REMOVAL OF METHYLENE BLUE DYE CONTAMINANT

PRESENT IN WASTEWATER USING ALAKLI-TREATED

ACTIVATED CHARCOALS OBTAINED FROM DIFFERENT
BIOWASTES

A DISSERTATION SUBMITTED TO THE KARNATAKA UNIVERSITY DHARWAD

IN PARTIAL FULFILLMENT FOR THE AWARD OF DEGREE OF

MASTER OF SCIENCE
IN
ANALYTICAL CHEMISTRY
By

VARSHA DAMODAR NAIK

Reg. No. PO2JF21S0018

Project supervisor
Dr. Bhaskar Devu Mukri M.Sc., Ph.D. (IISc)

ACKNOWLEDGEMENTS
 We would like to avail this opportunity to thank all of the who have stood by us in
encouraged us, inspired us and have contributed greatly in providing us with the
achievement thrill of creative effort experienced by us all the way through the
accomplishment of project.

I wish to express my deep sense of gratitude to my project guide Dr. Bhaskar Devu
Mukri, Assistant Professor, Motilal Nehru National Institute of Technology, Allahabad,
Prayagraj, UP, India for his able guidance and useful suggestion, which helped me in
completing my project work.

I take immense pleasure in thanking our principal Dr. S. V. Gaonkar, Dr. A. V. Baliga
College of Arts and Science, Kumta, Dr. N. K. Nayak, Co-ordinator, P.G. Department
of Analytical Chemistry, Dr. A. V. Baliga College of Arts and Science, Kumta for
providing all the necessary facilities during my project work. I would like to thank all
staff members.

Finally, yet importantly, I would like to express my heartfelt thanks to my beloved

parents for their blessings, my friends for their help and wishes and to everybody who
have directly or indirectly helped and supported me for the successful completion of
this project.

Place: Kumta

Date:

Karnataka University’s
KANARA COLLEGE SOCIETY’S
 POST GRADUATE DEPARMENT OF STUDIES IN ANALYTICAL CHEMISTRY
DR. A V BALIGA COLLEGE OF ARTS AND SCIENCE, KUMTA - 581343

DECLARATION
I declare that the project work entitled “Removal of Methylene Blue Dye
Contaminant Present in Wastewater using Alkali-treated Activated Charcoals
Obtained from Different Biowastes”, submitted to the Karnataka University for the
award of Master of Science in Analytical Chemistry is based on the result of the
experiments and observations carried out by me under the supervision of Dr. Bhaskar
Devu Mukri.

Place: Kumta
Date:

(Varsha Damodar Naik)

KANARA COLLEGE SOCIETY’S

POST GRADUATE DEPARMENT OF STUDIES IN ANALYTICAL CHEMISTRY
 DR. A V BALIGA COLLEGE OF ARTS AND SCIENCE, KUMTA - 581343

CERTIFICATE

This is to certify that the project report entitled “Removal of Methylene Blue Dye
Contaminant Present in Wastewater using Alkali-treated Activated Charcoals
Obtained from Different Biowastes”, submitted by Varsha Damodar Naik, Reg. No.
P02JF21S0018 under the prescription of the Karnataka University Dharwad for her
Master of Science degree in Analytical Chemistry is based on the result of experiments
carried out by her under my supervision.

Place: Kumta
Date:
Dr. Bhaskar Devu Mukri
Project Supervisor
(Department of Chemistry, MNNIT Allahabad, Prayagraj)

Examiners
1.

Head of Department
2.

CONTENT
Chapter 1: Introduction
1.1. Background: Wastewater treatment
1.2. Water pollutants
1.3. Activated charcoal as a good adsorbent
1.4. Methylene blue as an organic pollutant

Chapter 2: Modification of raw charcoal obtained from wood, coconut and groundnut
shell
2.1. HCl treatment
2.2. NaOH treatment
2.3. Na2CO3 treatment

Chapter 3: Instrumental techniques and methods for the characterization and analysis
3.1. Double beam UV Vis spectrophotometer

Chapter 4: Adsorption study of methylene blue by different activated charcoals

4.1. Experimental set-up
4.2. Results and discussion
4.2.1. Kinetic study
4.2.2. Thermodynamic study

Chapter 5: Conclusions
References
 CHAPTER 1: INTRODUCTION

Chapter1: Introduction

Activated carbon is a form of carbon that has been processed with oxygen to create
millions of tiny pores between the carbon atoms. The internal surface area of
commercial activated carbon is ranging from 500 to 1500 m2/g. Because of its large
surface area and high adsorption capacity it has been used for various applications
like medical uses, adsorption of natural gas, cosmetics use, for removal of heavy
metals, water purification etc. As per the demand of human life, industrial revolution
polluting our lakes, oceans and rivers. For which it is damaging our planet and
organism die very rapidly. So, water Purification is major and is the most essential
component for our life. The deficiency to access clean and fresh water can lead many
troubles including sickness, malnutrition and death. So, it is becoming most important
for future due to the increase in population, changes in climate, expansion of
agricultural and industrial activities with enhancing the living standards. The
contamination of water occurs because the industries release many toxic organic
dyes, heavy metals and micropollutants into water. Methylene blue used as a
traditional dye for silk wool and cotton also used to make certain body fluids and
tissues easier to view during surgery, is one of the toxic dyes. Consuming water which
contains methylene blue may cause vomiting, mild bladder irritation, dizziness,
diarrhea and the burn effect of eyes. Recently different techniques have already been
used for the removal of dye from water and wastewater are biodegradation,
electrochemical oxidation, solvent extraction, ion exchange biological purification,
coagulation & sedimentation techniques and adsorption. However, most of these
techniques are comparatively expensive and complicated. But adsorption technique
has been preferred because it is quite easy and cost effective as adsorbents, porous
solids which generally have a high surface area. So now a days it is quite challenging
for developing countries to produce high-efficient and low cost activated carbon. But
many problems arise at the time of regeneration of used activated carbon. Many
commercial activated carbons have been widely used for the adsorption process.
However, from economical point of view, it has expensive in production process. So,
producing low-cost and effective activated carbon may give a healthy environmental
to our society and offer benefits for future commercial applications. The activated
carbon prepared from unused biomaterials is very low-cost compared to the cost of
commercial activated carbon. Many people obtained activated carbons from
agricultural by-products including soybean straw, coconut shell, date pit, rattan
sawdust, and sewage sludge. But to produce activated carbon by using very low-cost
equipment’s or without equipment is quite interesting topic for us. Therefore, the main
aim of this study is to prepare the active charcoal from the normal burned wood,
coconut fibre, groundnut shell residue and utilize in the removal of methylene blue dye
contaminants from wastewater.

1.1. Wastewater Treatment

Wastewater Treatment Methods for methylene blue’s removal dye users, industrial
entities, and the government should take all appropriate steps in the treatment of dye
effluents in order to improve public health and protect the environment. In general,
industrial wastewater treatment technologies are divided into several stages, including
pre-primary, primary, secondary, and tertiary processes. The initial one is a preliminary
process that is applied for the removal of contaminants (such as papers, grits, wood,
plastics, cloths, etc.) with minimal effort, as well as the comminution and screening of
floating, suspended particles, and oil and grease traps. The following process is the
primary treatment, which includes skimming to remove frothy solids and flotation and
sedimentation to remove settleable inorganic and organic impurities. Secondary
wastewater treatment involves the microbial breakdown of dissolved organic and
colloidal materials, which maintains the waste’s stability. Biological agents are used in
advanced and tertiary treatment (i.e., anoxic, aerobic and anaerobic, facultative, or a
mix of these), chemical (ozonation, fenton reagents, chemical precipitation, ion
exchange, photocatalysis ultrasound, and solar-driven processes) or physical
(sedimentation, membrane filtration, coagulation and flocculation, ultrafiltration,
nanofiltration, adsorption, and reverse osmosis) strategies for treating effluents that
are incapable of being removed during secondary treatment. Likewise, during
treatment of effluent-containing dye, there could be substances left in treated
wastewater which require post treatment including the application of bio-waste-derived
adsorbent. Previous studies reported on the disadvantages of various wastewater
treatment, including lower efficiency, greater capital or operating costs, a large amount
of sludge production, and high costs of maintenance, that make these technologies
inappropriate for economic application.
Figure 1.1. Sewage treatment plant.

Current color removal treatment approaches involve chemical, physical and biological
processes. There are two sorts of dye molecules: chromophores, which provide colors,
and auxochromes, which not only act as a substitute for the chromophore but also
increase the solubility of dye in water, thus increasing its affinity (ability to join) to fibers.
Chemical, physical, and biological remediations are the most often used ways for
treating colored wastewater. These technologies, however, have both advantages and
disadvantages. Most of these traditional procedures are inapplicable on a broad scale
because of the high expense and disposal issues associated with the significant the
quantity of sludge produced in the final treatment process.

1.2. Water pollution

We all rely on a source of clean water to lead healthy lives; it is a vital resource that is
very often taken for granted. It is easy to understand why this is the case as 70% of
the earth is covered in water and most of us experience rainfall to varying degrees.
Many, in recent years, have become more aware about water conservation and water
quality. This is because water pollution has become an important issue that requires
immediate action. Contaminated waterways can affect the health of people, animals,
and vegetation that use them. Water is highly effective as a solvent, and most
pollutants can easily be dissolved in it.

Here are five of the most common sources of this water pollution;

1. Wastewater and Sewage

The wastewater and sewage that is produced by every home is treated with chemicals
and then released into the sea. This sewage carries bacteria and chemicals that pose
a serious health risk. Waterborne pathogens, such as E. coli, cholera,
campylobacteriosis and others are also a water pollution risk. These pathogens are a
mix of microorganisms that are the cause of many deadly diseases. Their existence
also acts as a breeding ground for creatures and parasites that spread the disease.
Possibly the most well-known example of this is the relationship between malaria and
mosquitos.

2. Industrial Waste
Some industries, produce an enormous amount of toxic waste that is laden with
pollutants. Some of these pollutants are released into the environment as air pollution.
Others are drained into fresh water that is then introduced into canals, rivers and
eventually the sea. Some of the most common chemicals are lead, sulfur, mercury,
asbestos, and nitrates. These chemicals can change the water color and temperature.
They also cause Eutrophication, which is an increase in the mineral content of the
water. These chemicals are hazardous to local flora and fauna, including fish and other
water borne organisms.

3. Fossil Fuels
The burning of fossil fuels, such as coal and oil, produces ash that is released into the
atmosphere. The particles are toxic when they become mixed with water vapor in
clouds, they cause acid rain. Additionally, when fossil fuels are burned, carbon dioxide
is released, which is a contributor to global warming.

4. Sewer Line Leaks

Even a small leak in a sewer line can cause the surrounding groundwater to become
contaminated. This will make the water unfit for human consumption. If the sewer line
is not repaired for a while, other problems will occur. Leaking sewer water will
eventually find its way to the surface, and it will become a breeding ground for
mosquitoes, a particular issue these days with the recent arrival of the Zika virus to
the continental United States.

5. Fertilizers and Pesticides

Many fertilizers and pesticides are chemical products that are used by farmers to
protect their crops. They are beneficial for plants because they protect against attacks
from insects and harmful bacteria. Unfortunately, when these chemicals are mixed
with rainwater, they can become a problem as they flow off the land into streams,
rivers, and canals. They are harmful to both animal and plant life. Eventually, they will
make their way to the water sources where they damage aquatic life.

1.3. Activated Charcoal as a good adsorbent

Activated charcoal is a great adsorbent because of its huge surface area. While it
doesn't bind very many ions/atoms/molecules per surface area (which is the
characteristic of a 'good' adsorbent), due to very big surface area per unit of mass it
can adsorb a lot of particles.
• Charcoal isn't a particularly good adsorbent even though it is chemically very
similar to activated carbon.
• Activated carbon is usually made by more specialized processes that guarantee
the final product will have a very large surface area (often >1,000 m2/g).
Manufacture usually involves pyrolyzation with hot gasses, but many forms are
also further activated by partially oxidising the surface (using gas containing
oxygen) or bay adding chemicals such as phosphoric acid or potassium
hydroxide before pyrolysis. These activation reactions create some functional
groups on the surface that can enhance specific types of adsorption on the
surface. But the primary feature that matters is the high surface area, which
normal methods for making charcoal do not achieve.
• Charcoal is a good absorbent because it’s quite selective and cheap. Its high
surface area means nothing if it doesn't bond to the components that you want
 absorbed and not a lot else- witness a household sponge which has high
surface area and mercury- the mercury just slides off. Charcoal is used in the
gold mining/processing industry. The gold (and other metals) is oxidized to form
cyanide complexes. The charcoal mostly only absorbs the cyanide complexes
not all the other rubbish and water. Charcoal wouldn't be much good for the
water purification industry if it absorbed water.
• Carbon’s adsorbent quality is determined by its sorption capacity. The
characteristics of the adsorbent are considered to be the most critical factors
that can affect MB’s adsorption, and include the surface area, pore structure,
carbon particle size, surface acidity, and functionality. Usually, carbon
adsorbents can be classified as superior (adsorption capacity >1000 mg/g),
excellent (500–1000 mg/g), moderate (100–500 mg/g), and weak (adsorption
capacity 100 mg/g) based on their MB adsorption capacities. The surface area
of carbon adsorbent was reported to be positively correlated with its adsorption
capacity. Nonetheless, not all carbon adsorbents follow this trend, as some
have low adsorption capabilities due to having excessive surface areas. The
highest MB adsorption capacity, exceeding 800 mg/g, was found in adsorbents
with large surface areas but small pore diameters.
• Charcoal-derived activated carbon was revealed to be the most superior
adsorbent with an efficiency of 99.8%, and it can handle different types of dyes.
Researchers discovered that MB performed better as an adsorbate as
compared to Rhodamine B in wastewater.
• Despite the good functioning of activated carbon, which has successfully
removed dyes from industrial wastewater effluents, it has drawbacks such as
high capital costs, high energy consumption, and sorption–desorption cycles.
For color and heavy metal elimination, bio adsorbents made from bacteria or
fungi are promising ecologically acceptable adsorbents.
 (a) (b)

Figure 1.2. (a) Raw charcoal, and (a) prepared the activated carbon from charcoal.

1.4. Methylene blue as an organic pollutant

Methylene blue (MB) is categorized as an organic dye (OD) released as effluents after
various industrial activities and is extensively used in the dye, textile, and plastic
industries. Furthermore, MB is employed in the field of biology for preparing different
staining procedures, such as Jenner’s and Wright’s stains. Therefore, it is one of the
most abundant pollutants in the aquatic environment. MB can cause severe problems
to humans such as blood pressure increasing, nausea, shock, vomiting, Heinz body
formation, profuse sweating, jaundice, and mental confusion. Significantly, because of
its potential toxicity in human and animal bodies, removing MB from wastewater has
been a matter of necessity in recent times.
CHAPTER 2: MODIFICATION OF RAW CHARCOAL OBTAINED FROM
WOOD, COCONUT FIBRE AND GROUNDNUT SHELL

Chapter 2: Modification of raw charcoal obtained from wood, coconut and

groundnut shell

The raw charcoals are obtained from wood, coconut fibre, and groundnut shell. The
raw charcoal is not more active for the adsorption of water pollutants. It requires some
modifications that mean treatments such as acid treatment, base or alkali treatment,
temperature treatment under inert atmosphere, etc.
Before treatment, the raw charcoal was made into powder, washed with distilled water,
and dried at 80 °C for 12 h.
2.1. HCl treatment
1M HCl solution was prepared by taking 9 mL of concentrated HCl in a 100 mL
volumetric flask and diluted upto the mark. 5 g of dried charcoal was added in a 250
mL beaker containing 100 mL of 1M HCl solution, stirred it for 10 min and kept without
disturbance for 24h. The HCl treated charcoal was filtered, washed with distilled water
until the filtrate turned into neutral, and dried at 80 °C for 12h.
The trace amount of metal oxides present in raw charcoal is dissolved in HCl solution.
Metal oxides + x HCl → Metal nitrates + x/2 H2O

2.2. NaOH treatment

For the preparation of 3M NaOH solution, 12 g of NaOH was taken in a 100 mL
volumetric flask and diluted upto the mark. 5 g of acid treated charcoal was added in
a 250 mL beaker containing 100 mL of 3M NaOH solution, stirred for 10 min, and kept
without disturbance at room temperature for 24h. The NaOH treated charcoal was
filtered, washed with distilled water until the filtrate became pH 7 which means excess
NaOH has to be removed from the NaOH treated charcoal, and dried at 80 °C for 12h.
SiO2 present in the charcoal is dissolved in NaOH solution in the form of sodium
metasilicate. This treatment is developed the porous in the NaOH treated charcoal.

SiO2 + 2NaOH → Na2SiO3 + H2O

The resultant alkali-treated activated charcoals are collected and stored for the
characterization and the wastewater treatment, which contained the organic
contaminant, methylene blue by adsorption process. The alkali-treated activated
charcoals obtained from wood, coconut fibre, and groundnut shell raw charcoals are
denoted as AC−W, AC−CF, and AC−GS, respectively.
CHAPTER 3: INSTRUMENTAL TECHNIQUES AND METHODS FOR
THE CHARACTERIZATION AND ANALYSIS

Chapter 3: Instrumental techniques and methods for the characterization and

analysis

3.1. BET surface area measurement

Brunauer-Emmett-Teller (BET) surface area analysis is the multi-point measurement

of an analyte’s specific surface area (m2/g) through gas adsorption analysis, where an
inert gas such as nitrogen is continuously flowed over a solid sample, or the solid
sample is suspended in a defined gaseous volume. Small gas molecules adsorb to
the solid substrate and its porous structures due to weak van der Waals forces, forming
a monolayer of adsorbed gas. This monomolecular layer, and the rate of adsorption,
can be used to calculate the specific surface area of a solid sample and its porous
geometry, informing studies into the reactivity and bioavailability of pharmaceutical
products.
BET theory aims to explain the physical adsorption of gas molecules on
a solid surface and serves as the basis for an important analysis technique for the
measurement of the specific surface area of materials. The observations are very
often referred to as physical adsorption or physisorption. In 1938, Stephen
Brunauer, Paul Hugh Emmett, and Edward Teller presented their theory in the Journal
of the American Chemical Society. BET theory applies to systems of multilayer
adsorption that usually utilizes a probing gas (adsorbate) that do not react chemically
with the adsorptive (the material upon which the gas attaches to and the gas phase is
called the adsorptive) to quantify specific surface area. Nitrogen is the most commonly
employed gaseous adsorbate for probing surface(s). For this reason, standard BET
analysis is most often conducted at the boiling temperature of N2 (77 K). Other probing
adsorbates are also utilized, albeit less often, allowing the measurement of surface
area at different temperatures and measurement scales. These include argon, carbon
dioxide, and water. Specific surface area is a scale-dependent property, with no single
true value of specific surface area definable, and thus quantities of specific surface
area determined through BET theory may depend on the adsorbate molecule utilized
and its adsorption cross section.
The concept of the theory is an extension of the Langmuir theory, which is a theory for
monolayer molecular adsorption, to multilayer adsorption with the following
hypotheses:
• Gas molecules physically adsorb on a solid in layers infinitely;
• Gas molecules only interact with adjacent layers; and
• The Langmuir theory can be applied to each layer.
• The enthalpy of adsorption for the first layer is constant and greater than the
second (and higher) layer.
• The enthalpy of adsorption for the second (and higher) layers is the same as
the enthalpy of liquefaction.
Figure 3.1. BET model of multilayer adsorption.

The resulting BET equation is

……………………. (1)

where c is referred to as the BET C-constant, p0 the vapor pressure of the adsorptive
bulk liquid phase which would be at the temperature of the adsorbate and θ is the
"surface coverage, defined as:

……………………… (2)

where nads is the amount of adsorbate and nm is called the monolayer equivalent. The
above equation is usually rearranged to yield the following equation for the ease of
analysis:

..…………………… (3)

where p and p0 are the equilibrium and the saturation pressure of adsorbates at the
temperature of adsorption, respectively; v is the adsorbed gas quantity (for example,
in volume units) while vm is the monolayer adsorbed gas quantity, and c is the BET
constant,

……………………… (4)

where E1 is the heat of adsorption for the first layer, and EL is that for the second and
higher layers and is equal to the heat of liquefaction or heat of vaporization.
To determine BET surface area, required quantity of charcoal was sampled in the BET
surface area analyzing instrument

3.2. Double beam UV Vis spectrophotometer

A spectrophotometer is an analytical instrument used for the objective calculation of

visible light, UV light, or infrared light emission or reflection. Spectrophotometers
measure intensity as a function of the wavelength of the light source. Many modern
photometers and spectrophotometers are based on a double beam design. In a
double-beam instrument, the light is split into two beams before it reaches the sample.
One beam is used as the reference; the other beam passes through the sample. The
reference beam intensity is taken as 100% Transmission (or 0 Absorbance), and the
measurement displayed is the ratio of the two beam intensities. Some double-beam
instruments have two detectors (photodiodes), and the sample and reference beam
are measured at the same time. In other instruments, the two beams pass through a
beam chopper, which blocks one beam at a time. The detector alternates between
measuring the sample beam and the reference beam in synchronism with the chopper.
There may also be one or more dark intervals in the chopper cycle. In this case, the
measured beam intensities may be corrected by subtracting the intensity measured in
the dark interval before the ratio is taken.
Samples for UV/Vis spectrophotometry are most often liquids, although the
absorbance of gases and even of solids can also be measured. Samples are typically
placed in a transparent cell, known as a cuvette. Cuvettes are typically rectangular in
shape, commonly with an internal width of 1 cm. This width becomes the path length,
L in the Beer–Lambert law. Test tubes can also be used as cuvettes in some
instruments. The type of sample container used must allow radiation to pass over the
spectral region of interest. The most widely applicable cuvettes are made of high-
quality fused silica or quartz glass, because these are transparent throughout the UV,
visible and near infrared regions. Glass and plastic cuvettes are also common,
although glass and most plastics absorb in the UV, and so, these cuvettes can useful
only for visible wavelength region.
 (a)

(b)

Figure 3.2. (a) Schematic diagram, and (b) photograph of the double beam UV Vis
spectrophotometer.
A typical double beam UV-visible spectrophotometer consists of:
• A light or energy source, which is typically a lamp i.e. tungsten lamp for visible
light and deuterium lamp for ultraviolet (UV) light.

• A filter or a monochromator that is attached to the device for the selection of

the wavelength of light.

• A place for cuvettes containing a solvent sample has to be measured the

absorption of light.
 • A sensitive detector such as a charge-coupled device (CCD) or photomultiplier
tube (PMT).

Schematic diagram and photograph of the double beam UV Vis spectrophotometer

are shown in Figures 3.2 (a) and (b), respectively.

The double beam UV Vis spectrophotometer can be applied to characterize the rate
of a chemical reaction. Also, it is used to identify and confirm the presence of chemical
species present within the biological specimens based on their chemical structures,
the concentration, etc. From the spectrum of burning gases, it is possible to determine
a chemical composition of a fuel, temperature of gases, and air-fuel ratio.
To measure the remaining concentration of methylene blue in the solution after the
adsorption on NaOH treated activated charcoals, which obtained from different
biowastes, the solution was centrifuged, 1 mL of supernatant was taken and diluted to
the proper concentration for analysis in a double beam UV Vis spectrophotometer.
CHAPTER 4: ADSORPTION STUDY OF METHYLENE BLUE BY
DIFFERENT ACTIVATED CHARCOALS

Chapter 4: Adsorption study of methylene blue by different activated charcoals

4.1. Experimental set-up

NaOH treated activated charcoal was introduced to remove the methylene blue from
water. Methylene blue dye adsorption study was carried out by batch methods. 7
beakers of 100 mL capacity were labeled as 1, 2, 3, 4, 5, 6, and 7 for 5, 10, 20, 30,
40, 60, and 90 min to undergo adsorption, respectively. In each beaker, 10 mg of
activated charcoal was taken and 10 mL of methylene blue solution with a proper ppm
level was added into the beaker. After 5 min, the resultant solution in the beaker 1 was
centrifuged and 1 mL of supernatant was transferred into a test tube. This remained
concentration after adsorption by activated charcoal was diluted into a proper
concentration in such a way that it should come under the absorbance range in the
double beam UV Vis spectrophotometer. And, absorbance of remaining concentration
after 5 min was recorded and the maximum absorbance value of methylene blue was
observed at ~ 664 nm. Similarly, this procedure was continued for other time intervals
until observed the saturated adsorption that means almost the same concentration of
pollutants remaining in the water. The saturation of adsorption or adsorption
equilibrium is reached within 90 min in all the experiments. Experimental set-up for the
removal of methylene blue present in water sample by activated charcoal is shown in
Figure 4.1.

Figure 4.1. Experimental set-up for removal of water pollutants by activated charcoal.
The adsorption percentage (%) of methylene blue or was determined using below
equation,

Adsorption (%) = ………………….. (5)

Where C0 is the initial concentration and Ct is the concentration at time t of methylene

blue or phenol in the solution. Concentration of the solution was calculated by
corresponding absorbance.

4.2. Results and discussion

Brunauer–Emmett–Teller (BET) surface area of the alkali treated charcoals are
measured by BET surface area analyzer. The BET surface area plots of AC−W,
AC−CF, and AC−GS are shown in Figures 4.2, 4.3, and 4.4, respectively. The surface
area of AC−W, AC−CF, and AC−GS are 172, 157, and 205 m2/g, respectively. It
confirms that the charcoal obtained from groundnut shell is created more surface area
by NaOH treatment as compare to other charcoals obtained from wood and coconut
fibre.

60

55

50

45
1/[Q(P0/P-1)]

40

35

30

25

20
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

Relative pressure (P/P0)

Figure 4.2. BET surface area plot of AC−W.

60

50

40
1/[Q(P0/P-1)]

30

20

10

0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
Relative pressure (P/P0)
Figure 4.3. BET surface area plot of AC−CF.

70

60

50
1/[Q(P0/P-1)]

40

30

20

10

0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
Relative pressure (P/P0)

Figure 4.4. BET surface area plot of AC−GS.

Since, alkali-treated charcoals have a large surface area, those are considered for the
adsorption study of methylene blue. The absorbance vs wavelength plot of the
remained methylene blue in 10 ppm solution after adsorption by AC−GS obtained from
groundnut shell is shown in Figure 4.5. It observed that AC−GS adsorbed the
methylene blue from the 10 ppm solution and it reached adsorption equilibrium within
20 min, which 0.5
indicates the maximum adsorption of methylene blue by this adsorbent.
0 min
10 min
0.4 20 min
30 min
40 min
Absorbance (a. u.)

0.3 50 min
60 min
70 min
0.2 80 min
90 min

0.1

0.0

400 450 500 550 600 650 700 750 800

Figure 4.5. Absorbance vs wavelength plot for methylene blue adsorption by AC−GS.

A plot of concentration vs time for the methylene blue adsorption by AC−W from the
different concentrations is shown in Figure 4.6. The AC−W showed the 2.84 ppm,
15.90 ppm, 39.65 ppm, and 57.70 ppm of methylene blue remained in the solution
within 10 min from the 10 ppm, 25 ppm, 50 ppm, and 75 ppm solutions, respectively
and after 60 min, those reached almost saturation in the adsorption of methylene blue.
In Figure 4.7, the plot about the amount of methylene blue adsorbed by per g of AC−W
with respect to time is shown. 3.76 mg, 4.54 mg, 5.17 mg, and 8.64 mg of methylene
blue are adsorbed from 10 ppm, 20 ppm, 30 ppm, 40 ppm, and 50 ppm solutions by 1
g of AC−W within 10 min, respectively. After some times, those reached the
equilibrium of adsorption on alkali treated activated charcoals, means that the
activated charcoal reached the maximum adsorption of methylene blue, which
denoted as ‘qe’. The qe values of methylene blue per g of AC−W from the 10 ppm, 25
ppm, 50 ppm, and 75 ppm solutions are 4.75 mg/g, 6.72 mg,/g 8.77 mg/g, and 12.33
mg/g, respectively. Quantity of methylene blue adsorption per g of AC−W before
reaching an equilibrium condition can denote as ‘qt’ with respect to time, t.

100

10 ppm
25 ppm
80 50 ppm
75 ppm
Concentration (ppm)

60

40

20

0
0 10 20 30 40 50 60 70 80 90 100
time (min)
Figure 4.6. A plot of concentration vs time of the methylene blue adsorption by AC−W.

14

12
Amount of adsorbed (mg/g)

10

4
10 ppm
25 ppm
2 50 ppm
75 ppm

0
0 10 20 30 40 50 60 70 80 90 100
time (min)
Figure 4.7. Amount of adsorbed vs time plot of the methylene blue adsorption by
AC−W.
The graphs of the concentration of methylene blue in solution and quantity of adsorbed
by 1 g of AC−CF with respect to time are shown in Figure 4.8 and Figure 4.9,
respectively. The maximum amounts of methylene blue adsorbed per g of AC−CF are
3.42 mg, 6.16 mg, 7.82 mg, and 10.70 mg from the solutions of 10 ppm, 25 ppm, 50
ppm, and 70 ppm, respectively.

100
10 ppm
25 ppm
80 50 ppm
75 ppm
Concentration (ppm)

60

40

20

0
0 10 20 30 40 50 60 70 80 90 100
time (min)
Figure 4.8. The concentration vs time plot of the methylene blue adsorption by
AC−CF.

12

10
Amount adsorbed (mg/g)

10 ppm
2 25 ppm
50 ppm
75 ppm
0
0 10 20 30 40 50 60 70 80 90 100
time (min)

Figure 4.9. Amount adsorbed vs time plot of the methylene blue adsorbed per g of
AC−CF.

100

10 ppm
25 ppm
80
50 ppm
75 ppm
Concntration (ppm)

60

40

20

0
0 10 20 30 40 50 60 70 80 90 100

time (min)
Figure 4.10. A plot of concentration vs time of the methylene blue adsorption by
AC−GS.

14 10 ppm
25 ppm
12 50 ppm
75 ppm
Amount adsorbed (mg/g)

10

0
0 10 20 30 40 50 60 70 80 90 100
time (min)

Figure 4.11. Amount of adsorbed vs time plot of the methylene blue adsorption by
AC−GS.

In Figure 4.10, the remained concentration of methylene blue after adsorption by

AC−GS with respect to time is shown. The qe values of methylene blue per g of AC−W
from the 10 ppm, 25 ppm, 50 ppm, and 75 ppm solutions are 5.87 mg/g, 8.11 mg/g,
11.17 mg/g, and 13.11 mg/g, respectively, which are shown in Figure 4.11.
4.2.1. Kinetic study
In order to understand the mechanism of adsorption on alkali-treated activated
charcoals, the experimental data of different methylene blue concentrations are fitted
into several kinetic models, such as first-order, pseudo-first-order, second-order, and
pseudo-second-order models, etc. The coefficient of determination (R2) value confirms
which kinetic model undergoes the adsorption. If R 2 value of any models is nearly
equal to 1, adsorption occurs by that kinetic model behavior.
The first-order adsorption kinetic of methylene blue on AC−W with various initial
concentrations is shown in Figure 4.12 and it was calculated by using the formula;

……………………… (6)

The R2 values are summarized in Figure 4.12 and those confirm that methylene blue
adsorption on AC−W is not the first-order kinetic behavior.

6
10 ppm
25 ppm
5 50 ppm
75 ppm
Concentration R2 value
4
10 ppm 0.496
ln Ct

25 ppm 0.499 3

50 ppm 0.596
2
75 ppm 0.494
1

0
0 10 20 30 40 50 60 70 80 90 100
time (t, min)

Figure 4.12. A plot of the first-order adsorption kinetic of methylene blue on AC−W
with different initial concentrations. R2 values are summarized in Table.

The adsorption of methylene blue on AC−W by the pseudo-first-order kinetic model is

shown in Figure 4.13 and it was calculated by using the formula;
 ……………………. (7)

The R2 values, which are shown in Figure 4.13 indicate that methylene blue
adsorption on AC−W is not followed the pseudo-first-order kinetic model.

4
10 ppm
3
25 ppm
2 50 ppm
Concentration R2 value 75 ppm
1
10 ppm 0.972
ln (qe-qt)

0
25 ppm 0.980
-1
50 ppm 0.862
-2
75 ppm 0.973
-3

-4

-5

-10 0 10 20 30 40 50 60 70
time (t, min)

Figure 4.13. A plot of the pseudo-first-order adsorption kinetic of methylene blue on

AC−W with different initial concentrations. In Table, R2 values are summarized.

To confirm the adsorption by the second-order kinetic model, the following equation
(3) is used.

………………………….. (8)

A plot of the second-order adsorption kinetic of methylene blue on AC−NaOH is shown

in Figure 4.14 and also, summarized the R2 values, which confirm that the second-
order is not the kinetic model followed by the adsorption of methylene blue on AC−W.
The pseudo-second-order adsorption kinetic of methylene blue on AC−W with different
initial concentrations and their R2 values are shown in Figure 4.15 and it was
calculated by using the formula;
 ……………………….. (9)

1.0
10 ppm
0.9
25 ppm
50 ppm
0.8
Concentration R2 value 75 ppm
0.7
10 ppm 0.690
0.6
25 ppm 0.570
0.5
50 ppm 0.646 1/Ct
0.4
75 ppm 0.538
0.3

0.2

0.1

0.0
0 10 20 30 40 50 60 70 80 90 100
time (t, min)

Figure 4.14. A plot of the second-order adsorption kinetic of methylene blue on AC−W
with different initial concentrations. R2 values are summarized in Table.
22

20 10 ppm
25 ppm
18
Concentration R2 value 50 ppm
16 75 ppm
10 ppm 0.999 14
25 ppm 0.999
t/qt

12

50 ppm 0.999 10

8
75 ppm 0.999
6

0
0 10 20 30 40 50 60 70 80 90 100
time (t, min)

Figure 4.15. A plot of the pseudo-second-order adsorption kinetic of methylene blue

on AC−W with different initial concentrations. R2 values are summarized in Table.
The R2 values of 10 ppm, 25 ppm, 50 ppm, and 75 ppm solutions of methylene blue
are equal to 0.999, which is nearly 1. Hence, the adsorption of methylene blue on
AC−W is followed the pseudo-second-order kinetic behavior.

30
10 ppm
25 ppm
25 50 ppm
75 ppm
 Concentration R2 value
10 ppm 0.999
25 ppm 0.999
50 ppm 0.999
75 ppm 0.999

Figure 4.16. A plot of the pseudo-second-order adsorption kinetic of methylene blue

on AC−CF with different initial concentrations. In Table, R2 values are summarized.

45

40 10 ppm
25 ppm
35 50 ppm
75 ppm
Concentration R2 value
30
10 ppm 0.999
25
25 ppm 0.999
t/qt

20
50 ppm 0.999
15
75 ppm 0.999
10

0
0 10 20 30 40 50 60 70 80 90 100
time (t, min)

Figure 4.17. A plot of the pseudo-second-order adsorption kinetic of methylene blue

on AC−GS with different initial concentrations. R2 values are summarized in Table.

Since the adsorption of methylene blue by activated charcoal follows the pseudo-
second-order kinetic behavior, the equation (9) is used to confirm the methylene blue
adsorption by the pseudo-second-order kinetic behavior on the AC−CF and AC−GS,
which are shown in Figure 4.16 and Figure 4.17, respectively. The R2 values of both
plots confirmed that methylene blue adsorption on AC−CF and AC−GS occurs in the
way of pseudo-second-order of adsorption.

4.2.2 Thermodynamic study

For the thermodynamic study, the adsorption of methylene blue on the activated
charcoals obtained from different biowastes was carried out with 25 ppm of methylene
blue solution at different temperatures. A plot of amount adsorbed with respect to time
on AC−W at different temperatures is shown in Figure 4.18. 6.72 mg/g, 4.24 mg/g,
3.17 mg/g, and 2.42 mg/g are the qe values for AC−W at 25 °C, 40 °C, 50 °C, and 60
°C, respectively.

7
Amount adsorbed (mg/g)

2 0
25 C
0
40 C
1 0
50 C
0
60 C
0
0 10 20 30 40 50 60 70 80 90 100
time (min)

Figure 4.18. Amount adsorbed vs time plot of the methylene blue adsorbed per g of
AC−W at different temperatures.

The graphs of the methylene blue adsorbed quantity vs time for AC−CF and AC−GS
at different temperatures are shown in Figure 4.19 and Figure 4.20, respectively. The
qe values of methylene blue per g of AC−CF at 25 °C, 40 °C, 50 °C, and 60 °C are
6.17 mg/g, 3.94 mg/g,
10 2.89 mg/g, and 1.83 mg/g, respectively. Similarly, the maximum
0
25 C
methylene blue adsorbed
9
40quantities
C on 1 g of AC−GS are 8.11 mg, 6.59 mg, 4.94, and
0

0
3.28 mg at 25 °C,8 40 °C, 50
50C°C, and 60 °C, respectively.
ount adsorbed (mg/g)

0
60 C
7

3
Figure 4.19. Amount adsorbed vs time plot of the methylene blue adsorbed per g of
AC−CF at different temperatures.

10

8
Amount adsorbed (mg/g)

3
0
25 C
2 0
40 C
0
1 50 C
0
60 C
0
0 10 20 30 40 50 60 70 80 90 100
time (min)

Figure 4.20. Amount adsorbed vs time plot of the methylene blue adsorbed per g of
AC−GS at different temperatures.

4.0

3.5

3.0
ln Ct

2.5
 Temperature R2 value
25 °C 0.499
40 °C 0.409
50 °C 0.392
60 °C 0.426

Figure 4. 21. A plot of the first-order adsorption kinetic of methylene blue on AC−W at
different temperatures. R2 values are summarized in Table.
4
0
25 C
0
40 C
2 0
50 C
0
60 C
Temperature R2 value
0
25 °C 0.980
ln (qe-qt)

40 °C 0.997 -2

50 °C 0.939
-4
60 °C 0.972
-6

-8
-10 0 10 20 30 40 50 60 70
time (t, min)

Figure 4.22. A plot of the pseudo-first-order adsorption kinetic of methylene blue on

AC−W at different temperatures. In Table, R2 values are summarized.

To understand the mechanism of methylene blue adsorption on activated charcoal at

different temperatures, reaction kinetic models are applied. The plot of first-order
adsorption kinetic of methylene blue on AC−W at different temperatures is shown in
Figure 4.21. The methylene blue adsorption on AC−W at different temperatures is not
followed the first-order kinetics because the R2 values are not equal to 1. Also, it is not
followed both pseudo-first-order and second-order adsorption kinetics, which are
confirmed by the Figure 4.22 and Figure 4.23 with their coefficient of determination,
R2 values. Figure 4.24 and the R2 values confirm that the methylene blue adsorption
on AC−W at different temperatures is followed by the pseudo-second-order adsorption
kinetic.

0.10

Temperature R2 value 0.09

25 °C 0.570 0.08
40 °C 0.435
0.07
50 °C 0.413
1/Ct

0.06
60 °C 0.439
0.05

0
0.04 25 C
0
40 C
0
0.03 50 C
0
60 C
0.02
0 10 20 30 40 50 60 70 80 90 100
Figure 4.23. A plot of the second-order adsorption kinetic of methylene blue on AC−W
time (t, min)
at different temperatures. R2 values are summarized in Table.
40
0
25 C
35 0
40 C
0
50 C
Temperature R2 value 30 0
60 C
25 °C 0.999
25
t/qt

40 °C 0.998
20
50 °C 0.998
15
60 °C 0.998
10

0
0 10 20 30 40 50 60 70 80 90 100
time (t, min)

Figure 4.24. A plot of the pseudo-second-order adsorption kinetic of methylene blue

on AC−W at different temperatures. In Table, R2 values are summarized.

80
0
25 C
72 0
40 C
0
64 50 C
0
60 C
56

48
 Temperature R2 value
25 °C 0.999
40 °C 0.999
50 °C 0.999
60 °C 0.998

Figure 4.25. A plot of the pseudo-second-order adsorption kinetic of methylene blue

on AC−CF at different temperatures. The R2 values are summarized in table.

32
0
25 C
28 0
40 C
0
50 C
24 0
60 C
Temperature R2 value
20
25 °C 0.999
t/qt

16
40 °C 0.998
50 °C 0.999 12

60 °C 0.998 8

0
0 10 20 30 40 50 60 70 80 90 100
time (t, min)

Figure 4.26. A plot of the pseudo-second-order adsorption kinetic of methylene blue

on AC−GS at different temperatures. In Table, R2 values are summarized.

The methylene adsorption on activated charcoal at different temperatures follows the

pseudo-second-order kinetic behavior. Therefore, the data of methylene blue
adsorption on AC−CF and AC−GS at different temperatures are plotted in the pseudo-
second-order kinetic model, which are shown in Figure 4.25 and Figure 4.26,
respectively. The coefficient of determination values confirm that these adsorptions
are also followed by the pseudo-second-order kinetic behavior.
Thermodynamic parameters, like Gibbs free energy (ΔG), enthalpy (ΔH), and entropy
(ΔS) determine the nature of methylene blue adsorption on the activated charcoals.
The change in Gibbs free energy (ΔG), change in enthalpy (ΔH), and change in
entropy (ΔS) can calculate using the following equations,

Kd = …………………….. (10)

ΔG = − RT lnKd ……………………. (11)

ΔG = ΔH – TΔS ……………………. (12)

where Kd is the distribution constant, qe is the amount adsorbed at equilibrium (mg/g),

Ce is the concentration of methylene blue in solution at equilibrium (mg/mL), R (8.314
J/mol∙K) is the universal gas constant, and T (K) is the absolute temperature.

Table 4.1. The distribution constant and Gibbs free energy changes in the methylene
adsorption on activated charcoals at different temperature.

Activated Temperature qe Ce Kd = qe/Ce ΔG = -RT ln Kd

charcoal (K) (mg/g) (mg/mL) (kJ/mol)

298 6.72 0.94 7.15 -4.873

313 4.24 1.04 4.07 -3.652
AC−W 323 3.17 1.09 2.91 -2.868
333 2.42 1.13 2.14 -2.106
298 6.17 0.94 6.56 -4.660
313 3.94 1.05 3.75 -3.439
AC−CF 323 2.89 1.1 2.63 -2.597
333 1.83 1.16 1.58 -1.266
298 8.11 0.84 9.65 -5.616
313 6.59 0.92 7.16 -5.122
AC−GS 323 4.94 1.00 4.94 -4.289
333 3.28 1.08 3.04 -3.078

-5

-10
Figure 4.27. ΔG vs T plot of methylene blue adsorption on AC−W at different
temperatures.

-5

-10
G (kJ/mol)

-15

-20

-25

-30

-35

-40
0 50 100 150 200 250 300 350
Temperature (K)

Figure 4.28. ΔG vs T plot of methylene blue adsorption on AC−CF at different

temperatures.

-5

-10
ol)

-15
Figure 4.29. A graph of ΔG vs T of methylene blue adsorption on AC−GS at different
temperatures.

Table 4.2. Change in enthalpy (ΔH) and entropy in the methylene blue adsorption
process on activated charcoals.

Activated charcoal ΔH ΔS
(kJ/mol) (kJ/mol/K)
AC−W -28.3 -77.3
AC−CF -27.1 -73.5
AC−GS -32.7 -102.2

In Table 4.1, the distribution constant and change in Gibbs free energy of methylene
adsorption on activated charcoal at different temperatures are summarized. Since, the
ΔG is negative value, the methylene adsorption on AC−W, AC−CF, and AC−GS
adsorbents is spontaneous. The ΔG vs T plots for the methylene blue adsorption on
AC−W, AC−CF, and AC−GS are shown in Figure 4.27, Figure 4.28, and Figure 4.29,
respectively. From these graphs, the –slope and intercept values are the change in
enthalpy (ΔH) and change in entropy (ΔS), respectively and those values are
summarized in Table 4.2. The ΔH values of methylene blue adsorption on AC−W,
AC−CF, and AC−GS are -28.3 kJ/mol, -27.1 kJ/mol, and -32.7 kJ/mole, respectively.
The ΔH values are negative, which indicates that the adsorption of methylene blue on
these activated charcoals is exothermic process. The ΔS values are -77.3 kJ/mol/K, -
73.5 kJ/mol/K, and -102.2 kJ/mol/K corresponding to the methylene blue adsorption
on AC−W, AC−CF, and AC−GS, respectively. These negative values of ΔS indicate
that the methylene adsorption on activated charcoals is favorable at these
experimental temperatures. Overall, the methylene blue adsorption on AC−W,
AC−CF, and AC−GS is spontaneous, exothermic, and favorable at lower
temperatures.
 CHAPTER 5: CONCLUSIONS

Chapter 5: Conclusions
In the first chapter, wastewater treatment, water pollutants, active charcoal, and
organic water pollutants, such as methylene blue are introduced. For the removal of
pollutants from water and wastewater, the adsorption technique by using high surface
area materials i.e. activated carbon is quite easy and cost effective than
biodegradation, electrochemical oxidation, solvent extraction, ion exchange biological
purification, coagulation & sedimentation techniques and adsorption. The activated
carbon prepared from unused biomaterials is very low-cost compared to the cost of
commercial activated carbon. It will be further cheap when activated carbon produced
with low-cost equipment or without equipment. The organic pollutants, methylene blue
in water are highly toxic to humans and animals. It is necessary to remove from the
wastewater. The activated charcoal of high surface area is can remove these
pollutants from the wastewater.
In chapter 2, the normal burned wood, coconut fibre, and groundnut shell that means
raw charcoals were converted into activated charcoals by various treatments. For the
treatments, easily available acid and base or alkali are used to get highly active
charcoal and it is a simple technique. Hence, the preparation of activated charcoal is
a low cost and easy method to obtain high surface area activated charcoal.
In chapter 3, BET surface area measurement and Double beam UV Vis
Spectrophotometer are introduced. BET surface area analysis can be determining the
specific surface area of a solid sample and its porous geometry. A double beam UV
Vis spectrophotometer is an analytical instrument used to determine an unknown
colour solution or UV active solution. It is extremely helpful to determine the remaining
concentration of methylene blue in solution after adsorption on the activated charcoal.
The results about the BET surface area analysis and double beam UV Vis
spectrophotometer are discussed in chapter 4. NaOH treated charcoals i.e. AC−W,
AC−CF, and AC−GS have the surface area of 172, 157, and 205 m2/g, respectively.
An adsorption study of methylene blue was conducted and NaOH treated charcoal s
have shown extreme adsorption within a short time. Also, the kinetic studies on
methylene blue adsorption by AC−W, AC−CF, and AC−GS were determined and the
mechanism of methylene blue adsorption on these activated charcoals followed the
pseudo-second-order kinetic behavior. The thermodynamic studies confirmed that the
methylene blue adsorption on AC−W, AC−CF, and AC−GS adsorbents is
spontaneous because of negative values of ΔG, exothermic due to the negative values
of ΔH, and favorable at lower temperatures, which observed by the negative values of
ΔS.
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