Professional Documents
Culture Documents
JULY 2013
ADSORPTION OF METHYLENE BLUE ONTO
XANTHOGENATED-MODIFIED CHITOSAN MICROBEADS
JULY 2013
This Final Year Project Report entitled Adsorption of Methylene Blue onto
Xanthogenated-Modified Chitosan Microbeads was submitted by Siti Nadzifah
Binti Ghazali, in partial fulfillment of the requirements for Degree of Bachelor of
Science (Hons.) Chemistry, in the Faculty of Applied Science, and was approved by
___________________________________
Zurhana Binti Mat Hussin
Supervisor
B. Sc. (Hons.) Chemistry
Faculty of Applied Sciences
Universiti Teknologi MARA
26400 Jengka
Pahang
_______________________________ _______________________________
Sarah Laila Binti Mat Jan Prof. Madya Mohd Supi Bin Musa
Project Coordinator Ketua Pusat Pengajian (KPP)
B. Sc. (Hons.) Chemistry Faculty of Applied Sciences
Faculty of Applied Sciences Universiti Teknologi MARA
Universiti Teknologi MARA 26400 Jengka
26400 Jengka Pahang
Pahang
Date:_________________
ii
ACKNOWLEDGEMENT
supervisor, Madam Zurhana Mat Hussin, Lecturer in the Faculty of Applied Sciences
and Miss Sarah Laila binti Mat Jan, the BSc.(Hons.) Chemistry Project Coordinator at
for providing required facilities and supporting this research work to be successfully
I am thankful to Prof. Madya Dr Megat Ahmad Kamal Bin Megat Hanafiah as the
and Prof. Madya Mohd Supi bin Musa, Ketua Pusat Pengajian (KPP), School of
Applied Science UiTM Jengka, for providing me the opportunity to utilise every
facilities available to make this research a reality. The motivation, assistance and
recommendations received from all staff in the UiTM Chemistry Department and all
other faculty members including non-teaching staff who are involved directly or
Million thanks to my parents and family members whose selfless, whose always with
me through hard and rough moments, whose supporting me in every phase of life
until I reach to this level. Finally, I would like to thank everyone who has helped me
directly or indirectly during the completion and success of this thesis. Any personnel
iii
TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
TABLE OF CONTENTS iv
LIST OF TABLES vi
LIST OF FIGURES vii
LIST OF ABBREVIATIONS viii
ABSTRACT ix
ABSTRAK x
CHAPTER 1 INTRODUCTION
1.1 Background and Problem Statement 1
1.2 Significance of the study 4
1.3 Objectives of the study 8
CHAPTER 3 METHODOLOGY
3.1 Materials and Instruments 23
3.2 Research Methodology 25
3.3 Preparation of XMCM 25
3.4 Characterization of XMCM 26
3.4.1 FTIR 26
3.4.2 pHslurry 26
3.4.3 pHzpc 27
3.5 Batch Mode Study 27
3.5.1 Effect of Adsorbent Dosage 27
3.5.2 Effect of Initial pH 28
3.5.3 Isotherm study 28
iv
4.3.2 Effect of Initial pH 35
4.4 Adsorption Isotherm 37
4.4.1 Langmuir Isotherm 39
4.4.2 Freundlich Isotherm 41
CITED REFERENCES 47
CURRICULUM VITAE 51
v
LIST OF TABLES
iv
LIST OF FIGURES
v
LIST OF ABBREVIATIONS
CTS : Chitosan
H20 : Water
Km : Kilometer
M : Mole
MB : Methylene Blue
Mg : Magnesium
mg : Milligram
mL : Milliliter
g : Gram
Na : Sodium
nm : Nanometer
OH : Hydroxyl
Pb : Lead
Cu : Copper
Zn : Zinc
m : Micrometer
: Degree Celsius
viii
ABSTRACT
Methylene Blue (MB) is thiazine dyes that widely use to color product in
many industry such as textile, printing, leather, cosmetic and paper.
Xanthogenated-Modified Chitosan Microbeads (XMCM) is use to observe the
new alternative adsorbent in removing MB from water body through
adsorption process. The interactions between MB and functional group in
XMCM were confirmed by Fourier Transform Infrared (FT-IR). Several
parameters that influence adsorption ability such as the effect of adsorbent
dosage of XMCM and the effect of initial pH of MB aqueous solution were
studied. This study were done at optimum condition which is at pH 4 of initial
pH of MB solution, 0.01 g of initial XMCM dosage, 6 hours stirring time and
temperature of (30 2 ). The adsorption data fit well Langmuir model more
than Freundlich model. Based on Langmuir model, the maximum monolayer
adsorption capacity of MB was 21.62 mg g-1 which indicated that XMCM can
be a new alternative adsorbent for removing MB.
ix
ABSTRAK
Metilen Biru (MB) adalah pewarna yang selalu digunakan untuk mewarna
produk daripada pelbagai industri seperti industri pembuatan pakaian,
pencetakan, kulit, kosmetik dan penghasilan kertas. Xanthogenated-Modified
Chitosan Microbeads (XMCM) diperkenalkan sebagai agen alternatif
penjerap baru dalam proses menjerap kandungan MB yang terkandung di
dalam air. Fourier Transform Infrared (FT-IR) digunakan untuk
mengenalpasti interaksi antara MB dengan kumpulan berfungsi yang
terkandung dalam XMCM. Beberapa parameter yang mempengaruhi
keupayaan penjerapan seperti kuantiti XMCM dan pH awal larutan MB telah
dikaji melalui eksperiment ini. Kajian ini dilakukan pada keadaan optimum
iaitu pada pH 4 untuk pH awal larutan MB, 0.01 g berat awal XMCM, 6 jam
waktu pengacauan dan pada suhu (30 2 ). Data yang terhasil lebih
menepati model Langmuir berbanding model Freundlich. Berdasarkan model
Langmuir, nilai penjerapan maksima MB adalah 21.62 mg g-1. Kajian ini
membuktikan XMCM boleh menjadi agen alternatif penjerapan baru untuk
menyingkirkan MB.
x
CHAPTER 1
INTRODUCTION
Water is vital for the entire aspects of life and also an important feature that
management is a crisis faced by every country in the world. This crisis affects
ecosystem that act as our life support system. There are many factors affecting
due to its characteristics that give harmful effects on human and the nature
(Wang et al., 2011). Dye pollution in industrial waste are from textile, leather,
itself, there are a few types of dye pollutant such as reactive, direct, acid, and
1
The most common effluent found in textile industry is called methylene blue
(MB) which is classified as a basic dyestuff and widely used for dyeing cotton,
silk and wool (Rafatullah et al., 2010). Even though, MB is not classified as
amount of this chemical can lead to adverse effect to human health and
difficulties, while direct contact with MB may lead to permanent eye injuries,
There are a variety of method were used in terms of treating wastewater due to
of dyes was found to be effective and economical compared to the use of other
excessive discharge of this compound into water body, many cases related to
its biodegradability have been reported to have negative impact on the natural
2
with the use of this compound to understand and effectively participate in the
process of discharging this chemical to the most safely and hazard-free in our
Eco-system.
have been studied and developed in these past three decades such as a
et al., 2009).
without producing chemical sludge (Zhu et al., 2012). Activated carbon was
materials because of its large surface area and functional groups on its
structure that makes adsorption possible in high capacity (Vargas et al., 2011).
However, activated carbon requires high operating cost (Weng et al., 2009).
3
1.2 Significance of the study
Each year, the world faces with the critical issues involving management of
two million tons waste components from industrial, domestic and agricultural
discharge that goes into the global water channels (Corcoran et al., 2010). This
phenomenon has been reported to affect more than 1.8 million of children age
derived from the most common effluent found in textile industry called
methylene blue (MB), which was classified as a basic dyestuff and widely
used for dyeing cotton, silk and wool (Rafatullah et al., 2010).
and other pollutants due to its effectiveness and unique chemical structure
(Wan Ngah and Hanafiah, 2008; Zhu et al., 2012). Studies proven that
4
remove pollutant completely, non-practical, produces toxic sludge, sometimes
because its molecules are intractable, tough over aerobic digestion and steady
when matched with oxidizing properties (Crini and Badot, 2008). Treating
methods found useful in removing dye molecules were reported not only have
poor performance in favor to the economic point of view, but also would be
(Crini and Badot, 2008). In the actual wastewater management, there is more
than one process that required to satisfy the process of dye removal within a
manufacturing lines would be highly necessary (Crini and Badot, 2008). This
adsorbent that is reasonably priced, yet comes with higher efficiency profile as
the main solution in water treatment. Two most important efficiencies that are
5
relevant to the profile would be i) the amount or dosage of the adsorbent use
per unit of the untreated water, and ii) its disposal residues.
which are natural and can easily be found in massive quantities (Crini and
which was reported as one of the more preferable and common methods in
removing dye pollutants from the water body (Crini and Badot, 2008). Its
Previous literature also suggests greater potential for chitosan is possible when
modifications (Wan Ngah et al., 2011; Zhu et al., 2012). It was revealed in the
recent years that chitosan is pH sensitive; hence, modifying the process of its
The literature also suggests that the use of modified chitosan beads could be
treatment.
6
This paper demonstrates that XMCM can be used in treating wastewater due
to MB pollution. This study was focused on three main stages which are
the adsorbent, batch mode study and isotherm study. The adsorbent were
characterized by using FTIR, pHslurry and pHzpc analysis. Whereas, in the batch
mode study, several parameters that influence the adsorption capacity are
and the effect of initial pH. For isotherm study, the data were analyzed using
during productions and saves the marine ecology. Through this study,
revealed.
polluted wastewater.
7
1.3 Objectives of Study
onto XMCM.
methylene blue.
Freundlich model).
8
CHAPTER 2
LITERATURE REVIEW
higher death prevalence more than the total of people killed in wars (Steiner
and Tibaijuka, 2010). Illnesses due to contaminated water affects more than
of marine ecosystems involving food chain are badly affected (Lange and
Jiddawi, 2009). These impacts are all due to poor management of wastewater,
into the mainstreams, thus adding significant risks to the fragile marine lives
actions taken to reduce risks associated to water pollution, the world larger
(UN Habitat, 2009). To cope with the world marines ecosystem would bring
component, while marine lives are part of our food and nutritional sources
9
3400% depending on the area and technology used for the treatment (Steiner
phenomenon. This could be achieved when the governing bodies may be able
to offer better public health to the local population, protect vulnerable marine
Tibaijuka, 2010). Meeting the criteria set to fulfill acceptable standards and
dealing with the costs associated to the discharge process are among the duties
(Steiner and Tibaijuka, 2010). Although good system comes at high expenses,
industrial waste from spreading into the mainstreams and the utilization of
closed water system are two main approaches central to cost effective
wastewater onsite, industries may have better access to cleaner water supply,
thus minimize the production costs. This, when seen from the general
economic point of view would means that consumers may enjoy huge
10
2.2 Dye Pollution
The presences of dye pollutant in water body not only affect the aesthetic
nature but also interferes the sunlight transmission into water which will
several types of dyes pollution that can be classified based on their properties
and usage with are acid dyes, basic (cationic) dyes, direct (anionic) dyes and
Acid dyes are soluble in water, which is generally contained azo (including
anthraquinone group. These dyes have been widely used as coloring agents for
food, cosmetic, silk, wool, nylon, and ink-jet printing. Basic dyes are also
dye also has been used medicine sector. The other water soluble dyes are
direct (anionic) dyes. The principal chemical classes of these anionic dyes are
broadly used for paper, rayon and cotton but not widely used for dyeing nylon.
bands were obtained on absorption spectra. These dyes are better than direct
dyes due to it bright color than direct dyes. Its contain chromphoric groups
11
anthraquinone. They form covalent bond with the fiber. They are widely used
for dyeing cotton but not broadly used for dyeing nylon and wool (Gupta and
Suhas, 2009).
Rafatullah et al. (2010) estimated that more than 100 000 commercially
available dyes with over 7 x 105 were generated by many industries to color
their product. It is important to remove the present of dyes from water body
because some dyes highly visible and undesirable even in very small amounts
water pollution is color since any color change in water body can be detected
directly with naked eyes. According to Crini and Badot (2008), it is difficult to
azo dyes are recalcitrant molecules, stable to oxidizing agent and resistant to
aerobic digestion. The low biodegradability and inert properties of dyes make
Ngah et al., 2008; Zhu, et al., 2012). This technique has been used in many
fields including but not limited to environment, oil and gas, and medicine in
order to remove heavy metal, dyes, storage and oil spillage control (Auta and
Hameed, 2011). Adsorption process has proven to be more reliable, safe and
12
coagulation, chemical oxidation and reduction, and electrolytic method
and yields a blue solution when dissolved in water. It has strong adsorption
H3C + CH3
N S N
CH3 CH3
Figure 2.1 Molecular structure of methylene blue
Activated carbon are porous materials that have been reported by recent
literature as the most effective adsorbent to remove heavy metal and dyes
pollution due to its fast adsorption kinetic, high adsorbing capability and also
having a high surface area (reach up to 3000 m2 g-1) (Cazetta et al., 2011;
13
Nasuha et al., 2010). However it is relatively expensive due to its processes.
The cost to produce activated carbon would increase accordingly with the
In recent years, removal of methylene blue using biomass and biopolymer has
Many researchers developed a new effective low cost adsorbent that comes
ball clay (100 mg g-1), sugar extracted spent rice biomass (8.13 mg g-1), garlic
peel (82.64, 123.45 and 142.86 mg g-1) , sugar beet pulp (714.29 mg g-1) and
lotus leaf (8.13 mg g-1) (Auta et al., 2012; Rehman et al., 2012; Hameed and
Vuurovi et al. (2012) reported the use of sugar beet pulp in order to remove
methylene blue from aqueous solutions is the one of the most effective agro-
indusrial solid waste adsorbent. Even though this adsorbent used do not
capacity which is 714.29 mg g-1. The high ability of this adsorbent to remove
revealed that this adsorbent was found fit well the Langmuir models which
14
indicate that the monolayers adsorption occurs. Scanning Electron Micrograph
analysis also showed that the surface of adsorbent before after adsorption is
different. It was found that this study was carried out at pH 8 of initial pH of
noticed that the adsorption of MB onto sugar beep increase with the increasing
of clay onto MB (cationic dyes) due increasing of pore size and surface area.
Acid react with a various type of cations and form chlorates and sulfates
study, it was found that adsorbent porous structure not the only influenced the
Nasuha et al. (2011) reported that NaOH treatment onto rejected tea increase
pores of NaOH-modified rejected tea surface. The author also stated that the
FTIR spectra of NaOH-modified rejected tea at 3112 cm-1 show the intense
and broad absorption peaks indicate the present of hydroxyl group on the
15
can be used in other to remove methylene blue from aqueous solution which is
biopolymer chitosan.
2.3 Chitosan
to remove dyes and heavy metal ions even at low concentration (Wan Ngah
and Hanafiah, 2008). The presence of high amine and hydroxyl groups in
al., 2010; Zhu et al., 2012). The cationization of amino groups in chitosan
acidic media (Wan Ngah et al., 2011). This adsorbent is a natural biopolymer
that formed from deacetylation of chitin which comes from seafood cells such
as crabs and prawns (Wan Ngah et al., 2011). It also known as an ideal natural
Ngah et al., 2011). In addition, they are cheaper and effective as alternatives to
activated carbon due to the highly cost of activated carbons (Wan Ngah and
Hanafiah, 2008).
O O
OH
O
NH 2
Figure 1.2 Molecular structure of chitosan
Although chitosan alone has been proven effective in adsorption dyes and
16
the pH values of the environment due to the characteristic of chitosan that is
sensitive to pH (Wan Ngah et al., 2011). This means that its chemical property
Hence, its performance could still be improvised (Wan Ngah et al., 2011).
solubility of chitosan in dilute mineral and organic acid. From the previous
research by Wan Ngah et al. (2004) shows that chitosan is soluble in 5% (v/v)
acetic acid but insoluble in 0.10 M NaOH and distilled water. However, the
treated chitosan beads with cross-linking agent shows that chitosan are
insoluble in that three medium solution. Cross-linking agent has been applied
Ngah et al., 2011). There are several reagent that have been selected as a
chitosan. Hence, there is still a gap to which method is the best among many
17
2.3.1 Modified Chitosan
According to Liu et al. (2010), Chitosan are not effective to remove cationic
dyes unless undergo some modification. Recent literature found that there are
from wastewater, inter alia; chitosan-g-poly acrylic acid (1873 mg g-1) and
al., 2011; Liu et al., 2010; Huang et al., 2011; Guo and Wilson, 2012; Fan et
al., 2012)
Wang et al. (2011) reveal that the adsorption of methylene blue by using
also reveal that the adsorption rate of both modified chitosan were fast. In the
initial 15 min, about 90% of MB was removed. This study was conducted at
noticed that the adsorption of methylene blue onto both modified chitosan
groups that present in acrylate were dissociated and form COO-. Hence,
generates electrostatic repulsion forces among the adjacent ionized group due
18
Wang et al. (2011) also reveal that there is a relationship between temperature
temperature shifted from 40C to 60C. It was described that the increase
temperature of the tested water does create a swelling effect within the
adsorbents core structure, thus allowing more adsorption of the dye molecules
composition; hence, decrease its capacity to adsorb further. This means that
with increased exposure to extreme heat, the chitosan solution would not
preform effectively.
However, it was also noticed that the adsorption capacity decrease with the
groups on the attapulgite surface. Attapulgite react with acrylic acid and act as
capacity. Through this study, the author adding 30% attapulgite into modified
19
Liu et al. 2010 also used acrylic acid in modification of chitosan-g-poly
group that can adsorb Methylene blue (cationic dyes) from aqueous solutions,
inter alia; sulfonic acid, hydroxyl, amine and carboxylic acid groups.
Hydrogel able to adsorb and retain water and solute molecule because it is has
higher porous network structures and water content which allow solute to
by Fan et al. (2012). The study was conducted to improve the ability of natural
removal from aqueous solutions. It was found in through the study that the
transformed into functional graphene oxide with the existence of oxygen. The
extended surface widening was found not only benefits the mechanical
strength of the stable chitosan, but also extended the capability of the modified
20
2.3 Xanthogenate
form cellulose xanthogente derived from Eichornia Species has been done by
Deng et al., 2012; Zhou et al., 2009 and Tan et al., 2008. The principle of
Xanthate group have been chosen due to the presence of sulfur atoms. Sulfur
groups are well known as having a greatly strong affinity for the most heavy
metal and dyes. In addition, the metal-sulfur is really stable even in basic
Based on Zhu et al. (2012) previous study, It was proven that magnetic
has been used previously on modified magnetic chitosan (Chen and Wang,
21
2008) and chitosanepichloroydrin (Kannamba et al., 2010) to enhance the
Zhou et al. (2011), state that sulphur and magnesium content in xanthogenates
copper with magnesium also increases the adsorption of copper. FTIR spectra
alkali treatment removed hemicelluloses and lignin from the raw plant
materials. However, new functional group which is O-CS-C and C=S was
greatly strong affinity for the most heavy metal and dyes.
Tan et al. (2008) also stated that adsorption capacity cellulose xanthogente
derived from Eichhornia Species was higher than other plant materials. It was
noticed that, adsorption of copper ions increase with the increasing of pH and
capacity of Cu2+ but lowest in the solutions that containing proves that
almost the same which indicates that adsorption of Cu2+ not affected by
sodium ion.
22
CHAPTER 3
METHODOLOGY
All reagent used were analytical grade chemicals, and distilled water was used
wavelength.
4. Chitosan flakes
7. Methylene blue
23
8. Sodium chloride (NaCl)
2. Grinder
3. Sieve
Model
24
3.2 Research Methodology
below:
Sample Treatment
FTIR Dosage
pHslurry pH
pHzpc Isotherm
(Kannamba et al., 2010; Wan Ngah et al., 2013; Zhou et al., 2011). 2.0 g
chitosan powder was soaked in 75 mL of 5% (v/v) acetic acid and was stirred
for 3 hours to make sure the chitosan completely dissolved. The dissolved
adsorbent was neutralized by dropping the adsorbent gel into 500 mL of 0.5 M
NaOH solution under continuous stirring. White beads were left for 3 hours
under continuous stirring. The beads were washed with distilled water for
25
several times to remove the excess NaOH. The modified chitosan microbeads
were treated with 100 mL of 14% NaOH solution and were stirred for 2 hours.
continuously and was stirred for 2 hours. Next, 10 mL of 0.42 M MgSO4 was
added into the mixture and was stirred for another 1 hour. The Xanthogenate
distilled water. Lastly, the resulting beads were air-dried and sieved to obtain
3.4.1 FTIR
into 10 mg/L MB solution and was stirred for 24 hours. After the stirring
process completed, the solution was filtered. The adsorbents after adsorption
was air dried and the effect of chemical treatments was determined by
comparing any shift of band before and after adsorption. The functional
groups present in chitosan flake, XMCM before and after adsorption with
3.4.2 pHslurry
meter. The initial pH of distilled water was checked by using pH meter. After
that, 0.1 g of adsorbent was added into 100 mL distilled water and the mixture
26
was stirred for 24 hours. After the stirring process completed, the pH of the
3.4.3 pHzpc
solution was transferred into a series of conical flask. The initial pH (pHi) of
to 9 by adding 0.1 M HCl or 0.1 M NaOH. 0.1 g adsorbent was added to each
conical flask and the mixture was stirred for 24 hours. After the stirring
process had completed, the solution was filtered and the final pH (pHf) of the
The optimum dosage was determined by adding various doses of XMCM into
dosages used were 0.01 g, 0.02 g, 0.03 g, 0.5 g and 0.1 g. The mixture was
27
stirred at 120 rpm stirring rate for 6 hours. After the process was completed,
the solution was centrifuged at 3000 rpm for 5 min. The solution was analyzed
adding 0.1 M HCl and 0.1 M NaOH. The mixture was stirred for 6 hour at 120
rpm. After the adsorption process had completed, the solution was centrifuged
at 3000 rpm for 5 minutes and then it was analyzed by using UV-Vis
For the isotherm study, the concentration of adsorbate was varied ranging
0.01 g XMCM was added into each of solution. All solutions were stirred at
120 rpm for 6 hours. This study was done at 30 . After the stirring process
had completed, the solution was centrifuged at 3000 rpm for 5 minutes and
28
CHAPTER 4
4.1 Introduction
This chapter presents and discusses the result of experiment that had been
4.2.1 pHslurry
pH aqueous slurry is used to confirm either the adsorbent was acidic or basic
(Kamal et al., 2010). pHslurry obtained from this study was 9.91,which indicate
4.2.2 pHzpc
positively or negatively charged (Kamal et al., 2010). Figure 4.1 show the
value of pHzpc was 9.80 which indicate that XMCM was basic adsorbent.
29
Kamal et al. (2010) stated that when the pH of adsorbate is greater than pHzpc,
the surface of adsorbent will carry negative charge and vice versa. Hence,
higher than pHzpc value. In this study, pHzpc value was found to be near to the
pH of aqueous slurry (pHslurry), which matched the previous finding that the
0
0 2 4 6 8 10 12
-1
-2
-3
pHi - pHf
-4
-5
-6
-7
-8
pH
4.2.3 FTIR
spectrum of chitosan before and after treatment and XMCM before and after
MB loaded shown in Figure 4.2 and Figure 4.3 indicates the presence of
30
peak at 3272 cm-1 corresponds to the presence of R-OH (hydroxyl group) and
-NH2 (amine group). Kamari et al. (2009) stated that the broad and strong
peak ranging from 3200 cm-1 to 3600 cm-1 indicates the overlapping of R-OH
(hydroxyl group) and -NH2 (amine group) stretching vibrations. The peak that
vibration.
The NH2 group was observed at peak 1744 cm-1. Peak located at 1636 and
1560 cm-1 represent the deformation of amine which similar to peak (around
1650 cm-1) that observed by Kamari et al. (2009). The appearance sharp
group). The bands that observed at 1375 and 1321 cm-1 can be attributed to the
deformation of -CH3 and C-N stretching which similar to peak that observed
Peak located at 1298, 1229 and 1147 cm-1 can be assigned as C-O-C
et al., 2009), 1153 (Zhu et al., 2012) and 1115 cm-1 (Azlan et al., 2009). Peak
al., 2009) and 1026 cm-1 (Zhue et al., 2012) can be assigned as C-O-C
31
After modification process with xanthogenated, several changes in XMCM
spectra were observed. Peak that observed at 3455 and 3187 cm-1 indicate the
(Deang et al., 2012). A new peak appear at 1654 cm-1 indicate the present of
imine bond (C=N). NH2 peak of chitosan was found to be shifting slightly to
the right (1445 cm-1) and increase the intensity due to modification treatment
Figure 4.3 shows the spectrum of XMCM before and after adsorption with
Methylene Blue. Based on the observation, there are new peak appear at 1546
cm-1 after adsorption process which prove that a chemical interaction was
occur. This conclusion was proven with the studies done by Ngah et al.
(2006), they concluded that no new peak was observed after adsorption
charge do not occur through their study. The reduction of intensities of peak
that observed at 1464 and 1370 cm-1 which also shift more to the left
compared to peak 1445 (N-H group in amine) and 1429 cm-1 (C=S group)
before adsorption process indicated that nitrogen and sulfur atoms are the
adsorption sites for MB on XMCM. Therefore, the main functional groups that
sulfur.
32
CHITOSAN
707
739
3273 2875 1744
1453 1229 896
1637
1147
1560
%T
1375
1033
XMCM
706
1730 739
3187
1654
1225 848
1035
1429
1145 865
4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650
cm-1
XMCM- MB
706
1730 739
3451 3187 1654
2941
1225
1145 848
1034 865
%T
1429
T
1445 706
3566 XMCM
3190 739
33
4.3 Batch mode study
Batch mode study is used to determine the optimum condition for adsorption
of MB onto XMCM.
in Figure 4.4 shows that the percent removal of MB increased with the
to the mass of adsorbent in the solution as the particle size range used in this
zer et al. (2007), the increase in the adsorption of MB with the adsorbent
dosage can be associated with the increase of surface area and the sorption
sites. The decreases of the effective surface area explained the reduction in
optimum dosage for further adsorption study due to the highest value of
adsorption capacity.
34
40 10
Removal (%)
qe (mg g-1)
20
Removal (%)
qe (mg/g)
0 0
0.00 0.02 0.04 0.06 0.08 0.10 0.12
Dosage (g)
hydroxyl and hydrogen ion will be adsorbed easily. Initial pH of the solution
also affects the adsorption of other ions (Han et al., 2011). Therefore, the
adsorption of MB dye was studied at different pH. This study was performed
range for dye adsorption onto adsorbent. The accumulation of competitor ions
below this range would limits the adsorption capacity of MB onto XMCM.
drastically from 2.24 to 6.83 mg g-1 due to the reaction of cationic dye with
surface attract positive charge by adsorb H+ ions. Hence, the competition and
35
electrostatic repulsion between MB and H+ ions for the adsorption site prevent
However, this does not explain the adsorption capacity of MB after pH 4 that
Therefore, it is proven that electrostatic mechanism was not the only reason
According to Han et al. (2011), chemical reaction between the dye molecules
and adsorbent also affects the adsorption capacity. Therefore, the experiment
36
8
qe (mg/g) 5
0
2 3 4 5 6 7 8
pH
Isotherm study was done to show the relationship between amount adsorbed
per unit weight of adsorbent (known in this equation: qe mg g-1) and the
the adsorbent are equivalent to the amount of adsorbent being desorbed. Here,
MB onto XMCM shown in Figure 4.6 clearly shows that adsorption capacity
37
in Giles classification system was obtained from this study indicates that
adsorption sites would be saturated due to the ratio of the number of MB ions
are the most common use of isotherm models. Isotherm models were applied
38
25
20
qe, mg/g 15
10
0
0 10 20 30 40 50 60 70
Ce, mg/L
According to Crini and Badot (2008), Langmuir model was found to be the
recent study. The Langmuir equation as shown in Table 4.1 was used to
theoretical maximum adsorption capacity per unit weight adsorbent (mg g-1).
39
mg-1) and a measure of the energy of adsorption, and Ce is the equilibrium
Ce
Figure 4.7 shows the Langmuir plotting against Ce gives a straight line of
e
et al., 2009). A similar adsorption isotherm was also found in the adsorption
studies of MB onto a various type chitosan carried out by (Liu et al., 2010;
Fan et al., 2012; Huang et al., 2011; Wang et al., 2011). The maximum
favourable adsorbent. (Kamari et al., 2009) stated that based on the separation
factor on isotherm shape, the adsorption of dye on chitosan are favorable if the
40
4.0
y = 0.0463x + 0.3503
R = 0.9885
3.5
3.0
2.5
Ce/qe
2.0
1.5
1.0
0.5
0.0
0.000 10.000 20.000 30.000 40.000 50.000 60.000 70.000
Ce (mgL-1)
Freundlich model was developed from the assumption that the adsorption
This model also assumes that the stronger adsorption site are occupied first
and the increasing of degree site occupation degree will leads the decreasing
the binding strength. The model as shown in Figure 4.8 explained multilayer
(heterogeneous surface). Table 4.2 shows the non-linear and linear equation of
Freundlich.
e
Ce n log e
log + log Ce
n
41
Where and n are Freundlich constant that represents adsorption capacity
(mg g-1) and adsorption intensity (unit less). This Freundlich constant value
respectively.
correlation coefficient value obtained from this study is shown in Table 4.3.
et al. 2012) stated that if Freundlich constant n value is greater than 1 indicate
the adsorption of MB onto XMCM does not follow the Freundlich isotherm. It
is because the value obtained does not correlate well compared to the
42
1.60
1.40
1.20
0.60
0.40
0.20
0.00
0.00 0.50 1.00 1.50 2.00
log Ce
Langmuir Freundlich
1 2
(mg g- ) (L mg-1) R KF n R2
21.62 0.13 0.9885 1.15 1.29 0.9351
43
CHAPTER 5
are due to the XMCM volume used during the experiment, its initial pH value,
chemical process and uptake rate of XMCM against MB was assessed and
wastewater.
The aims and objectives of this study have been achieved in practice, where
another alternative adsorbent has been developed and tested onto MB from
44
Through the experiment, it was proven that the preparation and modification
certain variables such as OH group from the modified chitosan has been
reported lost from the formulation. This has great impact on the functional
onto XMCM was found at pH 4 for of initial MB aqueous solution pH, and at
and effective when modified and tested with MB inter alia; chitosan-g-poly
poly(acrylic acid) (1.03 and 3.59 mmol g-1), and magnetic chitosan/graphene
oxide (180.83 mg g-1) (Wang et al., 2011; Liu et al., 2010; Huang et al., 2011;
Guo et al., 2012; Fan et al., 2012), the XMCM results in this study indicate
that the modified form of chitosan has underperform itself and incapable to
5.2 Recommendations
The outcome shows that there is very little benefit gained with the use of
XMCM on MB in this study. Based on the outcome of this research, there are
45
i) whether there is a method to be utilized in preserving the OH group
introduce sulfur atoms and also some ionic functional group (in hydrogel) that
can adsorb Methylene blue (cationic dyes) from aqueous solutions, inter alia;
Hydrogel able to adsorb and retain water and solute molecule because it is has
high porous structures and water content which allow solute to diffuse through
hydrogel structure.
serious attention and action worldwide. The findings of each studies related to
46
CITED REFERENCES
Auta, M., and Hameed, B. H. (2011). Optimized waste tea activated carbon for
adsorption of Methylene Blue and Acid Blue 29 dyes using response surface
methodology. J. Chem. Eng., 175(0), 233-243.
Azlan, K., Wan Saime, W. N., and Lai Ken, L. (2009). Chitosan and chemically
modified chitosan beads for acid dyes sorption. J. Environ. Sci., 21(3), 296-
302.
Cazetta, A. L., Vargas, A. M. M., Nogami, E. M., Kunita, M. H., Guilherme, M. R.,
Martins, A. C., Almeida, V. C. (2011). NaOH-activated carbon of high surface
area produced from coconut shell: Kinetics and equilibrium studies from the
methylene blue adsorption. J. Chem. Eng., 174(1), 117-125.
Chen, Y., and Wang, J. (2012). The characteristics and mechanism of Co(II) removal
from aqueous solution by a novel xanthate-modified magnetic chitosan. Nucl.
Eng. Des., 242(0), 452-457.
Corcoran E. C., Nellemann, E., Baker, R.,(2010). Sick Water? The Central Role of
Wastewater Management in Sustainable Development (p.5). Nairobi:UN
Habitat/UNEP/GRIDArendal.
Deng, H., Lu, J., Li, G., Zhang, G., and Wang, X. (2011). Adsorption of methylene
blue on adsorbent materials produced from cotton stalk. J. Chem. Eng.,
172(1), 326-334.
Deng, L., Geng, M., Zhu, D., Zhou, W., Langdon, A., Wu, H., Wang, Y. (2012).
Effect of chemical and biological degumming on the adsorption of heavy
metal by cellulose xanthogenates prepared from Eichhornia crassipes.
Bioresour. Technol., 107(0), 41-45.
Fan, L., Luo, C., Sun, M., Li, X., Lu, F., and Qiu, H. (2012). Preparation of novel
magnetic chitosan/graphene oxide composite as effective adsorbents toward
methylene blue. Bioresour. Technol., 114(0), 703-706.
47
Gupta, V. K., and Suhas. (2009). Application of low-cost adsorbents for dye removal
A review. J. Environ. Management, 90(8), 2313-2342
Hameed, B. H., and Ahmad, A. A. (2009). Batch adsorption of methylene blue from
aqueous solution by garlic peel, an agricultural waste biomass. J. Hazard.
Mater., 164(23), 870-875.
Hameed, B. H., and El-Khaiary, M. I. (2008). Sorption kinetics and isotherm studies
of a cationic dye using agricultural waste: Broad bean peels. J. Hazard.
Mater., 154(13), 639-648.
Han, X., Wang, W., and Ma, X. (2011). Adsorption characteristics of methylene blue
onto low cost biomass material lotus leaf. J. Chem. Eng., 171(1), 1-8.
Huang, X.-Y., Bu, H.-T., Jiang, G.-B., and Zeng, M.-H. (2011). Cross-linked succinyl
chitosan as an adsorbent for the removal of Methylene Blue from aqueous
solution. Int. J. Biol. Macromol., 49(4), 643-651.
Kamari, A., and Ngah, W. S. W. (2009). Isotherm, kinetic and thermodynamic studies
of lead and copper uptake by H2SO4 modified chitosan. Colloids B:
Biointerfaces, 73(2), 257-266.
Kannamba, B., Reddy, K. L., and AppaRao, B. V. (2010). Removal of Cu(II) from
aqueous solutions using chemically modified chitosan. J. Hazard. Mater.,
175(13), 939-948.
Lange, G.M., and Jiddawi, N. (2009). Economic value of marine ecosystem services
in Zanzibar: implications for marine conservation and sustainable
development. Ocean and Coastal Management, 52:521532.
Liu, Y., Zheng, Y., and Wang, A. (2010). Enhanced adsorption of Methylene Blue
from aqueous solution by chitosan-g-poly (acrylic acid)/vermiculite hydrogel
composites. J. Hazard. Mater., 22(4), 486-493.
Nasuha, N., Hameed, B. H., and Din, A. T. M. (2010). Rejected tea as a potential low-
cost adsorbent for the removal of methylene blue. J. Hazard. Mater., 175(1
3), 126-132.
48
Ngah, W. S. W., and Fatinathan, S. (2006). Chitosan flakes and chitosanGLA beads
for adsorption of p-nitrophenol in aqueous solution. Colloids Surf. A:
Physicochem. Eng. Aspects, 277(13), 214-222.
Ngah, W. S. W., and Fatinathan, S. (2010). Pb(II) biosorption using chitosan and
chitosan derivatives beads: Equilibrium, ion exchange and mechanism studies.
J. Environ. Sci. 22(3), 338-346.
zer, D., Dursun, G., and zer, A. (2007). Methylene blue adsorption from aqueous
solution by dehydrated peanut hull. J. Hazard. Mater., 144(12), 171-179.
Rafatullah, M., Sulaiman, O., Hashim, R., and Ahmad, A. (2010). Adsorption of
methylene blue on low-cost adsorbents: A review. J. Hazard. Mater., 177(1
3), 70-80.
Rehman, M. S. U., Kim, I., and Han, J.-I. (2012). Adsorption of methylene blue dye
from aqueous solution by sugar extracted spent rice biomass. Carbohydr.
Polym., 90(3), 1314-1322.
Tan, L., Zhu, D., Zhou, W., Mi, W., Ma, L., and He, W. (2008). Preferring cellulose
of Eichhornia crassipes to prepare xanthogenate to other plant materials and its
adsorption properties on copper. Bioresour. Technol., 99(10), 4460-4466.
Vargas, A. M. M., Cazetta, A. L., Kunita, M. H., Silva, T. L., and Almeida, V. C.
(2011). Adsorption of methylene blue on activated carbon produced from
flamboyant pods (Delonix regia): Study of adsorption isotherms and kinetic
models. J. Chem. Eng., 168(2), 722-730.
49
Wang, L., Zhang, J., and Wang, A. (2011). Fast removal of methylene blue from
aqueous solution by adsorption onto chitosan-g-poly (acrylic acid)/attapulgite
composite. Desalination, 266(13), 33-39.
Wan Ngah, W. S., Endud, C. S., and Mayanar, R. (2004). Removal of copper(II) ions
from aqueous solution onto chitosan and cross-linked chitosan beads. React.
Funct. Polym., 50(2), 181-190.
Wan Ngah, W. S., Teong, L. C., Toh, R. H., and Hanafiah, M. A. K. M. (2013).
Comparative study on adsorption and desorption of Cu(II) ions by three types
of chitosanzeolite composites. J. Chem. Eng., 223(0), 231-238.
Weng, C.H., Lin, Y.T., and Tzeng, T.W. (2009). Removal of methylene blue from
aqueous solution by adsorption onto pineapple leaf powder. J.Hazard. Mater.,
170(1), 417-424.
Zhou, W., Ge, X., Zhu, D., Langdon, A., Deng, L., Hua, Y., and Zhao, J. (2011).
Metal adsorption by quasi cellulose xanthogenates derived from aquatic and
terrestrial plant materials. Bioresour. Technol., 102(3), 3629-3631.
Zhou, W., Zhu, D., Langdon, A., Li, L., Liao, S., and Tan, L. (2009). The structure
characterization of cellulose xanthogenate derived from the straw of
Eichhornia crassipes. Bioresour. Technol., 100(21), 5366-5369.
Zhu, Y., Hu, J., and Wang, J. (2012). Competitive adsorption of Pb(II), Cu(II) and
Zn(II) onto xanthate-modified magnetic chitosan. J. Hazard. Mater., 221
222(0), 155-161.
50
A. Personal profile
Full name Siti Nadzifah binti Ghazali
National IC no 890923 03 5656
Birth date 23th September 1989
Citizenship MALAYSIA
Place of birth Kelantan, MALAYSIA
Gender Female
Correspondence address Lot 2104,
Belakang Hosp. Machang,
Kg. Cherodok, 18500,
Machang, Kelantan
Telephone no. (HP) 6019 454 3523
Email address nadzifahghazali@yahoo.com
I am fluent in written and spoken Malay and English. I have a basic knowledge of
Arabic language.
C. Academic qualifications
Degree Area Institution Year awarded
B.Sc. (Hons.) Chemistry Universiti Teknologi MARA, 2014
Malaysia
Diploma Industrial Universiti Teknologi MARA, 2010
Chemistry Malaysia
S.P.M Science Sek Menengah Zainab 1, Kelantan 2006
D. Work experience
Post Place Year
Chemical LDPE Processing Plant PETLIN (MALAYSIA) Sdn.Bhd 2010
Trainee
51
E. Related experience
Post Place Year
Facilitator Motivational Programe (Kem KACA), University 2011
Teknologi MARA, Jengka
Facilitator Minggu Mesra Siswa Semester Disember 2009- 2009-2010
April 2010, University Teknologi MARA, Arau
Facilitator Minggu Mesra Siswa Semester July November 2009
2009, University Teknologi MARA, Arau
Member Elite Squad (Secretariat MPP), University 2009-2010
Teknologi MARA, Arau
Member Chemsit Club, University Teknologi MARA, Arau 2007-2010
Member Chess Tournament in conjunction with Open Day 2009
UniKL MSI
Member Program Rakan Muda Wawasan Desa IPT, 2009
Peringkat Negeri Perlis
Member of Persembahan Silat Cekak Malaysia, Karnival 2008
Committee Gegar UiTM Perlis
Member of Persatuan Seni Silat Cekak Malaysia, University 2007-2008
Committee Teknologi MARA, Arau
52