PARAMETRIC AND KINETIC STUDIES ON THE DECOLORIZATION OF

AQUEOUS METHYL ORANGE DYE SOLUTION USING ACIDIC

ELECTROLYZED WATER

KRISTINE JOYCE LUNA EDROZO

SUBMITTED TO THE FACULTY OF THE

DEPARTMENT OF CHEMICAL ENGINEERING
COLLEGE OF ENGINEERING AND AGRO-INDUSTRIAL TECHNOLOGY
UNIVERSITY OF THE PHILIPPINES LOS BAÑOS
IN PARTIAL FULFILLMENT OF THE
REQUIREMENTS FOR THE
DEGREE OF

BACHELOR OF SCIENCE IN CHEMICAL ENGINEERING

OCTOBER 2017

This thesis manuscript can be accessed by:

By the general public -

Only after the consultation with author or adviser YES
Only by those bound by confidentiality agreement -

Signature of Student:
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 TABLE OF CONTENTS

PAGE

TITLE PAGE i

TABLE OF CONTENTS ii

1. INTRODUCTION 1

1.1 Background of the Study 1

1.2 Significance of the Study 3

1.3 Objectives of the Study 3

1.4 Scope and Limitations of the Study 4

1.5 Time and Place of the Study 5

2. REVIEW OF LITERATURE 6

2.1 Industrial Wastewater 6

2.2 Effluent Standards in the Textile Industry 6

2.3 Dye 8

2.4 Methyl Orange Dye 9

2.5 Physical Methods 11

2.6 Chemical Methods 14

2.7 Biological Methods 16

2.8 Advance Methods for Treatment of Textile 17

Industry Effluents

2.9 Electrocoagulation 18

2.10 Electrochemical Reduction Method 20

2.11 Electrochemical Oxidation Method 21

2.12 Electrochemical Photo-assisted Method 22

 2.13 Electrolyzed Water 23
2.14 Applications of Electrolyzed Water
24
2.15 Effect of temperature on the decolorization of methyl
orange
25
2.16 Effect of dye concentration on the decolorization of
methyl orange
26
2.17 Effect of reaction time on the decolorization of methyl
orange
26
3. MATERIALS AND METHODS 28

3.1 Materials and Reagents 28

3.2 Glassware and Equipment 28

3.3 Preparation and Characterization of Wastewater 29

3.4 Preparation and Characterization of Acidic Electrolyzed Water 29

3.5 Preliminary Experiment 30

3.6 Experimental Design 30

3.7 Decolorization of Aqueous Methyl 31

3.8 Parametric Study on the Decolorization of 32

3.9 Kinetics Study on the Decolorization of 35

3.10 Data Analysis 35

3.11 Statistical Analysis 36

REFERENCES 37
 1. INTRODUCTION

1.1 Background of the Study

Nowadays, the textile production industry is considered as one of the oldest and

most technologically complex of all industries (Environmental and Health Effects of

Textile Industry Wastewater, 2013). With escalating demand for textile products, textile

mills and their wastewater have been increasing proportionally, causing a major problem

of pollution in the world.

In fact, more than 3,600 individual textile dyes are being manufactured by the

industry today (Textile dyeing industry an environmental hazard, 2012). During textile

processing, dyeing and printing, large quantities of water are required. Consequently, the

daily water consumption of an average textile mill having a production of about 8,000 kg

of fabric dye per day is about 1.6 million liters, in which 16% of this is consumed in

dyeing and 8% in printing (Textile dyeing industry an environmental hazard, 2012).

Water pollution, which is considered as a serious worldwide environmental

problem, is usually caused by the discharge of untreated effluent and some of those are

because of use of toxic chemicals especially during the textile processing. Those effluents

are usually labelled as hazardous toxic wastes since sulfur, naphthol, vat dyes, nitrates,

acetic acid, soaps, chromium compounds and heavy metals like copper, arsenic, lead,

cadmium, mercury, nickel, and cobalt are usually present in this type of wastewater.

The effluent is of critical environmental concern since it drastically decreases

oxygen concentration due to the presence of hydrosulfides and blocks the passage of light
 2

through water body which is detrimental to the water ecosystem. About 40% of globally

used colorants contain organically bound chlorine, a known carcinogen (Environmental

and Health Effects of Textile Industry Wastewater, 2013).

With this found problems, it is necessary to treat textile wastewater. Many

treatment processes can be used to treat wastewater in an economic and efficient way;

this includes physical, chemical, biochemical, hybrid treatments and etc. However, in

many times these methods were practiced, several disadvantages of those techniques

were found, which then leads to the use of electrolyzed water in the decolorization of dye

solution.

Like for example, in adsorption, the usual treatment for textile wastewater, the

most effective and common used adsorbent which is the activated carbon is not that

recommended for economically practiceable application of the adsorption method

because of its high price and difficulty in its regeneration.

Also, unlike other methods, in which there is an introduction of another material

as a cleaning agent which requires further recovery, in electrolyzed water approach,

electron will be the reagent that will be introduced which may be used on the prevention

of environmental pollution without the additional cost of reagent recovery. Additionally,

the electrolyzed water is considered as a non-toxic and highly effective cleaning agent.

So far there have been no concrete studies regarding decolorization of aqueous

dye solution using electrolyzed water, thus, for this experiment, the concept of

incorporating electrolyzed water in treating dye solution will be done.

 3

1.2 Significance of the Study

Through this experiment, it is expected to determine the best parameters for the

decolorization of a dye solution particularly methyl orange dye solution, which will

surely help in the reduction of environmental hazards caused by the dye effluents

released by the textile factories.

In addition, it will be a great help for the textile companies to know an efficient

technique in decolorizing dye solutions since there is a protocol for the discharge of

effluents in the country. Also, the results of this study will surely contribute to maintain

the sustainability of the aquatic life. Furthermore, the parameters that will be identified as

the best conditions can be used in the development of a more advance method of treating

textile wastewater.

1.3 Objectives of the Study

The general objective of this study is to conduct parametric and kinetic studies on

the decolorization of aqueous methyl orange dye solution using acidic electrolyzed water.

Specifically, this study aims:

1. to characterize the electrolyzed water based on its pH and free chlorine

concentration of electrolyzed water;

2. to evaluate the effects of concentration of aqueous methyl orange dye

solution, ratio of electrolyzed water to synthetic wastewater, reaction

temperature and reaction time on the decolorization of methyl orange dye

solution;
 4

3. to assess the best combination of parameters that will have the highest color

removal of aqueous methyl orange dye solution using electrolyzed water; and

4. to determine the kinetic parameters: kinetic constant, k and order of reaction,

n, of the decolorization process at the best parametric conditions.

1.4 Scope and Limitations of the Study

The wastewater that will be used in this experiment is limited to aqueous

solutions of methyl orange to prevent the effects of other pollutants present in the real

textile wastewater. Also, although there are other parameters that may consider like the

agitation of the mixing of electrolyzed water and the dye solution, this will not be tested

in this experiment because there is no available equipment that will simultaneously heat

and agitate the sample. Only four (4) parameters will be considered in this experiment

which are: concentration of aqueous methyl orange dye solution, ratio of electrolyzed

water to synthetic wastewater, reaction temperature and reaction time. The electrolyzed

water that will be used in this experiment will be generated from Cawolo Disinfectant

Generator CA-5, which will be expected to generate acidic type of electrolyzed water; the

time that will be considered in the production of electrolyzed water is 20 minutes.

Moreover, no COD determination will be done since the concentration of methyl orange

can already be determined by the absorbance reading that will be recorded in the

generation of the standard curve.

 5

1.5 Time and Place of the Study

This study will be conducted in the Environmental Laboratory, which is located in

the Department of Chemical Engineering, College of Engineering and Agro-Industrial

Technology, University of the Philippines Los Baňos. The experiment will be done from

November 2017 – May 2018. On the other hand, the characterization of electrolyzed

water will be made at LARC laboratory located at Brgy. Malinta, Los Baňos, Laguna.
 2. REVIEW OF LITERATURE

2.1 Industrial Wastewater

Water is very essential to human. It is often use in every activities in our daily

lives. Aside from using it in our typical routines, water is also needed in many production

steps in the industry, particularly in manufacturing yarns and fabrics and during textile

finishing. Thus, large volume of wastewater is being produced in every production,

which contains a very diverse range of chemicals and dyes. This is because the use of

several thousand different substances, including resins from caustic soda to bleach, is

being practiced in the textile production (Wastewater Treatment Industry, n.d).

Additionally, it is unavoidable in the textile manufacturing to not produce huge amount

of wastewater since this production consists of rinsing, which is a necessary stage after

many of the process steps.

Since it is not that easy to discharge textile effluents in the bodies of water due to

the standards implemented by the Department of Environment and Natural Resources,

this makes wastewater treatment a necessity.

2.2 Effluent Standards in the Textile Industry

International Standards

Effluent Guidelines are national regulatory standards for the wastewaters that are

being discharged in the environment which come from different areas such as in

industrial plants. United Stated Environmental Protection Agency (US EPA) issues these
 7

regulations for industrial categories, based on the performance of treatment and control

technologies (Effluent Guidelines, n.d.).

The standards for effluents from textile industry, which are shown in Table 2.1,

should be regulated by all textile companies in the world. It should also be noted that the

quantity of effluent (liter per kilogram of product) shall not exceed 100, 250 and 80 in

composite cotton textile industry, composite woolen textile industry and textile

processing industry, respectively.

Table 2.1. Standards for effluents from textile industry

PARAMETER MEASUREMENT

pH 5.5 – 9.0
Total suspended solids, ppm 100
Bio-chemical oxygen demand (BOD) 30
Chemical oxygen demand (COD) 250
Total residual chlorine, ppm 1
Oil and grease , ppm 10
Total chromium as Cr, ppm 2
Sulphide as S, ppm 2
Phenolic compounds as C6H5OH, ppm 1
Source: The Environment Protection Rules (1986).

Local Standards

Through the Department of Environment and Natural Resources (DENR)

Administrative Order No. 2016-08, a revised version of DAO 1990-34/35, guidelines for

the classification of water bodies in the country and also the general effluent standards

(GES) are being set.

 8

Textile industries producing textile wastewater, which usually consists of textile

dyes, must comply with the general effluent standards for Class C effluents since

manufacturing of textile is under Class C effluents PSIC Code 13.

Table 2.2. Water Quality Guidelines for Primary Parameters for Class C effluent.

PARAMETER UNIT VALUE

BOD ppm 7

Chloride ppm 350

Color TCU 75

Dissolved Oxygen ppm 5

Fecal Coliform MPN/100mL 200

Nitrate ppm 7

pH 6-9

Phosphate ppm 0.5

Temperature °C 25-31

Total Suspended Solids ppm 80

Source: DENR Administrative Order 2016-08 (2016).

2.3 Dye

Dyes, as general, are any substance that when applied to a substrate, provide color

by a process that alters, at least temporarily, any crystal structure of the colored

substances (Textile Dyes: Dyeing Process and Environmental Impact, 2013). In addition,

the dyes can adhere to compatible surfaces by solution, by forming covalent bond or

complexes with salts or metals, by physical adsorption or by mechanical retention.

 9

Sometimes, dyes and pigments are used interchangeably, but the two terms are different.

Dyes are generally applied in an aqueous solution since they are usually soluble in water

whereas pigments are insoluble.

Dyes can be classified based on different areas such as their application and

chemical structure. The complete classifications of dye are shown in Figure 2.1.

Figure 2.1. Classifications of Dyes

Source: Classification of Dyes Based on Application (n.d)

2.4 Methyl Orange Dye

Methyl orange is an example of dye which is usually used as a pH indicator in

titrations because of its clear and distinct color change. Unlike those universal indicators,

methyl orange does not have a full spectrum of color change, but has a sharper end point

(Methyl orange, n.d). It was noticed that methyl orange shows red color in acidic medium

and yellow in basic medium.

Methyl orange has a chemical formula C14H14N3NaO3S and a molecular weight of

327.334 g/mol. The chemical structure of methyl orange is shown in Figure 2.2.
 10

Figure 2.2 2D Structure of Methyl Orange

Source: PubChem (n.d)

Furthermore, methyl orange is usually used to determine the concentration of

NaOH(aq) in the textile-chemical industry (Industry or home uses for methyl orange

indicator, n.d). However, methyl orange has mutagenic properties, thus, direct contact

should be avoided (Methyl orange, n.d).

In addition to that, methyl orange is considered as an azo dye because of the N=N

on its structure. This bond is called as chromophore which is responsible for the color of

the dye. As defined by Verma et. al (2011), in order to be considered as dye, the

compound must contain not only the chromophore group, but also additional group called

auxochrome which is an electron withdrawing or donating substituent that causes or

intensifies the color of chromophores. In the case of methyl orange, the auxochrome

group is the NaO3S.

 11

Since chromophore is the one responsible for the color of the dye, it is the target

structure so that decolorization of the dye will be bound to happen. The mechanism of the

decolorization of methyl orange is shown in Figure 2.3.

Figure 2.3. Mechanism of decolorization of Methyl

Orange
Source: TutorVista (n.d)

The decolorization of a dye solution can be done in different ways. Many

treatment processes can be used to treat textile wastewater in an economic and efficient

way; this includes physical, chemical, biochemical, hybrid treatments and etc.

2.5 Physical Methods

Several physical methods can be used in treating wastewater; one of these is the

coagulation-flocculation based physical method. This type of method is considered very

useful for the decolorization of wastewater containing disperse dyes, however, this

technique also limit their use due to the low decolorization efficiency and large
 12

generation of resultant sludge (Liang et al., 2014, as cited by Chandrakant R. Holkar et

al., 2016). However, on the other hand, due to technology advances, the feasibility of new

tannin-based coagulant-flocculant (Tanfloc) in surface water and textile wastewater

treatment at a pilot plant level was also tested. According to Ong et.al (2011), the result

of water purification and filtration has improved a lot particularly in the removal of

suspended solids, both flocs and turbidity. Also, Ong et. al (2011) added that for the

textile industry wastewater, approximately 95% dye removal was obtained and those

results from pilot studies were similar or even better than that obtained in batch trials.

Furthermore, adsorption is also an example of physical methods. Due to a high

decolorization efficiency for wastewater containing a variety of dyes, the adsorption

approach have attracted significant attention. As reported by Jadhav and Srivastava

(2013), as quoted by Holkar et al. (2016), high affinity, capability for the compounds and

adsorbent generation ability are the main characteristics that should be considered in

selecting an absorbent for color removal. There are numerous adsorbents that are

popularly known in the industry such as activated carbon, bentonite clay, polymeric

resins, and etc. Of all the mentioned adsorbents, activated carbon is known as the most

effective adsorbent for a wide range of dyes (Chandrakant R. Holkar, 2016). However,

activated carbon is not that recommended for economically practiceable application of

the adsorption method because of its high price and difficulty in its regeneration, thus,

leading the researchers to use a low cost adsorbent material like fly ash and bentonite

clay. Due to these circumstances, adsorption method have been restricted by the several

problems such as the adsorbent’s regeneration and/or dumping and sludge generation.

Therefore, adsorption is practically used only for wastewater that has low concentrations
 13

of pollutants or when the adsorbent has a low cost or can be easily regenerated

(Chandrakant R. Holkar, 2016). In addition to that, in a narrower context, in the case of

methyl orange, batch adsorption technique was employed in the study of methyl orange

onto calcined Lapindo volcanic mud. It was observed that the experimental results fitted

well to Langmuir isotherm with a maximum adsorption capacity of 333.3 mg/g. Also, the

thermodynamic parameters revealed that the reaction is spontaneous and endothermic.

Moreover, filtration techniques like ultrafiltration (UF), nanofiltration (NF) and

reverse osmosis (RO) are under the physical method. These practices use the membrane’s

micropores to filter and makes use of membrane’s slective permeability to separate

certain substances in wastewater (Wang, n.d). Likewise, the choice of the filter and its

permeability should also be taken into consideration for an effective filtration, it is also

important to test first the content and the temperature of textile wastewater essential for

the separation method (Chandrakant R. Holkar, 2016). But since, there is no such perfect

method, filtration techniques have significant disadvantages, too, such as its cost of initial

investment, possible fouling of membrane and the generation of another wastes

containing water insoluble dyes (e.g. indigo dye) and starch which need further treatment

(Koyuncu, 2013). Even though, the cost of filtration techniques is high, there are still

studies employing this technique. In fact, novel aromatic polyamide asymmetric

nanofiltration membrane has been used for the treatment of dye aqueous solutions. The

nanofiltration membrane was prepared using a phase inversion. The effects of various

parameters such as pH and feed temperature were evaluated and the results showed that

the rejection of acid, direct and reactive dyes were all above 95% (Ong et. al, 2011).
 14

2.6 Chemical Methods

Other than physical methods of treating wastewater, there are also chemical

methods that can also be employed in wastewater treatment. Chemical treatment methods

are applied both as stand-alone technologies and as an integral part of the treatment

process with physical methods (K. Ranganathan, 2007). As what its name implies,

chemical methods are those in which strictly chemical reactions occur, like precipitation

(Wang, n.d). This type of method can oxidize the pigment in the printing and dyeing

wastewater as well as bleaching the effluent.

Under the chemical methods are the Fenton oxidation and ozone oxidation which

are often used nowadays in the wastewater treatment.

Today, the main concern for the treatment of textile effluent is the decolorization

of the wastewater. One treatment for this is the Fenton oxidation which activated

hydroxyl radical formation from H2O2 (hydrogen peroxide). This technique is usually

used as a pre-treatment for wastewater resistant to biological and/or toxic to biomass

(Wang, n.d). Also, Fenton’s reaction has been introduced into wastewater treatment

processes, and it has been shown that a variety of refractory organics could be effectively

degraded through Fenton reaction without producing any toxic substances in water

environment (Youssef et. al, 2015). The Fenton reaction includes the following reaction:

Fe2+ + H2O2 Fe3+ + HO* + HO-

Fe3+ + H2O2 Fe2+ + HOO* + H+

Fe3+ + HOO* Fe2+ + H+ + O2

HO* + H2O2 HOO* + H2O

 15

HO* + Fe2+ Fe3+ + HO-

HO* + HO* H2O2

HO* + HOO* O2 + H2O

There are several studies related to using Fenton reaction for the treatment of azo

dyes (like methyl orange) wastewaters. Through these studies, it was noticed that the

degradation efficiency of dyes was mainly dependent on their chemical characteristics,

the generation rate and the concentration of HO* in the process (Youssef et.al, 2015).

However, the main disadvantage of this is the significant addition of acid and alkali to

reach the required pH, the necessity to decrease the residual concentration of iron, too

high for discharge in final effluent, and the related high sludge production (Sheng H. Lin,

1997).

Moreover, in the case of methyl orange, there was a study wherein the

degradation of methyl orange in aqueous solution by Fenton reaction has been studied on

different experimental conditions, including the dosages of H2O2 and Fe2+, different dye

concentration, and different pH value of solutions. It was noticed based on this study that

the suitable condition for the degradation of methyl orange was [MO] = 5.4 × 10 −5 M,

[Fe2+] = 1.9 × 10−4 M; [H2O2] = 2.93 × 10−3 M and pH = 2.79 at room temperature. In

these conditions, the degradation efficiency was more than 97.8% and was achieved

within 15 minutes of reaction (Youssef et.al, 2015).

 16

2.7 Biological Methods

Another type of method that can be applied in treating wastewater is biological

methods. In this type of method, this only removes the dissolved matter in the textile

wastewater. The removal efficiency is influenced by the ratio of organic load/dye and the

microorganism load, its temperature, and oxygen concentration in the system. Under this

method, there are subcategories on the basis of oxygen requirement, namely, aerobic,

anaerobic and anoxic or facultative or a combination of these.

To differentiate the different subcategories, in an aerobic method, it uses microbes

for the treatment of the textile wastewater in the presence of oxygen while an anaerobic

method uses microbes to treat it in absence of oxygen (Chandrakant R. Holkar, 2016). On

the other hand, the combination of aerobic and anaerobic methods is typically

implemented in real practice which use an anaerobic process to treat textile wastewater of

chemical oxygen demand (COD), followed by the use of aerobic polishing treatment to

treat the resulting textile wastewater of low COD (Wang, n.d).

Since this type of method uses microbes, the efficiency of biological methods for

degradation depends on the adaptability of the selected microbes and the activity of

enzymes. Thus, a large number of microorganisms and enzymes have been isolated and

tried for the degradation of several dyes. The isolation of potent microbes and its use for

degradation is an interesting biological aspect of textile wastewater treatment

(Chandrakant R. Holkar, 2016).

As mentioned above, biological methods are also applied in the degradation of

several dyes including methyl orange. Actually, in the microbial decolorization of methyl

orange dye by Pseudomonas spp., it was reported that methyl orange was efficiently
 17

decolorized in static compared with shaken cultures. Also, in the conditions of 50-200

mg/L dye concentration, pH of 6-10 and temperature of 30-40 °C, the bacterium

exhibited a remarkable color-removal capability. The Pseudomonas spp. decolorized the

repeated addition of methyl orange dye for up to four (4) cycles with variable

decolorization rates (10-94 %) (Shah et. al, 2013).

2.8 Advance Methods for Treatment of Textile

Industry Effluents

The textile industry uses electrochemical techniques in textile processes and in

wastewater treatment. Conventionally, these electrochemical techniques have been used

for the synthesis of compounds or for metal recovery treatments. However, due to

evolvements of new ideas, it was proposed to also be used in a wide range of other

applications.

Nowadays, as a practice, electrochemical methods are being use in the

degradation of non biodegradable dyes, like reactive dyes. This type of dyes requires

additional treatments to obtain uncolored effluents (Gutierrez-Bouzan, 2012). It was

stated by Gutierrez-Bouzan (2012) that one advantage of using electrochemical method is

that it does not produce solid residues unlike the other methods. It was further elaborated

that this kind of method is a way cleaner than physicochemical and membrane

technologies because they use electron as unique reagent.

There are several categories under electrochemical methods, this includes

electrocoagulation, reduction, oxidation, electrochemical photoassisted, etc. The

complete list of type of electrochemical methods is shown in Figure 2.1.

 18

Figure 2.1. Types of Electrochemical Methods.

Source: (Gutierrez-Bouzan, 2012)

Since electrochemical method uses electron, which is considered as a clean

reagent, it have been applied to industrial effluents. Also, this method are nowadays the

subject of a wide range of investigations at laboratory and pilot-plant scale. This is

because it has good versatility and high-energy efficiency and at the same time easy for

automation and safety since it is possible to operate at smooth conditions (Gutierrez-

Bouzan, 2012).

2.9 Electrocoagulation

Electrocoagulation technology is most commonly used in the oil and gas,

construction, and mining industries in order to treat emulsified oil, total petroleum

hydrocarbons, suspended solids, heavy metals, and other difficult-to-remove

contaminants (Martin, 2014).

To further understand electrocoagulation, the stages involved in the this

technology are shown in Figure 2.2.

 19

Figure 2.2. The stages of electrocoagulation.

Source: Advance Waste & Water Technology, Inc (n.d)

This technique is an indirect electrochemical method which produces coagulant

agents, like Fe3+ and Al3+, from the electrode material (Fe or Al) in hydroxide medium

(Gutierrez-Bouzan, 2012). Electrocoagulation is performed by applying an electric

current across metal plates that are submerged in water. In this setup, the charges that

hold the particles together are destabilized and separate from the clean water (Martin,

2014).

Furthermore, upon using electrocoagulation as a wastewater treatment, it was

observed that there is a sludge minimization compared to other methods and has low

operating costs (Electrocoagulation-new technology for the wastewater treatment, n.d).

Because of these, it even replaces traditional treatment process such as filtration and

chemical treatment which have proved to be less effective and expensive processes.

However, disadvantages also come up; this includes the requirement of high conductivity

of the wastewater suspension, the formation of impermeable oxide film on the cathode

which can be a cause of loss of efficiency of the electrocoagulation unit, and in some
 20

cases, the solubilization of gelatinous hydroxide (Electrocoagulation-new technology for

the wastewater treatment, n.d).

On the other hand, since electrocoagulation is considered as an attractive option

for the treatment of textile dyes, it was also applied in the color removal of methyl orange

which is an azo dye. In a study conducted by Pi et. al (2014), an electrocoagulation

process with periodic reversal of electrodes (PREC) was used in the decolorization of

synthetic wastewater containing methyl orange. The effects of cell voltage, current

density, initial methyl orange concentration, cycle of periodic electrode reversal and

distance between two adjacent electrodes on the color removal were optimized by

Response Surface Methodology (RSM). It was observed in this experiment that the

optimal conditions for the treatment of synthetic wastewater containing methyl orange

are: pH of 7.4, solution conductivity (к) equal to 9.4 mS/cm, cell voltage (U) equal to 4.4

V, current density equal to 185 mA/cm2, 14 minutes of electrocoagulation time, 15

seconds of cycle of periodic reversal of electrodes, inter-electrode distance equal to 3.5

cm and initial MO concentration of 125 mg/L.

2.10 Electrochemical Reduction Method

The information about this type of method is not that much because of its poor

yield in pollutants degradation compared to direct and indirect electrochemical oxidation

methods (Gutierrez-Bouzan, 2012). According to T. Bechtold, et.al (2002),

electrochemical reduction method is appropriate for the treatment of highly colored

wastewaters like residual pad-batch dyeing bath with reactive dyes.

 21

2.11 Electrochemical Oxidation Method

Electrochemical oxidation, or simply electrooxidation, is widely used in various

effluent treatments such as industrial wastewaters from distillery, agrochemical, pulp and

paper, oilfield, metal-plating wastes and textile dyes (Silvana B. Dimitrijević, 2013).

Additionally, it can also be used in treating hazardous effluent treatment like hospital

wastes, removal of pathogens and persistent, pharmaceutical residues and biological from

municipal wastewater treatment plant, removal of organic micro-pollutants such as

pesticides and heavy metals such as arsenic and chromium from water.

The main advantage of this technique is that, it does not produce any undesired

reaction nor use toxic or hazardous materials that is why it becomes a popular alternative

and is successfully applied for industrial wastewater treatment (Silvana B. Dimitrijević,

2013). In addition, the process of this treatment requires only a low temperature and

pressure which is the reason why volatilization and discharge of unreacted wastes are

avoided (Anglada, 2009). Moreover, this process is based on the removal of pollutants by

direct anodic oxidation or by chemical reaction with electrogenerated species such as

hydroxyl radical or metal oxide (Gutierrez-Bouzan, 2012).

Like in the study conducted by Yong et. al (2012), which is about the degradation

of methyl orange in artificial wastewater through electrochemical oxidation using

exfoliated graphite electrode, 98.6 % color removal and 58.5% chemical oxygen demand

reduction was achieved at a pH of 2.0, a current density of 13 mA/cm2, an electrolyte

concentation [NaCl] of 0.1 mol/dm3 an electrolysis time of 20 minutes.

 22

In contrast, the disadvantage of electrooxidation is its high operating cost due to

the high energy consumption. Also, this practice has a tendency of electrode fouling

because of the deposition of material on the electrode surface (Anglada, 2009).

2.12 Electrochemical Photo-assisted Method

Electrochemical photo-assisted method, as its name itself implies, is a type of

electrochemical method which is based on the exposure of the effluent to an ultraviolet

light source during the treatment (Gutierrez-Bouzan, 2012). This combination of

photochemical (UV) and electrochemical process has led to the enhanced degradation of

dissolved organic matter in reverse osmosis (Hurwitz, 2014). It was established that in

these technique, the intensity and the wavelength of the incident light should be

considered because it is one factor that affect the mineralization rate (Gutierrez-Bouzan,

2012).

Additionally, recent studies have shown that the combination of electrochemistry

with UV radiation can improve the degradation of dyes and simultaneously, decrease the

generation of haloforms. In the study conducted by Sala et. al (2016), the electrochemical

photo-assisted treatment performed until 99% color removal of azo and phtalocyanine

reactive dyes. At that point, the mineralization value is 26%.

2.13 Electrolyzed Water

Anode and cathode plates are divided by a membrane. Water added with sodium

chloride as electrolysis accelerator is supplied to the electrolysis tank of these anode

and
 23

cathode chambers. The principle of producing electrolyzed acid water is shown in the

diagram below.

Positive Pole:
2 H2O → 4H+ + O2+ 4e-
2 NaCl → Cl2 + 2e- + 2 Na+
Cl2 + H2O → HCl + HOCl

Negative Pole
2 H2O + 2e- → 2OH + H2

2 NaCl + 2 OH → 2 NaOH + Cl-

Figure 2.3. Principle of electrolyzed water production

Source: Principle and characteristics of electrolyzed acid water (n.d)
 24

Actually, electrolyzed water, both acidic and basic electrolyzed water, has

recently attracted the interest of researches in various fields such as medicine, agriculture

and food processing. In a study conducted by Koseki et. al (2000), it was found out that

acidic electrolyzed water could be preserved for one year under shaded and sealed

conditions. However, it became inert after three days when exposed to light, although pH

remained stable for one year. Additionally, for basic electrolyzed water, it was noticed

that it changes easily regardless of preservation conditions (Koseki et. al, 2000).

Moreover, electrolyzed acid water has many advantages. These include its strong

disinfection power, wide antimicrobial spectrum, non-toxic, short disinfection time and

very low running cost. In contrast, the disadvantages of electrolyzed acid water are its

very short life and strong dependency on protein and organics.

2.14 Applications of electrolyzed water

For more than two centuries, scientists have tinkered with electrolysis, the use of

an electric current to bring about a chemical reaction. It turns out that zapping salt water

with low-voltage electricity creates a couple of powerful yet nontoxic cleaning agents

(Simple elixir called a 'miracle liquid', 2009). It was also elaborated that sodium ions are

converted into sodium hydroxide, an alkaline liquid that cleans and degreases like

detergent, but without the scrubbing bubbles. Additionally, chloride ions become

hypochlorous acid, which is a potent disinfectant known as acid water.

 25

Nowadays, electrolyzed water is considered as a non-toxic and highly effective

cleaning agent. Nevertheless, the equipment used to electrolyze water is expensive. Also,

electrolyzed water has a relatively brief shelf life (Helmenstine, 2016).

2.15 Effect of temperature on the decolorization

of methyl orange

In a biological treatment of decolorization of methyl orange, it was found out that

the rate of chemical reaction is a direct function of temperature (Shah et al, 2013). The

operating conditions of the incubation process varied between 10°C, 30°C, 37°C and

50°C, to study the effect of temperature on the decolorization process. Figure 2.7 shows

the result of the experiment.

Figure 2.7. Effect of temperature on the decolorization of methyl

orange by Pseudomonas spp.
Source: Shah et.al (2013)
 26

2.16. Effect of dye concentration on the decolorization

of methyl orange

In the study conducted by Shah et.al (2013), various concentrations of dye (50,

100, 150, 250,and 400mg/L) were added into the culture medium in order to examine the

effect of initial dye concentration on the decolorization in static conditions at various

time intervals. It was noticed that as the dye concentration increased in the culture

medium, a decline in color removal was attained. Figure 2.8 shows the overall result for

the effect of dye concentration on the decolorization of methyl orange.

Figure 2.8. Effect of dye concentration on the decolorization

of methyl orange by Pseudomonas spp.
Source: Shah et.al (2013)

2.17. Effect of reaction time on the decolorization

of methyl orange

In the study on the decolorization and removal of methyl orange with

sweet potato peroxidise as biocatalyst and the toxicological assessment of its

degradation
 27

products, the results that the maximum removal percentage of methyl orange was

91.4% after 14 minutes of reaction tim.

 3. MATERIALS AND METHODS

3.1 Materials and Reagents

The practical dye that will be used, methyl orange in powdered form, will be

obtained from Unit Operation Laboratory II, Department of Chemical Engineering

(DChE), CEAT, University of the Philippines Los Baños, Laguna.

Moreover, for the calibration for pH meter such as pH 7 and pH 4 buffer

solutions, reagents will be obtained from the Analytical Laboratory while the commercial

grade sodium chloride will come from the Bio-fuels Laboratory, Department of Chemical

Engineering (DChE), CEAT, University of the Philippines Los Baños, Laguna.

Furthermore, for the determination of the free chlorine content of the electrolyzed

water, glycine and DPD (N,N Diethyl-1,4 phenylenediaminesulfate) tablets will be used

that will be obtained from LARC Laboratory.

3.2 Glassware and Equipment

The glasswares that will be used in the experiment are graduated cylinders,

pipette, beaker, volumetric flask, screw-capped test tubes and Hach vials.

The equipment that will be used in reading the absorbance of the dye solution is

the Hach Spectrophotometer DR-2800 in the analytical laboratory, DChE-UPLB. The

acidic electrolyzed water will be generated from Cawolo Disinfectant Generator CA-5,

while for the characterization of electrolyzed, pH and the free chlorine content of the

electrolyzed water, will be determined using the pH meter and Lovibond tintometer from

the LARC Laboratory.

 Furthermore, for the other equipments such as the analytical balance, which will

be used in the determination of the mass of the sample, the hot plate for the source of heat

for the effect of the temperature set-up, and the magnetic stirrer for the distribution of

heat throughout the system, these will be obtained in the analytical laboratory, DChE-

UPLB.

3.3 Preparation and Characterization of Wastewater

Three hundred milligrams of methyl orange dye powder will be dissolved in a one

(1) liter of distilled water using a 1-L volumetric flask, in order to obtain a 300 mg/L of

aqueous methyl orange solution that will be characterized based on its pH and color.

3.4 Preparation and Characterization of Acidic Electrolyzed Water

Cawolo Disinfectant Generator CA-5 will be used in the preparation of the

electrolyzed water. About 15 g of commercial grade NaCl will be prepared and will be

placed into the cup then 300 mL water will also be added. The salt solution that will be

formed will be stirred continuously until all the salt is completely dissolved. After this,

the salt solution will be poured into the generator tank and 200 mL of water will also be

dispensed into the generation tank together with the cup. Upon closing the cover, the

Cawolo Disinfectant Generator CA-5 will be plugged, a red LED light will be expected

to blink, which is the indication that the Cawolo Disinfectant Generator CA-5 is already

on. Then, the start button will be pressed and 20 minutes of electrolysis will be done until

the red LED light is turned off and the green LED light is started to blink which will be
the signal that acidic electrolyzed water is generated. The acidic electrolyzed water that

will be produced will be characterized based on its free chlorine content and pH.

3.5 Preliminary Experiment

For the preliminary experiment, a standard curve showing the relationship

between the absorbance and the concentration of methyl orange solution will be

determined first. In order to obtain a standard curve, the sample (methyl orange solution)

must be first diluted to a lower concentration so that Hach Spectrophotometer DR-2800

can read its absorbance. The linear equation of the standard curve that will be obtained

will be used to determine the actual concentration of the treated wastewater.

Additionally, the determination of the free chlorine content that is responsible for

the decolorization of the aqueous methyl orange dye solution will also be obtained. This

will be done by using the method that was presented by Lovibond Water Testing with the

reagents glycine and DPD tablet. Furthermore, the concentration of methyl orange will be

determined in such a manner that it will be completely degraded in a high dosage of

electrolyzed water, about 2 mL in volume, for 8 hours.

3.6 Experimental Design

In the parametric analysis of this experiment, in order to identify the effect of one

or two variables to another, two-level factorial design will be used. Table 3-1 shows the

constructed experimental design matrix for the four factors: concentration of aqueous
methyl orange dye solution, electrolyzed water to aqueous methyl orange dye solution

ratio, reaction time and reaction temperature.

Table 3.1. Combination of Different Parameters in the Decolorization of

Aqueous Methyl Orange Dye Solution.

Parameters
Volume ratio of
Concentration of
electrolyzed water to Reaction Reaction
Sample aqueous methyl
aqueous methyl Time, Temperature
# orange dye
orange dye hours (°C)
solution (ppm)
(mL/mL)
1 200 0.5: 9.5 2 RT
2 300 0.5: 9.5 2 RT
3 200 2: 8 2 RT
4 300 2: 8 2 RT
5 200 0.5: 9.5 8 RT
6 300 0.5: 9.5 8 RT
7 200 2: 8 8 RT
8 300 2: 8 8 RT
9 200 0.5:9.5 2 50
10 300 0.5:9.5 2 50
11 200 2:8 2 50
12 300 2:8 2 50
13 200 0.5:9.5 8 50
14 300 0.5:9.5 8 50
15 200 2:8 8 50
16 300 2:8 8 50

3.7 Decolorization of Aqueous Methyl

Orange Dye Solution

Determination of the Standard Curve of Methyl Orange Solution

The stock solution will be diluted using different dilution factor which are within

the range of the spectrophotometer readings. A 100-mL of 10 ppm methyl orange dye
solution will be prepared from the stock solution using the equation C1V1 = C2V2. Then a

100 mL of the target diluted concentrations for the aqueous methyl orange solution (0.1,

0.2, 0.3, 0.4, 0.5, 1, 3, 5, 7, and 9 ppm) will be prepared using the stock solution. The

maximum absorbance of the 10 ppm methyl orange dye solution at varying wave length

will be obtained using the spectrophotometer, and then using the same wavelength where

the maximum wavelength will be obtained, the absorbances at varying concentrations

will be checked and recorded. An absorbance versus concentration standard curve will

then be plotted.

Initial Characterization of Wastewater

The prepared wastewater is only composed of methyl orange dye and distilled

water. This aqueous methyl orange dye solution will be characterized based on its initial

pH and color.

3.8 Parametric Study on the Decolorization of

Methyl Orange Dye Solution

Different combinations of concentration of aqueous methyl orange dye solution,

free chlorine level of acidic electrolyzed water, reaction time and temperature will be

tested in this experiment. Furthermore, the volume of electrolyzed water-to-volume of

wastewater will be varied in the experiment so that the effect of free chlorine level in a

10-mL volume will be determined. Additionally, the response to determine the color

removal of each combination will be known through the TCU removed per amount of

free chlorine used.

 Also, the pH of each treated aqueous methyl orange solution will be measured in

order to conclude if the treated dye solution passed the effluent standards as presented in

DAO 2016-08. Lastly, the best condition for the decolorization of methyl orange dye

solution will obtained at the combinations with highest decolorization per amount of free

chlorine used.

Effect of Concentration of Methyl Orange Dye Solution

In order to determine the effect of the concentration of dye on the decolorization

efficiency, two different concentrations will be considered, this includes 200 ppm and

300 ppm at the specified combination of reaction time and volume of electrolyzed water

in the 10-mL sample that will be placed in a screw-capped test tube. The generated

electrolyzed water from Cawolo Disinfectant Generator CA-5 will then be added to 200

ppm and 300 ppm, respectively, following the specified condition presented in Table 3.1.

The final concentration of the treated sample will be determined using the standard curve

and the absorbance that will be read by the Hach Spectrophotometer DR-2800 located in

the analytical laboratory at the Department of Chemical Engineering, CEAT-UPLB.

Effect of Electrolyzed Water to Aqueous Methyl Orange Dye Solution Ratio

To determine the effect of volume of electrolyzed water on the decolorization

efficiency, different volume of electrolyzed water will be added to the aqueous dye

solution. The volumes of electrolyzed water that will be considered in this experiment are

0.5 mL and 2 mL at the specified combination of reaction time and concentration of

aqueous methyl orange dye solution in the 10-mL sample that will be placed in a screw-
capped test tube. The generated electrolyzed water from Cawolo Disinfectant Generator

CA-5 will then be added to the aqueous methyl dye orange solution following the

specified condition presented in Table 3.1. The final concentration of the treated sample

will be determined using the standard curve and the absorbance that will be read by the

Hach Spectrophotometer DR-2800 located in the analytical laboratory at the Department

of Chemical Engineering, CEAT-UPLB.

Effect of Reaction Time

In order to determine the effect of reaction time on the decolorization efficiency,

two different reaction times will be considered in this experiment. The reaction times that

will be considered are 2 hours and 8 hours at the specified combination of added volume

of electrolyzed water and concentration of methyl orange dye solution in the 10-mL

sample that will be placed in a screw-capped test tube. The generated electrolyzed water

from Cawolo Disinfectant Generator CA-5 will then be added to the aqueous methyl dye

orange solution following the specified condition presented in Table 3.1. The final

concentration of the treated sample will be determined using the standard curve and the

absorbance that will be read by the Hach Spectrophotometer DR-2800 located in the

analytical laboratory at the Department of Chemical Engineering, CEAT-UPLB.

Effect of Temperature

In order to determine the effect of reaction temperature on the decolorization

efficiency, two different reaction temperatures will be considered in this experiment. The

reaction temperatures will be considered are 50 °C and room temperature. The generated
electrolyzed water form Cawolo Disinfectant Generator CA-5 will then be added to the

aqueous methyl dye orange solution following the specified condition presented in Table

3.1. For the 50 °C – condition, this set-up will be submerged in a water bath together with

the thermometer and heat source, wherein a magnetic stirrer will be in-charge in

distributing the heat evenly in the system. When the decolorization of the aqueous methyl

orange dye solution is already seen, the final concentration of the treated sample will be

determined using the standard curve and the absorbance that will be read by the Hach

Spectrophotometer DR-2800 located in the analytical laboratory at the Department of

Chemical Engineering, CEAT-UPLB.

3.9 Kinetics Study on the Decolorization of

Methyl Orange Dye Solution

Among the conditions that will be tested, the best condition, the condition

wherein there is the highest removal of methyl orange per amount of free chlorine used,

will be considered. In this condition, the time profile versus the efficiency of

removal/free chlorine will be plotted. Through this, the order and the kinetic parameters

will be calculated by integral method. In integral method, the order of reaction will be

assumed first, among the assumed orders of reaction; the highest value for R2 for the

linear regression that will be obtained will be the final order of the reaction.

3.10 Data Analysis

The decolorization of the reaction will be computed using the formula:

Where:
Ci is the initial concentration in mg/L

Cf is the final concentration in mg/L

TCUi is the initial TCU of the treated solution

TCUf is the final TCU of the treated solution

V is the volume in mL

HOCl is hypochlorous acid

ew is electrolyzed water

3.11 Statistical Analysis

To analyze the statistical proposition of the result, Design Expert Version 10 will

be used, wherein two-way analysis of variance (ANOVA) at p-value = 0.5 will be

employed for the statistical analysis of the obtained data.

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