SUMMARY THESIS

MODIFICATION OF CHITOSAN-COATED IRON SAND MAGNETIC

MATERIAL WITH GLYCIDYLTRIMETHYLAMMONIUM CHLORIDE FOR
Cr(VI) ADSORPTION

SALWA KAMILIA
20/466489/PPA/06055

MAGISTER OF CHEMISTRY STUDY PROGRAM

CHEMISTRY DEPARTMENT
FACULTY OF MATHEMATICS AND NATURAL SCIENCE
GADJAH MADA UNIVERSITY
YOGYAKARTA
2022

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 APPROVAL SHEET

MODIFICATION OF CHITOSAN-COATED IRON SAND MAGNETIC

MATERIAL WITH GLYCIDYLTRIMETHYLAMMONIUM CHLORIDE FOR
Cr(VI) ADSORPTION

Written by:
SALWA KAMILIA
20/466489/PPA/06055

First Advisor

Prof. Dr.rer.nat. Nuryono, M.S. Date: 22/11/22

NIP. 196407141988111001

Second Advisor

Dr. Sutarno, M.Si Date: 21/11/22

NIP. 196108161988031002

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 TABLE OF CONTENTS

SUMMARY THESIS 1
APPROVAL SHEET 2
TABLE OF CONTENTS 3
CHAPTER I INTRODUCTION 4
CHAPTER II LITERATURE REVIEW 5
II.1 Chitosan 5
II.1 Material magnetic from sea sand 5
II.2 Quaternary ammonium 5
II.3 Adsorption of chromate anion in water 5
CHAPTER III RESEARCH METHODS 6
III.1 Material magnetic (MM) isolation 6
III.2 MM-Kit and MM-Kit-GTMAC composite synthesis 6
CHAPTER IV RESULT AND DISCUSSIONS 6
IV.1 Characterization of the MM, MM-Kit, and MM-Kit-GTMAC 6
IV.2 Cr(VI) Ion Adsorption Study by MM-Kit-GTMAC 9
IV.2.1 Effect of pH of Cr(VI) adsorption system by adsorbent 9
IV.2.2 Adsorption kinetics 10
IV.2.3 Adsorption isotherm 10
CHAPTER V CONCLUSION AND SUGGESTIONS 11
Conclusions 11
Suggestion 11
REFERENCES 11

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 CHAPTER I
INTRODUCTION
Chromium (Cr) is a pollutant that is considered as one of the most toxic
inorganic pollutants because it has many detrimental effects (mutagenic and
carcinogenic) on human health and the environment (Raghunathan et al., 2009).
The adsorption method is the most promising method for removing Cr(VI) anions
because of its high efficiency, environmental friendliness, and ease of
regeneration (Chen et al., 2015; Fallah et al., 2019).
Chitosan containing –NH2 and –OH functional groups has received more
attention as an effective adsorbent with its advantages such as non-toxicity,
biodegradability, low cost, wide applicability, and high adsorption potential
(Budnyak et al., 2015; Khapre and Jude, 2022 ). The drawback of using chitosan
adsorbents is that they cannot be used at low pH values (Kyzas and Bikiaris,
2015). Modifications need to be made to chitosan to increase its efficiency as an
adsorbent for various heavy metals. Glycidyltrimethylammonium chloride
(GTMAC), a low toxic quaternary ammonium salt reagent with a strong positive
charge in water (Rwei et al., 2014), was chosen to modify chitosan in increasing
its adsorption capacity. GTMAC has been used several times as a modifying agent
in chitosan (Mivehi et al., 2008).
The use of chitosan adsorbent has drawbacks in the difficulty of the
separation process with the adsorbate. The magnetic separation technique is an
effective method for accelerating the separation process and is widely applicable
in water treatment (Tang and Lo, 2013). Magnetite material is used into the
chitosan adsorbent in the form of a coating to achieve rapid separation from water
after its saturated adsorption. This study used iron sand from Glagah Beach,
Kulon Progo Regency, DIY.

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 CHAPTER II
LITERATURE REVIEW
II.1 Chitosan
Chitosan has more primary amine groups than chitin, making it more basic
and nucleophilic. When heated, chitosan tends to decompose rather than melt so
that this polymer has no melting point. Chitosan is insoluble in neutral or alkaline
solutions but dissolves in acidic solutions such as acetic acid, formic acid, lactic
acid and glutamic acid. When chitosan is dissolved in an acidic solution, the
primary amine groups in chitosan will be protonated and positively charged.
Therefore, solvated chitosan molecules are polycationic and can be coagulated if
particles or molecules carrying a negative charge are added, such as sodium
alginate, sulfate anions, and phosphates.
II.1 Material magnetic from sea sand
Iron sand in Indonesia can be found on the southern coast of Central Java,
Pandeglang, Banten, West Lampung, and Sunur Kota Pariaman (Wicaksono,
2011). Iron sand contains magnetic minerals such as magnetite (Fe3O4), hematite
(α–Fe2O3), and maghemite (γ–Fe2O3). These minerals have the potential to be
developed as basic materials for permanent magnets (Afdal and Niarti, 2013).
II.2 Quaternary ammonium
Glycidyltrimethylammonium chloride (GTMAC) with the formula
C6H14ClNO belongs to the cationic surfactant group which has a head in the
form of an ammonium group which is hydrophilic. GTMAC has been used
several times as a modifying agent in chitosan (Mivehi et al., 2008). In general,
the addition of GTMAC aims to increase the positive charge on the surface of
chitosan.
II.3 Adsorption of chromate anion in water
Hexavalent chromium (Cr(VI)) is a metal that has greater toxicity
compared to trivalent chromium Cr(III) because the Cr(IV) anion is soluble and
has high mobility in the environment, which is difficult to decompose, does not
precipitate and is stable. (Ngatijo et al., 2020). The preparation of chromate
solution was carried out in an adsorption study of chromate anions, by dissolving

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potassium dichromate in aquabides. Adsorption is a process of adsorption by
certain solids on a substance due to the attractive force of atoms or molecules on
the surface of the solid without seeping inside (Hiramatsu and Osterloh, 2003).

CHAPTER III
RESEARCH METHODS
III.1 Material magnetic (MM) isolation
MM was crushed with a mortar and then sieved through a 200 mesh sieve.
Materials measuring < 200 mesh were then washed with distilled water and dried
in an oven at 90 ºC for 18 hours. 0.5 g of MM was activated by adding 1 mL of 1
M HCl solution and soaked for 24 hours, then dried in an oven at 90 ºC for 18
hours.
III.2 MM-Kit and MM-Kit-GTMAC composite synthesis
A total of 0.15 g of chitosan was dissolved in 30 mL of 1% CH ₃COOH
placed in a beaker until a gel was formed. 0.5 g of activated MM was added to
chitosan then stirred for 5 hours at room temperature (25 ºC). 0.5 M NH ₄OH
solution was added to the mixture to a pH of 7. The mixture was stored in an oven
at 60 ºC for 24 hours to make MM-Kit composites which were further
characterized by FT-IR, XRD, SEM-EDX, and VSM. The addition of
glycidyltrimethylammonium chloride (GTMAC) was carried out after the
administration of NH4OH to the MM-Kit. The mixture was then stored in the
oven at 60 ºC for 24 hours.

CHAPTER IV
RESULTS AND DISCUSSION
IV.1 Characterization of the MM, MM-Kit Composite, and MM-Kit-
GTMAC
The infrared spectra of MM, MM-Kit, and MM-Kit-GTMAC for each
variation are shown in Figure IV.1. The characteristic vibration of MM (Figure
IV.1.a) was identified at wave number 578 cm–1 which is the vibration of the Fe–
O group of iron oxide minerals contained in iron sand. The characteristic

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absorption of chitosan is shown by the vibrations of several functional groups that
make up chitosan (Figure IV.1.b), namely the broadening peaks in the 3400-3600
cm–1 region indicating the stretching vibration of the –NH2 group of chitosan and
at wave number 2924 cm–1 indicating the C–H stretching vibration of chitosan.
The coating of GTMAC-modified chitosan on the MM surface (Figures IV.1.c,
IV.1.d, and IV.1.e) showed a shift in wave number 3425.58 cm–1, indicating that
the stretching vibration of the –NH2 group of chitosan had been replaced. cluster
belongs to GTMAC. In addition, the interaction between GTMAC and the –NH2
group led to a new peak at 1481 cm–1 indicating the ammonium group and at
1635.64 cm–1 which was a C–N–C bending vibration of the new bond between
chitosan and GTMAC.

Figure IV.1 FT-IR spectra (a) MM, (b) MM-Kit, (c) MM-Kit-GTMAC (1:2), (d)
MM-Kit-GTMAC (1:4), and (e) MM- Kit-GTMAC (1:6)

Identification of minerals in MM with XRD (Figure IV.2.a) shows the

dominance of the magnetite content. The content of α-Fe2O3 (hematite) is also
identified in MM which is indicated by 2θ at 30.66º. The diffraction pattern on the
chitosan-coated MM (Figure IV.2.b) still has characteristic MM peaks but there is
a decrease in intensity caused by a decrease in MM concentration due to the
addition of chitosan. Likewise with the addition of GTMAC to the MM-Kit

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(Figures IV.2.c, IV.2.d, and IV.2.e). Modification of quaternary ammonium in the
MM-Kit composite affects the crystallinity of the composite as seen in the
diffractogram changes.

Figure IV.2 XRD diffractograms (a) MM, (b) MM-Kit, (c) MM-Kit-GTMAC
(1:2), (d) MM-Kit-GTMAC (1:4), and (e) MM-Kit- GTMAC
(1:6)

From the MM SEM image (Fig. IV.3.a) it can be seen that the MM
particles have a rough surface, while the MM-Kit SEM image (Fig. IV.3.b) shows
that the surface of the MM-Kit composite produces a smoother layer which
indicates the presence of chitosan in the composite. The addition of GTMAC also
made the surface morphology color lighter (Figures IV.3.c, IV.3.d, and IV.3.e).

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Figure IV.3 SEM images of (a) MM, (b) MM-Kit, (c) MM-Kit-GTMAC (1:2), (d)
MM-Kit-GTMAC (1:4), and (e) MM-Kit- GTMAC (1:6)

Based on the VSM results in Figure IV.4, the three curves have a narrow
curve area, which indicates that the energy required for each sample is small.
There was a decrease in the value of Ms as the coating material increased. This is
because the thicker the coating, the more obstructed the MM is when it is
approached by an external magnetic field.

Figure IV.4 VSM MM, MM-Kit, and MM-Kit-GTMAC (1:6) hysteresis curves

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IV.2 Cr(VI) Ion Adsorption Study by MM-Kit-GTMAC
IV.2.1 Effect of pH of Cr(VI) adsorption system by adsorbent
Figure IV.5 shows a shift in the optimum pH of MM-Kit-GTMAC when
compared to MM-Kit, this is because the pH pzc of MM-Kit-GTMAC is higher than
that of MM-Kit indicating that the surface charge of the adsorbent is still positive
as the pH increases .

Figure IIV.5 Effect of pH on the adsorption process of Cr(VI) anions

IV.2.2 Adsorption kinetics
The effect of contact time on adsorption of Cr(VI) anions by MM-Kit and
MM-Kit-GTMAC (1:6) is shown in Figure IV.6. Adsorption of Cr(VI) anions by
MM-Kit and MM-Kit-GTMAC (1:6) reached equilibrium at 120 minutes. The
adsorption process of Cr(VI) anions by MM-Kit and MM-Kit-GTMAC (1:6)
followed a pseudo second order kinetic model.

Figure IV.6 Effect of contact time on adsorption of Cr(VI) anions by (a) MM-Kit
and (b) MM-Kit-GTMAC (1:6)

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IV.2.3 Adsorption isotherm
Figure IV.7 shows that the adsorption capacity of MM-Kit-GTMAC (1:6)
is greater than that of MM-Kit, MM-Kit-GTMAC (1:2), or MM-Kit-GTMAC
(1:4). Cr(VI) anion adsorption isotherms by MM-Kit, MM-Kit-GTMAC (1:2),
MM-Kit-GTMAC (1:4), and MM-Kit-GTMAC (1:6) followed the Langmuir
isotherm model.

Figure IV.7 Effect of Cr(VI) anion adsorption concentration

CHAPTER V
CONCLUSIONS AND SUGGESTIONS
Conclusions
1. Coating of a magnetic material with GTMAC-modified chitosan which
has quaternary ammonium groups produces a positively charged MM-Kit-
GTMAC adsorbent as evidenced by a pHpzc value of 7.42 which can be
used to adsorb Cr(VI) anionic metal.
2. Adsorption of Cr(VI) anions by MM-Kit-GTMAC (1:6) took place
optimally at pH 4 with an adsorption capacity of 86.1%.
3. The adsorption process of Cr(VI) anions by MM-Kit-GTMAC (1:6)
follows a pseudo second order kinetics model and the Langmuir
adsorption isotherm with an adsorption rate constant (k) of 10.2×10–5 mol
mg–1 minutes–1 and adsorption capacity of 104.167 mg g–1 which is
superior when compared to previous studies.

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Suggestion
1. It is necessary to study the selectivity of adsorbents in multi-metal
systems.
2. It is necessary to study the desorption of Cr(VI) anions on MM-Kit-
GTMAC adsorbents.
3. It is necessary to vary the mass of chitosan with GTMAC at a higher
concentration in order to obtain optimum adsorption of the MM-Kit-
GTMAC composite.

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