals or plants, etc.;

Gases such as hydrogen sulfide, carbon dioxide, methane, etc.;

3

Emulsions such as paints, adhesives, mayonnaise, hair colorants, emulsified oils, etc.;

Toxins such as pesticides, poisons, herbicides, etc.

Pharmaceuticals and hormones and other hazardous substances

Treatment
There are numerous processes that can be used to clean up wastewaters depending on the type
and extent of contamination. There are two basic approaches: to use the waste in the water as a
resource (such as constructed wetlands) or strictly as a pollution (such as the majority of
today's treatment plants). Most wastewater is treated in industrial-scale energy
intensive wastewater treatment plants (WWTPs) which include physical, chemical and
biological treatment processes. However, the use of septic tanks and other On-Site Sewage
Facilities (OSSF) is widespread in rural areas, serving up to 20 percent of the homes in the
U.S.
The most important aerobic treatment system is the activated sludge process, based on the
maintenance and recirculation of a complex biomass composed by micro-organisms able to
absorb and adsorb the organic matter carried in the wastewater. Anaerobic wastewater
treatment processes are also widely applied in the treatment of industrial wastewaters and
biological sludge.

1.1Wastewater treatment processes

Preliminary treatment
The objective of preliminary treatment is the removal of coarse solids and other large
materials often found in raw wastewater. Removal of these materials is necessary to enhance
4

the operation and maintenance of subsequent treatment units. Preliminary treatment operations
typically include coarse screening, grit removal and, in some cases, comminution of large
objects. In grit chambers, the velocity of the water through the chamber is maintained
sufficiently high, or air is used, so as to prevent the settling of most organic solids. Grit
removal is not included as a preliminary treatment step in most small wastewater treatment
plants. Comminutors are sometimes adopted to supplement coarse screening and serve to
reduce the size of large particles so that they will be removed in the form of a sludge in
subsequent treatment processes. Flow measurement devices, often standing-wave flumes, are
always included at the preliminary treatment stage.
Primary treatment
The objective of primary treatment is the removal of settleable organic and inorganic solids by
sedimentation, and the removal of materials that will float (scum) by skimming.
Approximately 25 to 50% of the incoming biochemical oxygen demand (BOD), 50 to 70% of
the total suspended solids (SS), and 65% of the oil and grease are removed during primary
treatment. Some organic nitrogen, organic phosphorus, and heavy metals associated with
solids are also removed during primary sedimentation but colloidal and dissolved constituents
are not affected. The effluent from primary sedimentation units is referred to as primary
effluent.
Secondary treatment
The objective of secondary treatment is the further treatment of the effluent from primary
treatment to remove the residual organics and suspended solids. In most cases, secondary
treatment follows primary treatment and involves the removal of biodegradable dissolved and
colloidal organic matter using aerobic biological treatment processes. Aerobic biological
treatment (see Box) is performed in the presence of oxygen by aerobic microorganisms
(principally bacteria) that metabolize the organic matter in the wastewater, thereby producing
more microorganisms and inorganic end-products (principally CO 2, NH3, and H2O). Several
aerobic biological processes are used for secondary treatment differing primarily in the

manner in which oxygen is supplied to the microorganisms and in the rate at which organisms
metabolize the organic matter.
High-rate biological processes are characterized by relatively small reactor volumes and high
concentrations of microorganisms compared with low rate processes. Consequently, the
5

growth rate of new organisms is much greater in high-rate systems because of the well
controlled environment. The microorganisms must be separated from the treated wastewater
by sedimentation to produce clarified secondary effluent. The sedimentation tanks used in
secondary treatment, often referred to as secondary clarifiers, operate in the same basic
manner as the primary clarifiers described previously. The biological solids removed during
secondary sedimentation, called secondary or biological sludge, are normally combined with
primary sludge for sludge processing.
Tertiary and/or advanced treatment
Tertiary and/or advanced wastewater treatment is employed when specific wastewater
constituents which cannot be removed by secondary treatment must be removed.Individual
treatment processes are necessary to remove nitrogen, phosphorus, additional suspended
solids, refractory organics, heavy metals and dissolved solids. Because advanced treatment
usually follows high-rate secondary treatment, it is sometimes referred to as tertiary treatment.
However, advanced treatment processes are sometimes combined with primary or secondary
treatment (e.g., chemical addition to primary clarifiers or aeration basins to remove
phosphorus) or used in place of secondary treatment (e.g., overland flow treatment of primary
effluent).
Why Electrocoagulation?
The technology removes metals, colloidal solids and particles, and soluble inorganic pollutants
from aqueous media by introducing highly charged polymeric metal hydroxide species. These
species neutralize the electrostatic charges on suspended solids and oil droplets to facilitate
agglomeration or coagulation and resultant separation from the aqueous phase. The treatment
prompts the precipitation of certain metals and salts.EC requires simple equipment and is easy
to operate with sufficient operational latitude to handle most problems encountered on
running. Wastewater treated by EC gives palatable, clear, colorless and odorless water. Sludge
formed by EC tends to be readily settable and easy to de-water,

compared to conventional alum or ferric hydroxide sludges, because the mainly metallic
oxides/hydroxides have no residual charge.

There is no use of any chemical in this process thus this makes the process chemical
free and the main advantage of this process is very efficient and is very time saving as the
6

process is entirely very fast. EC can produce effluent with less TDS content as compared
with chemical treatments, particularly if they can be precipitated as hydroxides. If this
water is reused, the lower TDS level contributes to a reduced water recovery cost.

Flocs formed by EC are similar to chemical floc, except that EC floc tends to be much
larger, contains less bound water, is acid-resistant and more stable, and therefore, can be
separated faster by filtration.

The EC process has the advantage of removing the smallest colloidal particles, because
the applied electric field neutralises any residual charge, thereby facilitating the
coagulation.

The EC process generally avoids excessive use of chemicals and so there is reduced
requirement to neutralize excess chemicals and less possibility of secondary pollution
caused by chemical substances added at high concentration as when chemical coagulation
of wastewater is used.

The gas bubbles produced during electrolysis can conveniently carry the pollutant
components to the top of the solution where it can be more easily concentrated, collected
and removed by a motorised skimmer.

The electrolytic processes in the EC cell are controlled electrically and with no moving
parts, thus requiring less maintenance.

Dosing

incoming

waste

water

with sodium

hypochlorite assists

reduction

of biochemical oxygen demand (BOD) and consequent chemical oxygen demand (COD)
although this should be avoided for wastewater containing high levels of dissolved
ammonia (NH4+) due to formation of trihalogenated methanes or THMs. Sodium
hypochlorite can be generated using electrochlorinators.

Due to the excellent EC removal of suspended solids and the simplicity of the EC
operation, tests conducted for the U.S. Office of Naval Research concluded that the most
promising application of EC in a membrane system was found to be as pretreatment to a
multi-membrane system of UF/RO or microfiltration/reverse osmosis (MF/RO). In this
function the EC provides protection of the low-pressure membrane that is more general

than that provided by chemical coagulation and more effective. EC is very effective at
removing a number of membrane fouling species (such as silica, alkaline earth metal
hydroxides and transition group metals) as well as removing many species that chemical
coagulation alone cannot remove.

C
HAPTER 2
LITERATURE REVIEW
1) Golder AK et al (2005) studied on electrocoagulation (EC) of aqueous dye solutions of
two different industrial dyes in a batch stirred cell. Experiments were carried out with 200
mg/l individual concentration of methylene blue (MB) and eosin yellowish (EY) in presence
of NaCl as electrolyte. Effect of operating time and current density on the decolorization of
dye solutions, reduction of chemical oxygen demand (COD) and variation in conductivity, pH
during treatment has been studied. Small difference between color diminution and COD
reduction has been found with the progress of treatment. Sludge formation during EC and
problems associated with this solid waste generation and disposal has been assessed. Energy
consumption in KWh/m(3) with reduction of COD (kg) during treatment has been reported.
Electric power consumption of 1.5 KWh reduces 0.21 and 0.11 kg COD from 0.24 and 0.14
kg of initial COD for MB and EY, respectively, starting from 200 mg/l dye concentration.
2) Yaln evki Yildiz (2008) studied on optimization of Bomaplex Red CRL dye removal
from aqueous solution by electrocoagulation using aluminum electrodes. An orthogonal
array (OA16) experimental design that allows to investigate the simultaneous variations of
five parameters (initial dye concentration, initial pH of the solution, supporting electrolyte
concentration, supporting electrolyte type and current density) having four levels was
employed to evaluate the effects of experimental parameters.Performance measure analysis
was followed by performing a variance analysis, in order to determine the optimum levels and
relative magnitude of the effect of parameters. Because the desired characteristic for response
has been maximum decolorization, Taguchi's the larger the better performance formula was
used. While the optimum conditions were found to be initial dye concentration of 100mg/L,
initial pH of the solution of 3, supporting electrolyte concentration of 0.0mM, supporting
electrolyte type of CaCl2 and current density of 0.50mA/cm2. Under these optimum
conditions, energy consumption is 0.607kWh/kgdye, when the system evaluated also based on
the energy consumptions it can be said that optimum conditions should be modified as
follows: supporting electrolyte concentration of 2.5mM; supporting electrolyte type NaCl, for
100mg/L initial dye concentration; initial pH of the solution of 3; current density of
0.50mA/cm2.

3) A. Fatehizadeh et al (2010) studied on Survey efficiency of electrocoagulation on nitrate

removal from aqueous solution. Water supply for consumption is one of the crucial objectives
of water supply systems. Using of excessive fertilizer is a main source of nitrate content in
water. The high amounts of nitrate in water have a determinable effect on the environment
which must be removed due to drinking and industrial water standards. The purpose of this
study is nitrate removal from aqueous solution by Electrocoagulation process. The applied
pilot was comprised of a reservoir, electrode and power supply. In this study pH, electrical
potential difference, nitrate initial concentration, total dissolved solid , kind of electrode,
electrode connection methods and number of electrode were studied. Moreover, obtained
optimum conditions were tested on Kerman water. The results showed that the
electrocoagulation process can reach nitrate to less than standard limit. pH, electrical potential
difference, total dissolved solids and number of electrodes have direct effect and initial
concentration of nitrate has reverse effect on nitrate removal. This study also showed that
under optimum condition, nitrate removal from Kerman water distribution system was 89.7 %.
4) B.Merzouk et al (2010) studied on the efficiency of electrocoagulation (EC) for the
abatement of COD, TOC, color and turbidity from a real textile wastewater, a pure red dye
solution (disperse dyes 2-naphthoic acid and 2-naphthol) and a solution combining the two
above fluids. The treatment of the dyestuff solution is satisfactory with high levels of color
and organic pollution abatement. The treatment of the industrial waste is less efficient.
Electrocoagulation seems to proceed with no interaction between the two types of matter to be
removed, namely the dye stuff, and the lot of pollutants contained in the industrial waste.
5) Aye Kuleyin et al (2010) studied on Decolorization of levafix brilliant blue E-B by
electrocoagulation method using aluminum and iron electrodes was investigated. The
influence of the operating variables such as current density, initial pH, time of electrolysis,
supporting electrolyte concentration on decolorization efficiency, and energy consumption
was determined. The results show that aluminum electrode (Al) was more effective than iron
(Fe) electrode in terms of decolorization efficiencies and operating costs. When the aluminum
electrode was used, 99% decolorization was obtained at current density of 100 A/m 2, initial
pH of 5.5, electrolyte concentration of 5 mM, and electrolysis time of 20 min. The
corresponding energy consumption and operating cost were found as 16.9 kWh/m3 and 2.921
$ per m3

10

6) R. Sridhar et al (2010) studied on treatment of pulp and paper industry bleaching effluent
by electrocoagulant process. The experiments were carried out in an electrocoagulation reactor
with aluminum as sacrificial electrodes. The influence of electrolysis time, current density,
pH, NaCl concentration, rotational speed of the stirrer and electrode distance on reduction of
color, COD and BOD were studied in detail. From the experimental results,
15 mA/cm2 current density, pH of 7, 1 g/l NaCl, 100 rpm, 28 C temperature and 3 cm
electrode distance were found to be optimum for maximum reduction of color, COD and
BOD. The reduction of color, COD and BOD under the optimum condition were found to be
94%, 90% and 87% respectively. The electrode energy consumption was calculated and found
to be varied from 10.1 to 12.9 kWh/m3 depending on the operating conditions. Under optimal
operating condition such as 15 mA/cm2 current density, pH of 7, 1 g/l NaCl, 100 rpm, 28 C
temperature and 3 cm electrode distance, the operating cost was found to be 1.56 US $/m3.
The experimental results proved that the electrocoagulation is a suitable method for treating
bleaching plant effluents for reuse.

7) Mitra Gholami et al (2011) studied on Dye Removal, Energy Consumption and Operating
Cost of Electrocoagulation of Textile Wastewater as a Clean Process. In this research, the
efficiency of electrocoagulation treatment process using aluminum electrodes to treat synthetic
wastewater containing Reactive Red198 (RR198) was studied. The effects of parameters such
as voltage, time of reaction, electrode connection mode, initial dye concentration, electrolyte
concentration, and inter electrode distance on dye removal efficiency were investigated. In
addition, electrical energy consumption, electrode consumption, and operating cost at
optimum condition have been investigated. The results showed that dye and chemical oxygen
demand removals were 98.6 and 84%, respectively. Electrode consumption, energy
consumption and operating cost were 0.052kg/m3, 1.303kWh/m3 and 0.256US$/m3,
respectively. Dye removal kinetic followed first order kinetics. It can be concluded that
electrocoagulation process by aluminum electrode is very efficient and clean process for
reactive dye removal from colored wastewater.
8) Xiangdong Li et al (2011) studied on Landfill leachate treatment using electrocoagulation. This
study investigated the efficiency of electrocoagulation in removing ammonia nitrogen (NH 3-N) and
chemical oxygen demand (COD) from leachate. The paper studies the factors affecting the efficiency
of removing NH3-N and COD of leachate, such as electrode material,current density, electrolysis time,
Clconcentration and pH of solution. Treatment was carried out in a discontinuous system,and the
results show that the electrocoagulation can be applied to leachate pre-treatment. The operating
11

conditions were current density of 4.96 mA/cm2, the raw pH, Cl concentration of 2319 mg/L,
operating time of 90 min with Fe electrode, the highest COD and NH 3-N removal efficiencies were
49.8% and 38.6%, respectively.

9) M. B. Kasiri et al (2011) studied on Removal of organic dyes by UV/H 2O2 process:

modelling and optimization.The effects of different operational parameters on the
decolorization of a dye solution containing C.I. Acid Blue 92 (AB92) or C.I. Acid Black 1
(AB1) by the UV/H2O2 process were optimized using response surface methodology (RSM).
The reaction time, dye and H2O2 initial concentrations and distance of the UV lamp from the
solution were chosen as input variables. The removal process was performed according to a
central composite design. Predicted results by the proposed models were in good agreement
with experimental values. The optimum points were located by graphical response surfaces
and contour plots. The removal process of the dyes was compared and the efficiency
difference justified by considering the chemical structure of the dyes.
10)Marius Sebastian Secula et al (2011),studied on the removal of Indigo Carmine dye from
aqueous solutions using a batch stirred electrocoagulation reactor. The experimental tests were
carried out in a discontinuous system provided with steel electrodes. The main purpose was to
investigate the effects of the operating parameters, such as pH, initial concentration,
electrolysis duration, current density, and electrolyte support concentration, on the treatment
of a synthetic wastewater containing indigo carmine dye in the batch electrocoagulation
process. The batch electrocoagulation reactor was operated at various current densities ranging
from 5.46 to 54.57 Am 2. Initial concentration of the dye was ranged between 25 and
100 mgL1. The initial value of pH was varied from 5 to 9, while the concentration of the
electrolyte support ranged from 0.2 to 4.5 gL1.It was shown that pH control during
electrocoagulation process is not beneficial in case of Indigo Carmine removal. The highest
rate constants were achieved for a current density of 54.57 Am 2, an initial dye
concentration of 25 mgL 1, an initial pH of 8, and a background electrolyte concentration of
77 mM.
11)Elmira Pajootan et al (2011) studied on binary system dye removal by electrocoagulation
(EC) process using aluminum electrode was studied in a batch electrochemical reactor. Acid
Black 52 and Acid Yellow 220 were used as model dyes. The effect of operating parameters
such as conductivity, current density, initial dye concentration and pH on the
electrocoagulation process was studied and the electrical energy consumption was calculated.

12

The dye removal from real colored wastewater by the electrocoagulation process has been
studied. It was found that the increasing of the current density up to 40 A/m2 had increased the
dye removal efficiency and the optimum pH for EC process was 5. The increasing of
electrolyte concentration from 0 to 8 g/L had a negligible effect on the color removal but it has
decreased the electrical energy consumption. Data for single and binary systems of dye
removal and the results for the synthetic solutions and the real colored wastewater were too
close and it can be concluded that the electrocoagulation process is an effective method to
remove dyes from colored wastewaters..
12) A.R. Amani-Ghadim et al (2012) studied on Optimization of electrocoagulation process
for removal of an azo dye using response surface methodology. The optimization and
modeling of the electrocoagulation process which conducted by means of iron (EC-Fe) and
aluminum (EC-Al) anodes, in the removal of C.I. Reactive Red 43 were performed through
the response surface methodology (RSM). Moreover, the occurrence of possible destructive
reactions during both EC-Fe and EC-Al processes was investigated using UVVis
spectrometry, total organic carbon (TOC) and GCMS analyses. The electrocoagulation
experiments were carried out in a monopolar batch reactor using two anodes and two cathodes
in parallel connections. Current density, time, pH and chloride concentration were considered
as input variables for RSM. The analysis of variance revealed a high coefficient of
determination between experimental removal efficiency and predicted one by RSM developed
models. The optimum conditions proposed by RSM to reach the maximum RR43 removal
through the EC-Fe were different from the ones proposed for the EC-Al. At the optimum
conditions, the removal efficiency of dye was more than 99% for both processes, whereas
90.58% and 98.37% of initial TOC concentration decreased during EC-Fe and EC-Al
processes, respectively.
14) S. Khald et al (2012) studied on Degradation of Disperse Red 167 Azo Dye by Bipolar
Electrocoagulation. This study investigates the influence of variables on the removal
efficiency of solution containing azo dye Disperse Red 167 by bipolar electrocoagulation
(BEC). Current density, time of electrolysis, interelectrode distance, supporting electrolyte
concentration, and total surface area were the variables that mostly influenced the azo dye
removal. The efficiency of different electrode materials (Fe, Al) for azo dye removal is
compared. The obtained results showed the effectiveness of the aluminum and iron electrodes
for azo dye removal. The present study allows achieving a high level of decolorization (100%)

13

with a short reaction time for both electrodes. The method was found to be highly efficient and
relatively fast compared to conventional existing techniques.
15) Abdil O zdemir et al (2012) studied on Simultaneous decolorization of binary mixture of
blue disperse and yellow basic dyes by electrocoagulation. In this paper, electrocoagulation
(EC) has been used for the removal of color from solution containing a disperse dye (Disperse
blue 56) and a basic dye (Basic Yellow 28) in the same solution. Iron electrodes were arranged
in a monopolar fashion. In the EC of the dye mixture, the effects of the supporting electrolyte,
initial pH, electrolysis time, and current density were examined. The results indicated that the
majority of the aforementioned dyes in the synthetic wastewater were effectively removed
when iron electrodes were used as a sacrificial anode. The amount of dye removed was found
by the application of the first derivative spectrophotometric method to the synthetic dye
mixtures. In the presence of both dye molecules, the optimum pH was found to be 7, optimum
NaCl concentration was 3,000mgL_1,and optimum current density was 10.89mAcm_2. The
experimental data were fit to a variety of isotherm models to determine the characteristics of
the EC process. The results indicated that the model provided the best fit for the removal of
dye mixture.
16) Azam Pirkaram et al (2013) studied on Treatment of colored and real industrial effluents
through electrocoagulation using solar energy. This study was undertaken to investigate the
removal of Acid Orange 2 (sodium 4-[(2E)-2-(2-oxonaphthalen-1-ylidene) hydrazinyl]
benzenesulfonate) and Reactive Blue 19 (2-Anthracenesulfonicacid,1-amino-9,10-dihydro9,10-dioxo-4-[[3-[[2-(sulfooxy) ethyl] sulfonyl] phenyl] amino]-,sodium salt (1:2)) from
synthesized and real effluents through electrocoagulation using solar cells for the purpose of
improving economic efficiency of the process. The impact of a number of key operating
parameters was explored including current density, anode type, temperature, pH, and
electrolyte concentration. The current density of 45 Am 2 proved to be the optimum level for
both dyes. The same optimum alternatives were found for the other parameters in both cases:
iron anode, a temperature level of 25C, a pH of 7, and an electrolyte concentration of 15 mg
L1. Both effluent samples were subjected to COD (chemical oxygen demand) and TOC (total
organic carbon) tests. Cost analysis was performed for the treatment process.

14

17) Bhaskar Mondal et al (2013) studied on treatment of textile printing dye-bath effluent. In
this study, treatment of textile printing dye-bath effluent (DBE) has been performed by
electro-coagulation (EC) method using aluminum (Al) electrode in a batch mode. Various
operating parameters such as initial pH (pHo), current density (J), electrolysis time (t) and
inter electrode distance (d) were varied so as to see their effect on multiple responses namely
chemical oxygen demand (COD) removal (Y1), color removal (Y2) and specific energy
consumed (kW h/kg of COD removed; Y3). Full factorial central composite design (CCD) has
been used for carrying out experiments and optimizing responses Y1, Y2 andY3. Multi-response
optimization with desirability function approach has been used to simultaneously
maximize Y1 and Y2,

and

minimize Y3.

Optimized

values

of

various

responses

were: Y1 = 94%, Y2 = 99.7% and Y3 = 0.011 kW h/kg of COD removed. Scum and sludge
generated during EC of DBE have also been analyzed for the possibility of their disposal.

18) Niyaz Mohammad Mahmood et al (2013) studied on Treatment of colored textile

wastewater containing acid dye using electrocoagulation process.In this study, dye removal
from synthetic colored wastewater using electrocoagulation process was studied. Acid Red 73
was used as model dye compound. The effects of operational parameters, such as current
density, reaction time, initial dye concentration, electrolyte concentration, initial pH, and
polyaluminum chloride (as a coagulant), on dye removal were investigated. The cost of
wastewater treatment at optimal condition was investigated. The results showed that
electrocoagulation process was able to remove 99% dye and 88% chemical oxygen demand.
Using polyaluminum chloride as a coagulant had significant impact on improving process
efficiency, time, and cost reduction. It can be concluded that electrocoagulation was a very
effective and fast method to remove acid dye from colored wastewater.

19) Bhaskar Mondal et al (2013) studied on Electrochemical treatment of dye-bath effluent

by stainless steel electrodes: Multiple response optimization and residue analysis. The aim of
this article is to maximize the chemical oxygen demand (COD) and color removal, and
simultaneously minimize the energy consumed per unit mass of COD removed for the
treatment of dye-bath effluent (DBE) by electrochemical (EC) method using stainless steel
15

(SS) electrode in a batch EC reactor. Response surface methodology involving central

composite design was employed to optimize the multiple responses.

The effects of operating parameters such as pH of DBE, and important process parameters
such as current density, electrolysis time and inter electrode space were studied. At the
optimized condition, 91.7% COD removal and 99.8% color removal was observed with
energy consumption of 7.71 kWh/kg of COD removed.

20)Salim Zodi et al (2013) studied on Direct red 81 (DR 81) dye removal by
electrocoagulation process using aluminum electrode was studied in a continuous
electrochemical reactor. The designed reactor includes an electrochemical cell and a sludge
separation cell. The effect of operating parameters such as current density and inlet flow rate
(Q) on the dye, COD and aluminum dissolution rate were studied and the electrical energy
consumption was calculated. The EC formed sludge has been investigated and the influence of
current density and inlet flow rate on it has been studied. It was found that the increasing of
the current density up to 200 A/m2 had increased the dye removal efficiency and the optimum
inlet flow rate for EC process was the minimum at 10 l/h and it has increased the electrical
energy consumption. Current efficiency was strongly depending on flow rates and current
densities.On the contrary a decrease in the electrical energy consumption is observed when the
inlet flow rate increases. Despite the increasing of the inlet flow rate, the specific electrical
energy consumption remained at 5258 kW h/kg Al at 150 A/m2. The total formed sludge was
corresponding with increasing applied current density.

16

CHAPTER 3
ELECTROCOAGULATION
Electrocoagulation (EC), is a rapidly growing area of wastewater treatment, less well known
as radio frequency diathermy or short wave electrolysis, is a technique used for wash water
treatment, wastewater treatment,

industrial

processed

water, and

medical

treatment.

Electricity-based electrocoagulation technology removes contaminants that are generally more

difficult to remove by filtration or chemical treatment systems, such as emulsified oil, total
petroleum hydrocarbons, refractory organics, suspended solids, and heavy metals. There are
many brands of electrocoagulation devices available and they can range in complexity from a
simple anode and cathode to much more complex devices with control over electrode
potentials, passivation, anode consumption, cell REDOX potentials as well as the introduction
of ultrasonic sound, ultraviolet light and a range of gases and reactants to achieve so-called
Advanced Oxidation Processes for refractory or recalcitrant organic substances.
The major challenges for the 21st century are water and energy. Due to increased pollution
from point and non-point sources quality of the water become a crucial problem, particular for
the Third-World Countries. The promising methods based on electrochemical technology are
electrocoagulation, electro flotation, electro decantation, and others. Electrocoagulation (EC)
consists of number of benefits: compatibility, amenability to automation, cost effectiveness,
energy efficiency, safety, and versatility. Though EC has received little scientific attention a
decade back, in the last couple of years, this technology has been widely used for the
treatment of dilute wastewaters having heavy metal , foodstuff, oil wastes, textile and dyes ,
fluorine , polymeric wastes , organic matter from landfill leachate , suspended particles ,
chemical and mechanical polishing wastes, aqueous suspension of ultrafine particles, nitrate,
phenolic waste, arsenic, and refractory organic pollutants including lignin and EDTA. Also,
17

electrocoagulation is applicable for drinking water treatment. This process has capability to
overcome the disadvantages of the other treatment techniques.
EC has a long history: the first plant was built in London in 1889 for the treatment of sewage.
Despite some promising results, the success of this technology has been limited. However,
there has been renewed scientific, economic and environmental interest in this technology in
recent years due to demand of alternative water treatment technologies. EC understandably
has several similarities with the chemical coagulation but also significant differences, such as

side reactions, which are discussed in this section. In the EC system there are multiple
electrochemical reactions occurring simultaneously at the anodes and cathodes. These
mechanisms can be divided into the main mechanisms that cause destabilisation of pollutants,
and side reactions, such as hydrogen formation. The most important reactions are summarised
in Fig3.1

Fig-3.1(Schematic representation of typical reactions during the EC treatment)

Advantages of EC
1. EC requires simple equipment and is easy to operate with sufficient operational latitude to
handle most problems encountered on running.
2. Wastewater treated by EC gives palatable, clear, colourless and odourless water.
18

3. Sludge formed by EC tends to be readily settable and easy to de-water, because it is

composed of mainly metallic oxides/hydroxides. Above all, It is a low sludge producing
technique.
4. Flocs formed by EC are similar to chemical oc, except that EC oc tends to be much
larger, contains less bound water, is acid-resistant and more stable, and therefore, can be
separated faster by ltration.

5. EC produces efuent with less total dissolved solids (TDS) content as compared with
chemical treatments. If this water is reused, the low TDS level contributes to a lower water
recovery cost.
6. The EC process has the advantage of removing the smallest colloidal particles, because the
applied electric eld sets them in faster motion, thereby facilitating the coagulation.
7. The EC process avoids uses of chemicals, and so there is no problem of neutralizing excess
chemicals and no possibility of secondary pollution caused by chemical substances added at
high concentration as when chemical coagulation of wastewater is used.
8. The gas bubbles produced during electrolysis can carry the pollutant to the top of the
solution where it can be more easily concentrated, collected and removed.
9. The electrolytic processes in the EC cell are controlled electrically with no moving parts,
thus requiring less maintenance.
10. The EC technique can be conveniently used in rural areas where electricity is not
available, since a solar panel attached to the unit may be sufficient to carry out the process.
Disadvantages of EC
1. The sacricial electrodes are dissolved in to waste water streams as a result of oxidation,
and need to be regularly replaced.
2. The use of electricity may be expensive in many places.
3. An impermeable oxide lm may be formed on the cathode leading to loss of efciency of
the EC unit.
4. High conductivity of the wastewater suspension is required.
19

5. Gelatinous hydroxide may tend to solubilise in some cases.

3.1Description of the technology
In its simplest form, an electrocoagulating reactor may be made up of an electrolytic cell with
one anode and one cathode. When connected to an external power source, the anode material
will electrochemically corrode due to oxidation, while the cathode will be subjected to
passivation.
But, this arrangement is not suitable for wastewater treatment, because for a workable rate of
metal dissolution, the use of electrodes with large surface area is required. This has been
achieved by using cells with monopolar electrodes either in parallel or series connections. A
simple arrangement of an EC cell with a pair of anodes and a pair of cathodes in parallel
arrangement is shown in Fig.3.2

Fig-3.2. Bench-scale EC reactor with monopolar electrodes in parallel connection.

It essentially consists of pairs of conductive metal plates placed between two parallel
electrodes and a dc power source as shown in Fig. 2. The experimental set up also requires a
resistance box to regulate the current density and a multimeter to read the current values.The
conductive metal plates are commonly known as sacrificial electrodes. The sacrificial
anode lowers the dissolution potential of the anode and minimizes the passivation of the
cathode. The sacrificial electrodes may be made up of the same or of different materials as the
anode. An arrangement of an EC cell with monopolar electrodes in series is shown in Fig.3.3.

20

Fig- 3.3 Bench-scale EC reactor with monopolar electrodes in series connection.

As can be seen from Fig-3. 3, each pair of sacrificial electrodes is internally connected with
each other, and has no interconnections with the outer electrodes. This arrangement of
monopolar electrodes with cells in series is electrically similar to a single cell with many
electrodes and interconnections. In series cell arrangement, a higher potential difference is
required for a given current to flow because the cells connected in series have higher
resistance. The same current would, however, flow through all the electrodes. On the other
hand, in parallel arrangement the electric current is divided between all the electrodes in
relation to the resistance of the individual cells. Some authors have, however, used bipolar
electrodes with cells in parallel. In this case, the sacrificial electrodes are placed between the
two parallel electrodes without any electrical connection as shown in Fig-3.4.

Fig-3.4( Bench-scale EC reactor with bipolar electrodes in parallel connection)

Only the two monopolar electrodes are connected to the electric power source with no
interconnections between the sacrificial electrodes. This cell arrangement provides a simple
21

set-up, which facilitates easy maintenance during use. When an electric current is passed
through the two electrodes, the neutral sides of the conductive plate will be transformed to
charged sides, which have opposite charge compared to the parallel side beside it. The
sacrificial electrodes in this case are also known as bipolar electrodes. Thus, during
electrolysis, the positive side undergoes anodic reactions, while on the negative side, cathodic
reaction is encountered. Consumable metal plates, such as iron or aluminum, are usually used
as sacrificial electrodes to continuously produce ions in the system. The released ions
neutralize the charges of the particles and thereby initiate co-agulation. The released ions may
remove the undesirable contaminants either by chemical reaction and precipitation, or by
causing the colloidal materials to coalesce and then re-moved by electrolytic flotation.

In addition, as water containing colloidal particulates, oils, or other contaminants move

through the applied electric field, there may be ionization, electrolysis, hydrolysis, and freeradical formation which may alter the physical and chemical properties of water and
contaminants . As a result, the reactive and excited state causes contaminants to be released
from water and destroyed or made less soluble. Inert electrodes, such as titanium and the
passage of alternating current, have been observed to remove metal ions from solution and to
initiate coagulation of suspended solids. To ensure more effective removal of the undesirable
ions, wastewater may be passed through a series of cells containing electrodes made up of
various metals. In such cases, the contaminated wastewater is passed through the annular
spaces between the electrodes and is exposed to sequential positive and negative electrical
fields. To optimize the removal efficiencies, the water characteristics such as pH, oxidation
reduction potential, and conductivity can be adjusted for specific contaminants. In the EC
process, an electric field is applied to the medium for a short time, and the treated dispersion
transferred to an integrated clarifier system where the watercontaminant mixture separates
into a floating layer, a mineral-rich sediment, and clear water. The aggregated mass settles
down due to gravitational force. The clear water can be extracted by conventional methods.
3.2 Main reactions
Electrocoagulation of wastewater using an aluminium electrode The electrolytic dissolution
of the aluminium anode produces the cationic monomeric species such as Al and Al(OH) at
low pH, which at appropriate pH values are transformed initially into Al(OH) and nally
polymerized to Aln(OH)n according to the following reactions:

22

Al Al (aq) +3e (1)

Al (aq) +3HOAl(OH) +3H (aq) (2)
nAl(OH)Aln(OH)n (3)
However, depending on the pH of the aqueous medium other ionic species, such as Al(OH),
Al(OH)and Al(OH) may also be present in the system. Examination of the pEpH
equilibrium diagram reveals that under appropriate conditions various forms of charged
multimeric hydroxo Al species may be formed. For example, the structures of dimeric and
polymeric Al hydroxo complexes are shown below:

These gelatinous charged hydroxo cationic complexes can effectively remove pollutants by
adsorption to produce charge neutralization, and by enmeshment in a precipitate. Ming et al.
have reported the deuorination of water by electrolysis using aluminum electrodes.
According to the proposed mechanism the Al ions under high F concentration may be
induced to form AlFwhich was transformed to insoluble salt NaAlF by adding sodium
ions according to the following reactions:
Al+6FAlF (4)
AlF+3Na NaAlF (5)

Side reactions
In addition to dissolving of aluminium production, other electrochemical reactions can also
take place in the EC system. They are:
hydrogen formation at the cathodes
increase of pH due to the formation of hydroxyl ions or the consumption of hydronium
ions/protons
reduction of metal ions on the cathodes
Some articles have also speculated that oxygen is also produced on the anodes . However, it
seems that this does not take place in typical conditions (electrochemical potential) of EC
systems as dissolution of anodes follows Faradays law .There is technology called
23

electroflotation (EF), which can be used to produce bubbles that can effectively separate
particles from the solution . In electroflotation technology, oxygen bubbles are produced on
the anodes and hydrogen bubbles on the cathodes, whereas in EC technology only hydrogen
bubbles are produced on the cathodes. The efficiency of the flotation in EC and EF
technologies depends on the size of the bubbles. Smaller bubbles can provide a larger surface
area for particle attachment. EF produces smaller diameter bubbles than commonly used
dissolved air flotation (DAF) technology. The mean diameter of the hydrogen and oxygen
bubbles generated in EF range from 17 to 50 m, whereas in DAF the typical mean diameter
of the bubbles range from 48 to 60 m .

Usually, the diameters of the electrolytically generated bubbles obey lognormal distribution.
Electrode material, current density and pH affect bubble size. The smallest hydrogen bubbles
are produced at neutral or acidic pH . Stainless steel plates have been found to produce the
smallest bubbles. There has been some controversy in the reported effects of current density
on the bubble size. Sarkar et al. studied the effect of current density and electrode on bubble
size produced on the cathodes. They discovered that a significant proportion of hydrogen
produced on the cathodes can be dissolved in the solution. According to their results, bubble
size diameter is a function of hydrogen production rate, bubble nucleation rate and dissolved
gas concentration field. In contrast to chemical coagulation, EC treatment increases the pH of
the solution when it is in an acidic, neutral or slightly alkaline region and decreases when it is
highly alkaline. This change of pH during the EC treatment affects the speciation of
aluminium hydroxides. At highly acidic pH (pH 2) the alkalinity produced during the EC is
not sufficient to increase the pH of the solution, whereas at pH 3 and higher initial pH values
pH rises during the treatment This is easily understandable, as concentration of hydronium
ions increases by factor 10 when pH decreases from pH 3 to pH 2. When initial pH is
significantly alkaline (pH > 9), pH probably decreases due to the formation of aluminate
[Al(OH) ], which is an alkalinity consumer . It seems that the pH change rate and final
steadystate pH depends on the concentration of anions in the solution. According to Trompette
and Vergnes , pH increases more in sulphate solution than in chloride solution. Sulphates can
replace hydroxyl ions in the hydroxide precipitates and therefore less hydroxyl ions are bound
to hydroxides. Because electrochemical reactions occur at the surface of the electrodes, the
concentration of reaction products is highest at the electrode surface and the concentration
gradient exists from the surface towards the bulk solution. Therefore, pH decreases at the
vicinity of the anodes and vice versa at the cathode surface. This can lead to precipitation of
24

inorganic salts on the electrode surface if their solubility changes as a function of pH, e.g.,
precipitation of calcium carbonate on the cathodes . If electrochemical potential at the
cathodes is in the right region, the direct electrochemical reduction of metal cations may occur
at the cathode surface (Eq. 6)
Me(aq)+neMee (s)

(6)

There are several studies where the removal of metals from wastewaters has been studied,

Results indicate that metals are mostly removed by coagulation and co-precipitation.
However, the reduction of metal ions may have some effect on removal efficiency even if they
are not reduced to the metallic state. Heidmann and Calmano studied the removal of Zn(II),
Cu(II), Ni(II), Ag(I) and Cr(VI) from aqueous solution by EC. They proposed that Zn(II),
Cu(II), Ni(II) and Ag(I) were removed from the solution by hydrolysation and coprecipitation, whereas Cr(VI) was reduced first to Cr(III), after which it was precipitated as
hydroxide. It is probable that dissolving of aluminium at the cathodes prevents plating of the
cathode with other metals. With iron or inert cathodes, some plating could be expected at least
with some metal ions, e.g., Ni(II) and Cu(II). It is possible that plating is a slow reaction in
typical concentrations and removal occurs mainly by coagulation co-precipitation due to these
kinetic reasons.
Properties of the sludge
The properties of produced sludge are important because sludge treatment and disposal are
one of the major cost factors in water and wastewater treatment, especially when sludge has
been produced by chemicals. The dried EC sludge produced by different combination
electrodes during arsenic removal Dried sludge formed by Al-Al electrodes contained
amorphous aluminium hydroxide and/or aluminium oxyhydroxide. Fe-Fe electrodes produced
crystalline phases, such as magnetite, and poorly crystalline phases, such as iron
oxyhydroxides and lepidocrocite. Sludge produced by combined Fe-Al electrodes contained
the aforementioned products as well as mansfeldite, diaspore and iron oxide. Crystallinity of
iron species decreased, possibly due to the substitution of iron by aluminium. Emamjomeh
and Sivakumar studied the sludge produced during the fluoride removal by EC using XRD .
Identified products were aluminium fluoride hydroxide complexes and aluminium hydroxide.
Shafael et al. identified amorphous manganese and aluminium species in sludge produced by
25

EC during Mn(II) removal. The settleability of sludge produced by EC during paper mill and
textile wastewater treatment has been studied . When paper mill wastewater was treated, the
sludge volume index (SVI) was 0.2070.310 L/g and 0.0810.091 L/g for aluminium and iron
electrodes, respectively. The sludge formed by iron electrodes was heavier and produced a
more compact layer. The authors observed similar results with textile wastewaters. Hydrogen
produced during the EC induces flotation of particles and decreases settling velocity.

The operating parameters of EC affect the properties of hydrogen bubbles. Lai and Lin treated
chemical mechanic polishing wastewater by Al-Fe electrodes and studied settling properties of
produced sludge. They concluded that complex models of third or fourth order described the
sludge settling data. The heat value of the sludge produced by EC has been measured using a
bomb calorimeter . Heat value was 5.3 MJ/kg and authors concluded that it could be used as a
fuel in the furnaces and the produced ash could be blended with the cementitious mixtures. It
is probable that sludge produced during the treatment of other wastewaters containing high
organic matter also has a high heat value. The combination of EC and electrodewatering has
been studied for the reduction of water content in sewage sludge . The combination of EC and
electrodewatering reduced water content of the sludge to 55%, whereas water content in
sludge treated with only pressure filtration was 78%.
3.3 Treatment parameters
There are various parameters which have an effect on the efficiency of the EC in removing the
pollutants from water. Parameters which are known to have an effect are:
Material of the electrodes can be iron, aluminium and/or inert material (typically
cathodes). Iron and aluminium ions and hydroxides have different chemistries and
applications.
pH of the solution has an effect on the speciation of metal hydroxides in the solution and
also on the -potential of the colloidal particles. It also affects the dissolution of aluminium
cathodes.
Current density is proportional to the amount of electrochemical reactions taking place on
the electrode surface.
26

 Treatment time or electric charge added per volume is proportional to the amount of
coagulants produced in the EC system and other reactions taking place in the system.
Electrode potential defines which reactions occur on the electrode surface.
Concentration of the pollutants affects the removal efficiency because coagulation does not
follow zeroth-order reaction kinetics but rather pseudo second or first-order kinetics.
Concentration of anions, such as sulphate or fluoride, affects the composition of
hydroxides because they can replace hydroxide ions in the precipitates.

Temperature affects floc formation, reaction rates and conductivity. Depending on the
pollutant, increasing temperature can have a negative or a positive effect on removal
efficiency.
Other parameters, such as hydrodynamical conditions and inter-electrode distance, may
have effect on efficiency of the treatment and electricity consumption. However, these
parameters have not been widely studied or they have a negligible effect on the removal
efficiency.

Electrode materials
Electrode material defines which electrochemical reactions take place in the EC system.
Aluminium and iron electrodes have both been used successfully in EC systems. Aluminium
dissolves in all cases as Al(III) whereas there is some controversy as to whether iron dissolves
as Fe(II) or Fe(III) . Most results indicate that iron dissolves as Fe(II), such as , and is oxidised
in bulk solution to Fe(III) if there are oxidants, such as oxygen, present in sufficient
concentration and pH is alkaline . Fe(II) is a poor coagulant compared to Fe(III) due to higher
solubility of hydroxides and lower positive charge, which explains some poor results obtained
with iron electrodes, such as in the study of Bagga et al. Optimal material selection depends
on the pollutants to be removed and the chemical properties of the electrolyte. In general,
aluminium seems to be superior compared to iron in most cases when only the efficiency of
the treatment is considered. However, it should be noted that aluminium is more expensive
than iron. Inert electrodes, such as metal oxide coated titanium, are used as cathodes in some
constructions. When water has significant amounts of calcium or magnesium ions, the inert
cathode material is recommended . There are also some studies where combinations of
27

aluminium and iron electrodes have been used. Linares-Hernndez et al.

obtained high

removal of colour with aluminium electrodes, while iron was more effective than aluminium
in reducing COD from industrial wastewater. A combination of iron and aluminium removes
both colour (71%) and COD (69%) with high efficiency. Similar results were obtained when
paper mill wastewaters were treated with various aluminium and iron electrode combinations .
Aluminium electrodes were most effective in removing colour of the wastewater, whereas iron
electrodes removed COD and phenol from the wastewater more effectively than aluminium
electrodes.

A combination of aluminium and iron electrodes removed colour, COD and phenol with high
efficiency. Combination electrodes have been studied for arsenic removal from groundwater .
Iron electrodes and a combination of iron and aluminium electrodes gave the highest arsenic
removal efficiencies. Similar results were obtained for copper, chromium and nickel removal
from metal plating wastewater . Fe-Al pair has been most effective in removing indium from
water .
pH of the solution
One key parameters of EC treatment is the pH of the solution to be treated. It has an effect on
the conductivity of the solution, dissolution of the electrodes, speciation of hydroxides and potential of colloidal particles. Aluminium cations and hydroxides cause destabilisation of
colloids. Effective coagulant species are formed in acidic, neutral and slightly alkaline pH. In
highly alkaline pH Al(OH) ions are formed and these ions have poor coagulation
performance. Fe(III) is effective in a wider pH area than Al(III) and works also in slightly
alkaline pH. It is also known that competing anions have an effect on the optimum pH of the
coagulation. The effect of water pH on the efficiency of pollutant removal can mostly be
explained by the aforementioned mechanisms. However, as discussed in section 1.2, pH
increases during the EC treatment, making it a constantly changing parameter; therefore
mechanistic studies of EC systems are difficult to conduct. In pHs lower than 3, the release
rate of aluminium during electrolysis with a constant charge per volume was lower than in
pHs above 3 . Chemical dissolution of aluminium cathodes occurs because pH increases to a
level where aluminate is formed. It is probable that acidic bulk solution inhibits this reaction
because produced hydroxyl ions are consumed by the acid in the solution. In acidic pH the
dissolution of iron electrodes was significant even without electricity, whereas oxidation of
Fe(II) to Fe(III) occurs only at pHs above 5 . The dissolution rate decreases at high pH, which
28

is understandable as the corrosion rate of iron decreases in alkaline pH in the presence of

oxygen because a passive layer forms on the surface. It has been suggested that initial pH is
key parameter when either chemical coagulation or EC is selected for the water treatment . EC
is more suitable when higher pH is desired (acidic solutions), whereas chemical coagulation is
preferred when pH should decrease before discharge. There are also some pollutants which
have specific optimum pHs of treatment, such as phosphorus and metal cations. The effect of
initial pH on phosphate removal from wastewater by EC with iron electrodes has been
studied .

The highest removal efficiency was observed at the lowest tested initial pH (pH 3).
Wastewater pH increased to a highly alkaline level (pH 1012) during the long treatment,
probably due to partial replacement of HO- by PO. In high pH the removal rate was poor
due to the formation of Fe(OH) and higher solubility of FePO. In higher pH there are more
HO ions to compete with PO and therefore less FePO is formed. Other researchers have
had similar results with iron electrodes when they studied the removal of phosphorus from
secondary effluent. According to Janpoor et al., phosphorus removal from laundry wastewater
with aluminium electrodes was poor when initial pH was lower than 6 or higher than 8 . As
with aluminium and iron, other metal cations can also form hydroxides in water. Most nonionic hydroxides have low solubility in water and can be removed by precipitation and coprecipitation with EC systems. Hanay and Hasar studied removal of Cu(II), Mn(II) and Zn(II)
by aluminium electrodes. Removal efficiency increased when initial pH of the wastewater
increased. Similar results have been obtained for the removal of Co(II) , As(V) , Cu, Cr and Ni
, Cu(II), Pb(II) and Cd(II) , Cu(II), Ni(II), Zn(II) and Mn(II) , In(III) , Mn(II) and Cr(III)
Hg(II) removal was not significantly affected by initial pH in the range of 37 .
Current density and treatment time
Current density is directly proportional to the rate of electrochemical reactions taking place on
the electrode surface and it also has an influence on the electrode potential, which defines the
reactions taking place on the electrode surface. It seems that on iron and aluminium anodes,
dissolution reaction is the primary reaction, and the proportion of other reactions is
insignificant at the typical current densities and electrode potentials when pH is neutral or
acidic . At alkaline pH the dissolution rate of iron anodes can be lower than the value
calculated by Faradays law, which indicates that there can be other reactions at the anode in
these conditions . Coagulant produced by electrolysis can usually be calculated according to
29

Faradays law when current and treatment times are known (Eq. 3). Coagulant concentration
produced by electrolysis on anodes is typically directly proportional to the electric charge
added per volume (coulombs per litre). However, the total amount of coagulant dissolved also
includes chemical dissolution of the electrodes in low pH and the dissolution of aluminium
cathodes. Current density probably has some influence on the chemical dissolution of
aluminium cathodes, as it affects the rate of hydroxyl ion production at the cathodes.

Mouedhen et al. studied aluminium dissolution from the cathodes with an electrochemical
cell constructed of platinised titanium anode and aluminium cathode. They used constant
charge per volume (540 C/L) and various current densities. According to their results, as the
current density decreases the amount of aluminium generated increases. These results indicate
that even low current density (< 1 A/dm2 ) initiates the dissolving reaction on the cathodes if
solution pH is not highly acidic and therefore the produced amount of aluminium on the
cathodes depends more on the treatment time than the electric charge added per volume.
Concentration of anions
Concentration of anions in the solution affects the stability of passive layer of the aluminium
electrodes. Sulphate anions are passivating agents and therefore reduce the production of
metal cations . Chloride, on the other hand, induces the breakdown of the passive layer and
pitting corrosion. The effect of supporting electrolytes on the efficiency of an EC system has
been studied by treating unskimmed milk samples and a cutting oil emulsion by aluminium
electrodes in the presence of NaCl, Na2SO4, NH4Cl and (NH4)2SO4 . According to results,
sulphate anions increase electrical consumption and have a negative effect on EC efficiency.
Ratio of [Cl- ]/[SO4 2-] should be 0.1 or higher to ensure breakdown of the passive film.
Mouedhen et al. reported that optimum concentration of Cl- ions was 61 mg/l. In addition to
the effect on the passive layer, some salts can precipitate on the cathodes if the concentration
of salts in water is sufficiently high . This insulating layer increases power consumption
significantly . Competing anions can replace hydroxyl anions in the precipitate, which has an
effect on the properties of hydroxide and therefore, also on efficiency and optimum conditions
of coagulation processes. Competing anions can also have a direct influence if the pollutant is
anion e.g. fluoride or phosphate. Hu et al. Studied fluoride removal in the presence of
chloride, nitrate and sulphate anions. They obtained the best results in the absence of these
anions. Sulphate ion concentration had a significant effect on the removal efficiency of the
30

fluoride, probably because it can compete with fluoride ions from Al(III). According to
Vasudevan et al. fluoride and arsenate compete with phosphate ion and reduce its removal by
EC.

Temperature
The effect of temperature on the removal of pollutants through EC has been studied in a few
articles. The effect of solution temperature on boron removal by EC has been studied in the
range of 293333 K . When temperature increased from 293 K to 333 K, the boron removal
efficiency increased from 84% to 96%. The opposite effect has been reported when paper mill
wastewater was treated at temperatures between 293 and 333 K . Removal of colour, COD and
phenol decreased by 1020% when temperature increased from 293 K to 333 K. The effect of
temperature on phosphate removal from wastewater by EC has been studied in the range of
293333 K. Removal efficiency was 29% lower at 293 K than in higher temperatures. Authors
concluded that at low temperatures the dissolution of anode occurs at a lower rate. However,
they did not present any results, such as concentrations of aluminium dissolved from
electrodes, which would support this conclusion. It has been suggested that when temperature
is too high, there is a shrinkage of large pores of the Al(OH)3 gel, which causes the formation
of dense flocs that are more likely to deposit on the electrode surface . Increasing temperature
also enhances the solubility of aluminium. However, it seems that increasing temperature can
have positive and negative effects on the removal efficiency. It is possible that the effect of
temperature on removal efficiency depends on the removal mechanism of pollutants.
Comparison of electrocoagulation and chemical coagulation
There are only a few published studies in which chemical coagulation and EC have been
compared. However, these technologies can be considered competing technologies and
therefore, the comparisons of treatment efficiencies are important. As previously mentioned,
reliable comparisons are difficult to conduct due to the dynamic nature of the EC process.
Change of pH during the EC and its effect on aluminium species formed has been studied .
The formation of monomeric and polymeric aluminium hydroxides were compared when
31

aluminium was added as AlCl or by EC. According to results, there are no significant
differences in the speciation of aluminium obtained by these two methods. Authors concluded
that both processes are similar in terms of removing the pollutants from the wastewater under
the same dynamic conditions, doses of aluminium and steady-state pHs. EC and chemical
coagulation have been compared in the treatment of ultrafine quartz suspensions , the removal
of Cr(VI) and as a pretreatment before microfiltration membranes .

Kili et al.

compared chemical coagulation and EC and the effect of initial pH and

aluminium dosage on the removal efficiency of a model pollutant.They used aluminium

anodes and stainless steel cathodes. The optimum pH for the removal of particles was 9 for EC
and 69 for chemical coagulation. Wider optimum coagulation pH with chemical coagulant
was probably a result of higher sulphate concentration because aluminium sulphate was used
as a chemical coagulant. The effect of aluminium dosage on the destabilisation of pollutants
and optimum aluminium dosages were similar with both technologies. Both technologies
removed turbidity equally well. Researchers suggested, based on the -potential
measurements, that destabilisation mechanisms are similar with both technologies. EC was
more effective (42%) than chemical coagulation (approximately 11.5%) at removing Cr(VI)
from aqueous solution . Some Cr(VI) was removed by deposition on the cathode. Alum and
aluminium sulphate showed poor Cr(VI) removal, which was probably due to competitive
adsorption of sulphate ions on the sludge matrix. Zhu et al. compared EC and chemical
coagulation pretreatment for enhanced virus removal using microfiltration membranes. Both
technologies improved virus removal but EC outperformed chemical coagulation in removal
efficiency. The researchers suggested that the enhanced removal by EC was due to
electrophoretic movement of viruses on electrodes. However, the effect of electrophoresis on
removal efficiency in EC has not been reliably verified by experimental studies.
Somewhat opposite results were obtained when chemical coagulation and EC were compared
at pretreatment for surface water microfiltration . Chemical coagulation with ferric chloride
was superior compared to EC with iron anode and stainless steel cathode. Iron dissolved in
Fe(II) form which had higher solubility and poor coagulation performance compared to Fe(III)
in ferric chloride. NOM can prevent oxidation of Fe(II) to more effective Fe(III) form . Zhu et
al. used synthetic freshwaters which did not include NOM in their studies, which may explain
better performance of EC in their research. According to studies in which EC and chemical
coagulation have been compared, it seems that these technologies have similar destabilisation
mechanisms. However, a chemical coagulant is added together with anion, such as sulphate or
32

chloride, which may have some influence on the efficiency of the process. In some cases, side
reactions, such as reduction on the cathode surface, may play an important role in the
destabilisation of pollutants. Iron is dissolved from the iron electrodes in Fe(II) form and
hence oxidation to more effective Fe(III) form is important in order to obtain high removal
efficiency. Therefore, it would be more descriptive to compare Fe(II) coagulants, such as
ferrous sulphate, and EC with iron electrodes.

3.4Practical considerations of electrocoagulation

Constructions of electrocoagulation systems
EC systems are typically constructed of plate electrodes and water flows through the space
between the electrodes . There are several methods how electrodes can be arranged in the EC
system. Flow between the electrodes can follow a vertical or horizontal direction. Electrodes
can be monopolar or bipolar. In the monopolar systems (Fig. 3a) all anodes are connected to
each other and similarly all cathodes are also connected to each other. In the bipolar systems
(Fig. 3b) the outermost electrodes are connected to a power source and current passes through
the other electrodes, thus polarising them. In the bipolar systems the side of the electrode
facing the anode is negatively polarised and vice versa on the other side facing the cathode.

Fig-3.5 Connections and electrode polarity in a) bipolar and b) monopolar EC systems.

33

The pollutant removal efficiencies and operating costs of monopolar and bipolar
configurations have been compared in several studies. Slaughterhouse wastewaters have been
treated with mild steel and aluminium electrodes arranged in bipolar or monopolar
configurations. The best performance was obtained using mild steel electrodes in bipolar
configuration.

Economic calculations were made based on the results but electrode consumption was
calculated according to Faradays law which gives false results, especially when aluminium
electrodes are used. Golder et al. [119] studied Cr3+ removal with EC by mild steel
electrodes. Current efficiency for the dissolving of the mild steel electrodes was lower when
electrodes were in bipolar configuration (64.5%) than when they were in monopolar
configuration (91.7%). This is probably due to the higher electrode potential of the electrodes
in bipolar arrangement and competing reactions taking place on the electrodes. A complete
removal of Cr was obtained when electrodes were in the bipolar arrangement. However,
treatment cost was lower with a monopolar arrangement when the treatment was continued to
the discharge limit. Similar results were reported when EC was used for the removal of
fluoride from drinking water. The bipolar connection removed fluoride more effectively but
operating costs of the treatment were higher with this configuration. Monopolar configuration
has been reported to be better in the treatment of laundry wastewater, oily bilge water and
textile wastewater. Results of the aforementioned studies could be summarised so that
monopolar configuration has lower operating cost but in some cases higher removal of
pollutants can be achieved with bipolar configuration, possibly due to additional side
reactions. Typically, direct current (DC) has been used in EC systems. However, there are a
few studies in which alternating current (AC) has been tested. Vasudevan et al. studied the
removal of fluoride from water with DC and AC EC systems. They observed similar removal
efficiencies with both technologies. However, energy consumption was slightly lower with AC
technology. Eyvaz et al.used alternating pulsed current in their study. Alternating pulsed
current enhanced removal efficiency compared to DC current. Pollutant removal decreases
over the course of time with DC systems, possibly due to passivation of electrodes, whereas in
an alternating pulse current system this was not observed. Polarity reversal has also been
suggested by other authors to reduce passivation of electrodes . In addition to actual
coagulation procedure, some sludge removal process has to follow EC. As with chemical
coagulation, these can be flotation, sedimentation or filtration. Due to hydrogen bubble
production, flotation is often the preferred choice.
34

3.5 Applications of electrocoagulation

Most of the articles published on EC concentrate on the removal of some specific pollutant or
pollutants from synthetic or real solutions. The majority of these application studies can be
divided into the following categories:

Removal of metal ions and/or hydroxides from synthetic solutions, groundwaters or

wastewaters (Table 1). Typically high or complete removal could be obtained when
treatment parameters are optimised. Aluminium, iron and combination electrodes can

be used in EC system.
Removal of organic material from wastewaters or synthetic solutions (Table 2).
High removal (> 70%) is typically obtained with optimum parameters. Aluminium,
iron and combination electrodes can be used. In general, iron electrodes give higher
organic matter removal, whereas higher colour removal is obtained with aluminium

electrodes.
Purification of surface waters from natural organic matter, inorganic pollutants or
microbes (Table 3). Typically high removal of pollutants (> 90%). Aluminium
electrodes are more commonly used than iron electrodes in these applications.

Combinations of electrocoagulation and other water treatment technologies

Besides the sludge separation technologies, filtration, flotation and sedimentation, other water
treatment technologies have also been combined with EC. EC has been combined with
chemical coagulants, Fenton-oxidation, hydrogen peroxide , ozone, photocatalysis and
biofiltration . The addition of oxidants such as hydrogen peroxide or ozone increases the
removal of organic material from wastewaters. Kabdali et al. studied the removal of organic
matter and heavy metals from metal plating effluents using a combined EC-Fenton process.
Stainless steel electrodes were used as anodes and cathodes. The combined process increased
the removal of organic matter compared to EC only. The optimal dose of hydrogen peroxide
was 1530 mM. Roa-Morales et al. treated wastewater from pasta and biscuit processing with
aluminium EC combined with peroxide additions. Hydrogen peroxide additions slightly
35

increased COD removal compared to pure EC. Ozonation of effluent after EC can further
decrease the concentration of organic matter in the effluent .

Higher removal efficiencies could be obtained when iron electrodes are used instead of
aluminium because the presence of Fe(II) catalyses the decomposition of oxidants to hydroxyl
radicals, which can mineralise organic pollutants. Residual organic matter after EC can be also
removed with photocatalysis according to our study and Boroski et al. Can et al. combined EC
with chemical coagulants PACl and alum. The addition of chemical coagulants decreases pH,
whereas EC increases it and with a combination system, the final pH can be stabilised to
neutral region. EC combined with PACl gave higher COD removals than combination with
alum. PACl has more prepolymerised species, which can be more efficient in pollutant
removal and it also contains chlorides which increase localised corrosion of electrodes and
reduce energy consumption. Yu et al. combined EC with biofiltration. Combining EC to
biofiltration increased the removal of COD and phosphorus from 69.1% and 9.6% to 76.6
83.7% and 70.793.0%, respectively.

36

CHAPTER 4
DYES

Dyes are a coloured element with an affinity to the substrate to which is being applied. Based
on the third edition of Colour Index list which is edited by the Society of Dryers and
Colourists and by the American Association of Textile Chemist and Colourists, there are more
than 8000 colorants used on a large scale for fibres, plastics, printing inks, paints and liquids.
There are many structural varieties of dyes that can be classified into either the cationic type,
non-ionic type or anionic type and the classification is as follow
Anionic : direct, acid and reactive dyes
Cationic : basic dyes; and
Non-ionic : disperse dyes
Dyes are widely used in various industries such as dyestuffs, textiles, leather, papers and
plastics and it contributes to the coloured wastewater. The waste effluents of these industries
normally are highly coloured. Thus, disposal of this coloured wastewater into receiving waters
will cause damage to the environment as it will undergo for chemical changes, consume
dissolved oxygen, and destroy aquatic creatures. The presence of dye in effluent even in a very
low concentration of dyes which is less than 1 mg/L, it is still highly visible and is considered
undesirable to the water user. Besides, these dye effluents reduces light penetrationand
affecting the photosynthetic activity in aquatic life. Some of the dye effluent may also be toxic
and carcinogenic to some aquatic living organism as it contains metals and chlorides.
Furthermore, increasing water demand for industrial and public uses, the needs of reclamation
of the effluents and treatment of wastewater become highly desirous. Thus, it is necessary to
develop an effective and efficient method to remove the colour from wastewater before being
discharged to natural water stream.
37

There are several methods that can be applied to remove dye such as biological treatment
(biodegradation using bacteria cells), coagulation or flocculation, chemical oxidation and
photocatalytic processes, ozone treatment, membrane processes, and adsorption. However,
there are some difficulties in treating the coloured wastewater as they are recalcitrant organic
molecules, resistance to aerobic digestion, and is stable to light, heat, and oxidising agents
Due to the presence of large degree of aromatic rings in the dye molecules, the treatment of
coloured wastewater via a biological process is difficulty and ineffective as dyes have low
biodegradability.
There are few limitations that taken into account when choosing the right techniques to treat
coloured wastewater such as excess amount of chemical usage, expensive plant requirements
and operational costs, lack of effective colour reduction and sensitivity to a variable
wastewater input.
Structure
Generally, synthetic dyes are made of aromatic organic compounds. The structure of synthetic
dyes consists of aryl rings that has delocalised electron systems. These structures named as
chromogen (electron acceptor) are responsible for the absorption of electromagnetic radiation
that has varying wavelengths based on the energy of the electron clouds, while auxochrome
(electron donor) is a part that regulates the solubility and dyeing properties. With the presence
of chromophore (chromo means colour and phore means bearer) in the dyes causes energy
changes in the delocalised electron cloud of the dye. This alteration invariably results in the
compound absorbing radiation within the visible range of colours and not outside it
Chromophore group is a color giver and is represented by the following radicals, which form a
basis for the chemical classification of dyes when coupled with the chromogen: azo (-N=N-);
carbonyl (=C=O); carbon (=C=C=); carbonnitrogen (>C=NH or -CH=N-); nitroso (-NO or NOH); nitro (-NO2 or =NO-OH); and sulfur (>C=S, and other carbon-sulfur groups). The
chromogenchromophore structure is not adequate to impart solubility and cause adherence of
dye to fiber. Thus, auxochrome (auxo means augment) or bonding affinity groups like
38

amine, hydroxyl, carboxyl, and sulfonic radicals or their derivatives are salt-forming which is
needed to aid the solubility and adherence of dye in acidic and basic medium.

There are several types of dyes which can be classified as acetate rayon dyes, acid dyes, azoic
dyes, basic dyes, direct dyes, mordant or chrome dyes, lake or pigment dyes, sulfur or sulfide
dyes and vat dyes. These dyes may be classified according to a dual system managed by the
Society of Dryers and Colourists and the American Association of Textile Chemists and
Colourists. Both of this society and association is in cooperation and has published the Colour
Index (C.I.) which provides a detailed classification of commercial dyes and pigments by
generic name and chemical constitution. Besides, this sourcebook also provides useful
information on technical performance, physical properties, and application areas. The
classification of dyes by usage is summarized in Table 5.1.
Table 4.1 Usage Classification of Dyes

Class

Applications

Method of app.

Chemical Type

Acid

Nylon, wool, silk,

Usually from neutral to

Azo

paper

acidic dye-baths

premetallized),

ink,

and

leather

(including

anthraquinone,
azine,
triphenylmethane,x
anthene, nitro, and
nitroso

Basic

Leather ,wool,
silk paper, modified
nylon,
polyacrylonitrile,
39

polyester,

Applied from acidic dye-

and inks

baths

Cyanine, azo, azine,

triarylmethane,xa

oxazine,

hemicyanine,

nthen,

anthraquinone

acridine,

and

diazahemicyanine,

Direct

Cotton, paper,
rayon, leather, and
nylon

Disperse

Polyester,
polyamide, acetate,
acrylic, and plastics

Applied from neutralor

Azo, phthalocyanine,

Slightly

stilbene,

baths

alkaline
containing

nitro,

andbenzodifurano

addition alelectrolyte

ne

Fine aqueous dispersions

Azo, anthraquinone,

Often applied by high

styryl,

temperature, pressure or

andbenzodifuran

lower temperature carrie

one

rmethods;
padded

dye
on

maybe

cloth

and

bakedon or thermo fixed

40

nitro,

Class

Typical Applied

Method of app.

Reactive

Cotton, wool,

Reactive siteon dye reacts Azo, anthraquinone,

silk, and nylon

Chemical Type

with functional group on phthalocyanine,

fiber to bind dye covalently formazan, oxazine,
under influence of heat and and basic
alkaline condition

Solvent

Plastics,
gasoline,

varnishes,

lacquers, stain sinks,

Dissolution in the

Phthalocyanine, azo,

appropriate solvent or

anthraquinone, and

medium

triphenyl methane

Dissolved in

Indeterminate

fats, oils, and waxes

Sulfur

Cotton and rayon

Water (with
the addition of sodium
sulfide for the insoluble
types); exhausted with
glauber's salts

structur

Basic Dye
Dyes can be defined as coloured, aromatic organic compounds that can be ionised. Hence, dyes
are able to interact with oppositely charged tissue constituents ). Basic dye is a stain that is
cationic (which ismpositively charged) and so it will react with material that is negatively
charged. Basic dyes are the class of dyes which is most commonly synthetic. Their primary
nature is to act as bases and basic dyes are actually aniline dyes. Initially, basic dyes colour base
is not water soluble but it can be solute in water with the base being converted into a salt. Basic
dyes are not generally light fast even it has great tinctorial strength and brightness. Thus, it is
largely restricted from using in the dyeing of archival materials and also to those materials not
requiring this characteristic
At chemical level, basic dyes are cationic or positively charged as it possesses functional groups
like NR3+ or =NR2+. Since basic dye is cationic, therefore it can react well with the material
that is anionic or negatively charged. Some commonly used examples of basic dyes includes of
methylene blue, crystal violet, basic fuchsin, and safranin

Acid Dye
Dyes are being grouped according to the lines of being coloured and also the aromatic
compounds contain in the structure that can be ionise. Acid dyes contain mainly negative charge
and it is used to bind with positively charged tissue components. Acid dyes are very complex in
structure but the groups that have ionising capability are known as the auxochromes.
Auxochromes is a salt-forming group which consist of hydroxyl, carboxyl or sulphonic groups
that attach to nonionising compound yet it can retain its ability to ionise and it will produce dye
when it is introduced into chromogen . Therefore, auxochromes is the coloured part of the
molecule which consequently has an overall negative charge. Besides, these auxochromes group
are the one that makes the acid dye to be soluble in water . There are few examples of acid dyes
which are acid yellow 24, acid red 66, acid red 87, and methyl orange

42

4.1 METHYLENE BLUE

FIG4.1 The chemical structure of Methylene Blue (MB).

Table 4.2
Physical properties of Methylene Blue dye.
Property

Value

Color Index (C.I.)

52030

Trade name

Methylene Blue

Scientific name

Basic Blue 9

Color

Dark green to blue crystals or powder

Maximum wavelength (max) (nm)

665

Molecular diffusivity (Dmol) (at 25 C)

4.7 106 (cm2/s)

Solubility in water

Soluble in water

Chemical formula

C16H18N3OS3H2O

Molecular weight

373.5 (g/g mol)

Molecular volume

390.2 (cm3/g mol)

43

Property

Value

CHAPTER 5

44

MATERIAL AND METHODS

Water that is treated is synthetically prepared by adding methylene blue to distilled water.
The electrocoagulator was made of plastic with the dimensions 16cm 12cm 7cm at constant
stirring . There are four electrodes, two anodes and two cathodes of the same dimensions.
Aluminum (99.53%) cathodes and anodes were made from plates with dimensions of 7.5cm
0.03cm 3.5cm. The total effective electrode area was 52.5cm2 and the spacing between
electrodes was 3cm. The electrodes were connected to a digital dc power supply ( 0-20 V, 5 A)
with potentiostatic or galvanostatic operational options. All the runs were performed at constant
temperature of 30C. In each run, 750ml of the water solutions was placed into the electrolytic
cell. The current density was adjusted to a desired value and the electro-coagulation was started.
At the end of electro-coagulation, the solution was filtered and the filtered and then was
analyzed. Before each run, electrodes were washed with acetone to remove surface grease, and
the impurities on the aluminum electrode surfaces were removed by dipping for 5 min in a
solution freshly prepared by mixing 100 cm3 HCl solution (35%) and 200 cm3 of
hexamethylenetetramine aqueous solution (2.80%) . At the end of the run, the electrodes were
washed thoroughly with water to remove any solid residues on the surfaces, dried and reweighted. The pH was measurement by a pH meter. Conductivity was determined by a
conductivity meter. The pH and conductivity were adjusted to a desirable value using NaOH or
H2SO4, and NaCl, respectively.

Fig. 5.1 Schematic diagram of experimental setup.

45

A brief description of electrocoagulation

Generally, three main processes occur serially during electrocoagulation:
(a) electrolytic reactions at electrode surfaces,
(b) formation of coagulants in aqueous phase,
(c) adsorption of soluble or colloidal pollutants on coagulants, and removal by sedimentation or
floatation. The inherent complexities of the above processes, and also the presence of secondary
processes, makes electrocoagulation quite complex in nature.
Main reactions at the electrodes are:
Al Al3+ (aq) + 3e (anode) (1)
3H2O + 3e 3 2H2 + 3OH (cathode) (2)
Meanwhile, if anode potential is sufficiently high, secondary reactions may occur also, such as
direct oxidation of organic compounds and of Cl ions present in waste water :

2Cl Cl2 + 2e (3)

46

The chlorine produced is a strong oxidant that can oxidize same organic compounds and promote
electrode reactions. In addition, the cathode, may be chemically attacked by OH ions generated
during H2 evolution at high pH values :
2Al + 6H2O + 2OH 2Al (OH)4 + 3H2 (4)
Al3+ (aq) and OH ions generated by electrode reactions (1) and (2) react to form various
monomeric species such as Al(OH)2+, Al(OH)2 +, Al2(OH)2 4+, Al(OH)4 , and polymeric
species such as Al6(OH)153+, Al7(OH)174+, Al8(OH)204+, Al13O4(OH)247+, Al13(OH)345+,
which transform finally into Al(OH)3 according to complex precipitation kinetics. Formation
rates of the different species play an important role in the decolorization process. Several
interaction mechanisms are possible between dye molecules and hydrolysis products and the
rates of these depend on pH of the medium and types of ions present. Two major interaction
mechanisms have been considered in recent years: precipitation and adsorption, each one being
proposed for a separate pH range. Flocculation in the low pH range is explained as precipitation
while it is explained as adsorption in the higher pH range (>6.5) . Precipitation: DYE +
monomeric Al [DYEmonomeric Al](s) (pH = 4.05.0) (5) DYE + polimeric Al [DYE
polimeric Al](s) (pH = 5.06.0) (6) Adsorption: DYE + Al(OH)3(s) [particle] (7) [DYE
polimeric Al](s) + Al(OH)3(s) [particle] (8) Freshly formed amorphous Al(OH)3 sweep
flocs have large surface areas which are beneficial for a rapid adsorption of soluble organic
compounds and trapping of colloidal particles. These flocs polymerize as nAl(OH)3
Aln(OH)3n (9) and are removed easily from aqueous medium by sedimentation and H2 flotation.

5.1 Spectrophotometer
47

Fig-5.2 Spectrophotometer
A spectrophotometer is employed to measure the amount of light that a sample absorbs. The
instrument operates by passing a beam of light through a sample and measuring the intensity of
light reaching a detector.
Working:
It is capable of focusing a beam of light of a specified wavelength or wavelength range on a
sample containing a constituent that absorbs the light. The instrument often measures the
absorbance of light by splitting the light beam (using optics) and comparing the amount of light
transmitted through a sample that doesnt contain the light absorbing constituent (a blank).
The basic law that governs the absorption of light by molecules is Beer-Lambert law:
log (Io/I) = cl
where,
Io is the intensity of incident light
I is the light transmitted through the sample solution
c is the concentration of the solute
l is the path length of the sample
48

 is the molar absorbtivity

log (Io/I)is the absorbance (A) of the solution formerly called the Optical Density (OD).
There are two major classes of devices: single beam and double beam.

Double Beam:
A double beam spectrophotometer compares the light intensity between two light paths, one path
containing a reference sample and the other the test sample. It is easy to operate and very stable.
Single Beam:
A single beam spectrophotometer measures the relative light intensity of the beam before and
after a test sample is inserted. Single beam instruments can have a larger dynamic range and are
optically simpler and more compact.
Depending upon the detection parameters there are major two classes:
UV-Visible Spectrophotometer:
The most common spectrophotometers are used in the UV and visible regions of the spectrum,
and some of these instruments also operate into the near-infrared region as well. Visible region of
400800 nm is used for detection. Traditional visible region spectrophotometers cannot detect if
a colorant or the base material has fluorescence.
IR Spectrophotometer:
Spectrophotometers designed for the main infrared region are quite different because of the
technical requirements of measurement in that region. One major factor is the type of photo
sensors that are available for different spectral regions, but infrared measurement is also
challenging because virtually everything emits IR light as thermal radiation, especially at
wavelengths beyond about 5 m.

49

The Configuration of a Spectrophotometer:

You will find from the above explanation that the indispensable elements of a spectrophotometer
consist, as shown in Fig. 4.5, of a light source, a spectrometer, a sample compartment, and a
detector. Although I said in the previous section that the sample is exposed to monochromatic
light, there are instruments in which white light is passed through the sample before being passed
into the spectrometer. This method is employed in high-speed photometry instruments that use
array detectors. In the next sections, I will give an explanation of each element.

Fig-5.3 Configuration of Spectrophotometer

Light Source:
The desirable properties of a light source are as follows:
a) Brightness across a wide wavelength range
b) Stability over time
c) A long service life
d) Low cost
Although there are no light sources that have all of these properties, the most commonly used
light sources at the moment are the halogen lamps used for the visible and near-infrared regions
and the deuterium lamps used for the ultraviolet region. Apart from these, xenon flash lamps are
sometimes used.

50

Detector:
The light beams that pass through the sample compartment enter the detector, which is the last
element in the spectrophotometer. Photomultipliers and silicon photodiodes are typical detectors
used with spectrophotometers for the ultraviolet and visible regions. For the near-infrared region,
PbS photoconductive elements have always been used in the past, but recently, instruments
incorporating InGaAs photodiodes have been sold. Silicon photodiode array detectors are used, in
combination with the back spectroscopy method, for high-speed photometry instruments.
Photomultipliers and silicon photodiodes are described below.

51

CHAPTER 6
RESULTS AND DISCUSSIONS

Spectrophotometer that gave good linearity for the absorbance versus MB concentration at its
maximum absorbance wavelength of 665 nm. Percentage of dye removal was calculated
according to the following equation:
equation

where Co and C are the initial and instant concentrations of the dye (mg/L), respectively
6.1Effect of pH

Fig. 6.1 Effect of pH, current density = 4.5 Amp, NaOH= 2 wt.%, dye conc. = 50mg/L

52

It has been established that ph is an important operating factor influencing the performance of
electro coagulation process. As we can see that by increasing pH values removal efficiency also
increases and thus we can conclude that optimum pH value is 6-8.

6.2 Effect of electrolyte concentration

Fig. 6.2 Effect of electrolyte conc. , current density = 4.5Amp ,dye conc. = 50mg/L

The greater ionic strength will generally cause an increase in current density at the same cell
voltage, or the cell voltage decreases with increasing wastewater conductivity at constant current
density . Therefore, it is necessary to investigate the effect of wastewater conductivity on EC in
terms of color removal. The conductivity of the wastewater is adjusted to the desired levels by
adding an appropriate amount of NaOH.
Hence, from the graph we conclude that the optimum electrolyte conc. Is between 2-4 wt.% of
NaOH

53

6.3 Effect of initial dye concentration

Fig. 6.3 Effect of initial dye conc. , current density = 4.5Amp, NaOH= 2 wt.%.

It observed clearly that the high concentration of dye in solution needs more time to reach the
desired removal efficiency that occurred to that of low concentration , however, in 10 ppm dye
concentration at 8 min. the color removal efficiency is 0.78 ,in 20 ppm the color removal is 0.71
at 8 min. and its almost 0.55 with 50 ppm at the same time , again the electrocoagulation time
offset the regression in color removal efficiency ,it can be reach a maximum value of 94 at 18
min. in 50 ppm dye concentration and 0.93 at 14 min in 20 ppm., also in 10 ppm. More than 90
can be reachs before this time. The reason behind that is high dye concentration needs for Extra
time to react with Alcoagulant that generated sequentially in solution.
According to the results in Fig.6.3 , percentage of dye removal decreases with increasing initial
dye concentration, however this decrease was not distinguishable. Up to 20 min for all different
concentrations, the adsorption capacity of flocs was not exhausted.
54

6.4 Effect of electrolysis time

Fig.6.4 Effect of electrolysis time, current density = 4Amp, NaOH= 2 wt.%, dye conc. = 50mg/L

Reaction time influences the treatment efficiency of the electrolytic process. During electrolysis,
the anodic electro-dissolution led to the release of the coagulating species. The dye removal
efficiency depends directly on the concentration of metal ions produced on the electrodes.
Increasing the time of electrolysis leads to an increase in both the concentration of metal ions and
the accumulation of hydroxide flocs.
From fig.6.4, an increase in the time of electrolysis from 10 to 60 min yields an increase in the
dye removal efficiency from 68% to 92%. It also could be noticed that after 20 min.

55

CHAPTER 7
CONCLUSION

The enhancement of EC of dye solution (Methylene Blue) by means of application of

electromagnetic field was studied and the following conclusions were obtained:
EC was affected by pH, the electrolyte concentration, initial dye concentration and time of
electrolysis.
The dye was effectively removed (80%) after 20 min.
The optimum conditions for the removal of MB dye with an initial concentration of 50 mg/L
are: 20 min electrolysis time, current density of 4Amp.
The optimum electrolyte concentration was found to be 2 wt.%
The optimum pH is 8.

56

57