vii
TABLE OF CONTENTS
CHAPTER
TITLE
PAGE
THESIS STATUS DECLARATION
SUPERVISOR’S DECLARATION
1
2
TITLE PAGE
i
DECLARATION
ii
DEDICATION
iii
ACKNOWLEDGEMENT
iv
ABSTRACT
v
ABSTRAK
vi
TABLE OF CONTENTS
vii
LIST OF TABLES
xii
LIST OF FIGURES
xiv
LIST OF SYMBOLS
xviii
LIST OF ABBREVIATIONS
xxi
LIST OF APPENDICIES
xxiv
INTRODUCTION
1
1.1 Background of Study
1
1.2 Research Description and Objectives
3
1.3 Organization of Thesis
6
LITERATURE REVIEW
7
2.1 Hazardous Elements and Their Impact on Health
7
2.1.1
Zinc (Zn)
11
viii
2.1.2
Cadmium (Cd)
12
2.1.3
Lead (Pb)
13
2.1.4
Selenium (Se)
14
2.2 Conventional and Advanced Methods for
15
Hazardous Elements Removal from the
Contaminated Water – A Brief Review
2.3 Features of Zeolites
2.3.1
General Aspects of Hydrothermal
19
22
Synthesis of Zeolites
2.3.2
Low Cost Synthetic Zeolites
2.4 Zeolites of the Gismondine Group (GIS)
2.4.1
Zeolites P with GIS Framework
2.5 Sorption Theory
3
23
24
26
27
2.5.1
Adsorption
27
2.5.2
Ion Exchange
30
2.5.3
Surface Complexation
34
EXPERIMENTAL
37
3.1 The Determination of Silica in Untreated Rice
37
Husk Ash
3.2 Syntheses of Zeolite P
3.2.1
Detailed Description of the Zeolite P
38
39
Synthesis Condition with Starting
Compositions of 4Na2O: Al2O3: 10 SiO2:
130H2O
3.3 Modification of Zeolites
40
3.3.1
Desilication
40
3.3.2
Ion exchange with Sodium or Calcium
41
Ions
3.3.3
Loading of Aluminium
3.4 Characterizations of Zeolite Samples
3.4.1
X-ray Diffraction (XRD)
41
42
42
ix
3.4.2
Fourier-Transform Infrared Spectroscopy
42
(FTIR)
3.4.3
Wavelength Dispersive X-ray
43
Fluorescence Spectroscopy (WDXRF)
3.4.4
Scanning Electron Microscopy (SEM)
43
3.4.5
Thermogravimetric-Differential Thermal
43
Analysis (TG-DTA)
3.4.6
Surface Analysis with Nitrogen
44
Adsorption
3.4.7
Solid-State Nuclear Magnetic Resonance
44
Spectroscopy (NMR)
3.5 Batch Sorption Experiments
3.5.1
44
Divalent Metals Removal
45
3.5.1.1
45
Kinetic of Divalent Metal Ions
Removal
3.5.1.2
Effect of pH towards Removal
46
of Divalent Metal Ions
3.5.1.3
Binary Ion Exchange of Divalent
46
Metal Ions with Indigenous Ions
in Zeolites
3.5.1.4
Multicomponent Ion Exchange
47
of Divalent Metal Ions with
Indigenous Ions In Zeolites
3.5.2
Selenium Oxyanions Removal
48
3.5.2.1
49
Kinetic of Selenium Oxyanions
Removal by Aluminium-loaded
Zeolite P
3.5.2.2
Construction of Adsorption
49
Isotherm
3.5.2.3
Effect of Ionic Strength towards
50
Removal of Selenium Oxyanions
by Aluminium-loaded Zeolite P
3.6 Flame Atomic Absorption Spectroscopy (FAAS)
50
x
4
RESULTS AND DISCUSSION: SORBENTS
53
DEVELOPMENT
4.1 Synthesis of Zeolite P
53
4.2 Modification of Zeolite Na-P2
60
4.2.1
Structural Change of Zeolite Na-P2 upon
61
Ion Exchange
4.2.2
Investigation of the Possibility of
69
Preparing Protonated Zeolite P through
Calcination
4.2.3
Loading of Aluminium onto Desilicated
72
zeolite Na-P2
5
RESULTS AND DISCUSSION: SORPTION
76
STUDIES ON THE SORBENTS
5.1 Cation Removal
5.1.1
76
Kinetic Studies of Ion Exchange on the
76
Zeolite
5.1.2
Characterization of the Ion Exchange
85
Products
5.1.3
Effect of Solution pH Value on the Metal
86
Uptake
5.1.4
Construction of Binary Ion Exchange
90
Isotherm
5.1.4.1
Exchanges with Pb2+ as the
90
Entering Cation
5.1.4.2
Exchanges with Zn2+ as the
91
Entering Cation
5.1.4.3
Exchanges with Cd2+ as the
92
Entering Cation
5.1.5
Kielland Plots
93
5.1.6
Multicomponent Ion Exchange
98
5.2 Anion Removal
101
xi
5.2.1
Selection of Optimum Aluminium-Loaded
101
Zeolite Na-P2 through Kinetic Studies
5.2.2
Modeling of Se (IV) and Se (VI)
106
Adsorption Isotherm
5.2.3
Effect of Ionic Strength of Solution on the
109
Selenium Uptake
6
5.2.3.1
Uptake of Selenite
109
5.2.3.2
Uptake of Selenate
111
CONCLUSION AND SUGGESTIONS
114
6.1 Conclusion
114
6.2 Contributions
116
6.3 Suggestions for Future Studies
116
REFERENCES
117
APPENDICES
134
xii
LIST OF TABLES
TABLE NO.
2.1
TITLE
Biological significance of classification of metals based on
PAGE
10
the last electron subshell in the atom to be occupied
3.1
Operating parameters of FAAS (Perkin-Elmer AAnalyst
52
400) in the measurement of the desired elements
4.1
Comparison of Si/Al ratio for original and desilicated
61
zeolite Na-P2
4.2
X-ray diffraction data of zeolite Na-P2 (Ori-P)
63
4.3
X-ray diffraction data of garronite (Homo-Ca)
64
4.4
Chemical compositions of zeolites determined by WDXRF
65
4.5
Unit cell compositions of zeolites (on the basis of 32
66
oxygen)
4.6
Assignment of 29Si NMR chemical shifts to the local Si
68
environment in the zeolites
4.7a
2θ values of desilicated zeolite Na-P2 and series of
74
aluminium-loaded zeolite Na-P2
4.7b
d-spacings of desilicated zeolite Na-P2 and series of
74
aluminium-loaded zeolite Na-P2
4.8
27
Al chemical shift for aluminium-loaded zeolite Na-P2 in
75
NMR spectra
5.1
Pseudo-second-order rate constant, calculated qe and
81
experimental qe values for the zeolites in the removal of
Pb2+, Zn2+ and Cd2+ ions
5.2
Intraparticle diffusion rate constant for the sorption of
2+
2+
2+
Pb , Zn and Cd onto zeolites
84
xiii
5.3
Maximum exchange capacity qmax, thermodynamic
98
equilibrium constants KA and standard free energy ∆G° of
investigated equilibria at 302 ± 2K
5.4
Pseudo second-order rate constant, calculated q e values
105
and initial sorption rate h for sample 10Al-P in the removal
of Se (IV) and Se (VI)
5.5
Intraparticle diffusion rate constant for the sorption of Se
105
(IV) and Se (VI) onto sample 10Al-P
5.6
The parameters for Langmuir and Freundlich isotherms for
108
Se (IV) and Se (VI) removal
5.7
Parameters for Langmuir and Freundlich isotherms for
111
selenite removal with the presence of different
concentration of electrolyte
5.8
Parameters for Langmuir and Freundlich isotherms for
selenate removal with the presence of different
concentration of electrolyte
112
xiv
LIST OF FIGURES
FIGURE NO.
2.1
TITLE
Classification of elements based on the last electron
PAGE
9
subshell in the atom to be occupied
2.2
Secondary Building Units (SBU) of Zeolites
21
2.3
Periodic building unit constructed from 4-fold connected
25
D8Rs
2.4
Connection mode and unit cell content in GIS seen along
a.
25
The bold part indicates a double crankshaft chain
which consists of 2-fold (1,2)-connected double 4-rings
2.5
Fused intersections viewed along a (left) and b (right)
26
2.6
Isotherms typically found for a binary ion exchange
32
2.7
The three mechanisms of cation adsorption on a siloxane
35
surface (e.g. montmorillonite)
4.1
X-ray diffractogram for field-burnt rice husk ash
53
4.2
X-ray diffractogram of final products when field-burnt
54
RHA was employed as silica source in synthesis
4.3
X-ray diffractogram of zeolite Na-P2
55
4.4
X-ray diffractogram of zeolite Na-P1
55
4.5
FTIR spectra of (a) zeolite Na-P1 and (b) zeolite Na-P2
56
4.6
SEM image of zeolite Na-P2
57
4.7
SEM image of zeolite Na-P1
57
4.8
X-ray diffractogram of three stable phases appeared in
58
product
4.9
X-ray diffractogram of products with different ratio of
reactant compositions
59
xv
4.10
X-ray diffractogram of zeolite Na-P2 after desilication at
60
60 °C
4.11
SEM image of zeolite Na-P2 after desilicated at 60 °C
61
4.12
X-ray diffractogram of desilicated- calcium ion
62
exchanged zeolite (garronite)
4.13a
29
Si NMR spectra of zeolite Na-P2 and garronite
67
4.13b
27
Al NMR spectra of zeolite Na-P2 and garronite
67
4.14
TG-DTA thermogram of sample Ori-P
69
4.15
TG-DTA thermogram of desilicated zeolite P2
70
4.16
TG-DTA thermogram of ammonium-exchanged
70
desilicated-zeolite P2
4.17
X-ray diffractogram for ammonium-exchanged
71
desilicated zeolite P2 and its H-form product at different
temperature
4.18
FTIR spectra for ammonium-exchanged desilicated
72
zeolite P2 and its H-form product at different
temperature
4.19
Comparison of the X-ray diffractogram between
73
desilicated zeolite Na-P2 and aluminium-loaded zeolite
Na-P2
4.20
27
Al NMR spectra of (a) desilicated zeolite Na-P2 and
75
(b) aluminium-loaded zeolite Na-P2
5.1
Plot of sorbed amount versus time for Pb2+ ions by the
77
zeolites
5.2
Plot of sorbed amount versus time for Zn2+ ions by the
77
zeolites
5.3
Plot of sorbed amount versus time for Cd2+ ions by the
78
zeolites
5.4
Pseudo-second-order sorption kinetics of Pb2+, Zn2+ and
80
Cd2+ ions onto zeolites
5.5
Morris-Weber kinetic plots for the uptake of Pb2+ions
onto zeolites
82
xvi
5.6
Morris-Weber kinetic plots for the uptake of Zn2+ions
83
onto zeolites
5.7
Morris-Weber kinetic plots for the uptake of Cd2+ions
84
onto zeolites
5.8
X-ray diffractogram of sample Ori-P after exchanged
85
with the targeted metal ions
5.9
Concentration of metal ions in the working solutions with
87
various pH value without the presence of zeolite
5.10
The effect of initial pH on Pb2+ ions removal by the
88
zeolites
5.11
The effect of initial pH on Zn2+ ions removal by the
89
zeolites
5.12
The effect of initial pH on Cd2+ ions removal by the
89
zeolites
5.13
Binary ion exchange in zeolites for Pb2+ ions at 302 K ±
91
2K
5.14
Binary ion exchange in zeolites for Zn2+ ions at 302 K ±
92
2K
5.15
Binary ion exchange in zeolites for Cd2+ ions at 302 K ±
93
2K
5.16
Kielland plots in zeolites for Pb2+ ions at 302 K ± 2K
95
5.17
Kielland plots in zeolites for Zn2+ ions at 302 K ± 2K
95
5.18
Kielland plots in zeolites for Cd2+ ions at 302 K ± 2K
96
5.19
Plot of sorbed amount of metal ions onto sample Ori-P
99
versus initial concentration in the multi-metal solution
5.20
Plot of sorbed amount of metal ions onto sample Homo-
100
Na versus initial concentration in the multi-metal solution
5.21
Plot of sorbed amount of metal ions onto sample Homo-
100
Ca versus initial concentration in the multi-metal solution
5.22
Plot of sorbed amount versus time for Se (IV) by the
103
series of aluminium-loaded zeolites
5.23
Plot of sorbed amount versus time for Se (VI) by the
series of aluminium-loaded zeolites
103
xvii
5.24
Pseudo-second order sorption kinetics of Se (IV) and Se
104
(VI) onto sample 10Al-P
5.25
Morris-Weber kinetic plots for the sorption of Se (IV)
105
and Se (VI) onto sample 10Al-P
5.26
Plot of sorbed amount of Se (IV) and Se (VI) onto sample
106
10 Al-P versus equilibrium concentration, Ce
5.27
Linearized Langmuir isotherms for Se (IV) and Se (VI)
107
removal by sample 10 Al-P
5.28
Linearized Freundlich isotherms for Se (IV) and Se (VI)
108
removal by sample 10 Al-P
5.29
Plot of sorbed amount of Se (IV) onto sample 10Al-P
109
versus equilibrium concentration, Ce with the presence of
different concentration of electrolyte
5.30
Linearized Langmuir isotherms for Se (IV) removal by
110
sample 10Al-P with the presence of different
concentration of electrolyte
5.31
Linearized Freundlich isotherms for Se (IV) removal by
110
sample 10Al-P with the presence of different
concentration of electrolyte
5.32
Plot of sorbed amount of Se (VI) onto sample 10Al-P
112
versus equilibrium concentration, Ce with the presence of
different concentration of electrolyte
5.33
Linearized Langmuir isotherms for Se (VI) removal by
113
sample 10Al-P with the presence of different
concentration of electrolyte
5.34
Linearized Freundlich isotherms for Se (VI) removal by
sample 10Al-P with the presence of different
concentration of electrolyte
113
xviii
LIST OF SYMBOLS
°C
-
Celsius degree
K
-
Kelvin degree
C0
-
Initial concentration
Ce
-
Equilibrium concentration
Ct
-
Concentration, after a prescribed duration
cm
-
Centimeter
g
-
Gram
kg
-
Kilogram
L
-
Liter
m
-
Meter
µm
-
Micrometer
nm
-
Nanometer
M
-
Molar
mA
-
Miliampere
λ
-
Wavelength
meq
-
Miliequivalent
mg
-
Miligram
µg
-
Microgram
h
-
Hour
min
-
Minute
s
-
Second
µs
-
Microsecond
mL
-
Mililiter
mm
-
Milimeter
mmol
-
Milimol
N
-
Normal
xix
qt
-
Sorbate uptake after a prescribed duration
qe
-
Sorbate uptake at equilibrium
qmax
-
Maximum uptake capacity
KA
-
Thermodynamic equilibrium constant
t
-
Time
V
-
Volume of solution
Å
-
Angstrom
2θ
-
2-Theta value in X-ray diffraction
%T
-
Percent transmission
KHz
-
Kilohertz
MHz
-
Megahertz
k1
-
Equilibrium rate constant of pseudo-first-order sorption
k2
-
Equilibrium rate constant of pseudo-second-order sorption
r2
-
Correlation coefficient
kid
-
Rate constant of intraparticle diffusion
∆Hhydr
-
Enthalpy of hydration
C
-
Concentration or activity of free metal in solution according to
Langmuir and Freundlich model
S
-
Quantity of the metal ions sorbed according to Langmuir and
Freundlich model
M
-
Maximum sorption capacity of the sorbent according to
Langmuir model
b
-
Coefficient related to bonding energy according to Langmuir
model
KF
-
Freundlich empirical constant which related to adsorption
capacity
n
-
Freundlich empirical constant which related to intensity of
adsorbent
zi
-
Valency of ion i
M
-
Molar concentration
W
-
Zeolite mass
γ
-
Solution-phase activity coefficient
I
-
Ionic strength of solution
xx
ai
-
Ion size parameter
A and
-
Constants in the Debye-Hückel term
ρo
-
Density of water
ε
-
Dielectric constant of water
T
-
Temperature
∆G˚
-
Gibbs standard free energy
∆H˚
-
Standard enthalpy
∆S˚
-
Standard entropy
B
xxi
LIST OF ABBREVIATIONS
FAO
-
Food and Agriculture Organization of the United
Nations
XRD
-
X-ray diffraction
FTIR
-
Fourier-transform infrared spectroscopy
MAS/NMR
-
Solid- state nuclear magnetic resonance
spectroscopy under magic angle spinning
WDXRF
-
Wavelength dispersive x-ray fluorescence
spectroscopy
FAAS
-
Flame atomic absorption spectroscopy
SEM
-
Scanning electron microscopy
TG-DTA
Thermogravimetric-differential thermal analysis
EDAX
Energy dispersive x-ray microanalysis
Pb
-
Lead
Cd
-
Cadmium
Zn
-
Zinc
Se
-
Selenium
GIS
-
Gismondine
IUPAC
-
International Union of Pure and Applied Chemistry
DNA
-
Deoxyribonucleic acid
RNA
-
Ribonucleic acid
FIAM
-
Free ion activity model
HDL
-
High density lipoprotein
LDL
-
Low density lipoprotein
HgbA1C
-
Glycated hemoglobin
SLI
-
Staring-lighting-ignition
xxii
CNS
-
Central nervous system
PKC
-
Protein kinase C
AC
-
Alternate current
DC
-
Direct current
ELM
-
Emulsion liquid membrane
EC
-
Electrocoagulation
ETS-10
-
Engelhard titanosilicate-10
SBU
-
Secondary building units
ANA
-
Analcime
TLM
-
Triple layer model
IIS
-
Ibnu Sina Institute for Fundamental Science Studies
LOI
-
Loss of ignition
H2SO4
-
Sulfuric acid
HF
-
Hydrofluoric acid
NaOH
-
Sodium hydroxide
NaAlO2
-
Sodium aluminate
DDW
-
Distilled-deionized water
NaNO3
-
Sodium nitrate
KCl
-
Potassium chloride
Ca(NO3)2
Calcium nitrate
NH4NO3
Ammonium nitrate
rpm
Revolution per time
KBr
Potassium bromide
CRM
Certified standard material
PP
Polypropylene
C2H2
Acetylene
HCL
Hollow cathode lamp
EDL
Electrodeless-discharged lamp
QCS
Quality control sample
RHA
Rice husk ash
PDF
Powder diffraction file
Ori-P
As-synthesized zeolite Na-P2
Homo-Na
Nearly-homoionic zeolite Na-P2
xxiii
Homo-Ca
Calcium exchanged zeolite Na-P2 (corresponded to
garronite)
CEC
Cation exchange capacity
H2SeO3
Selenious acid
10Al-P
Desilicated zeolite Na-P2 loaded with 10 mmol/L
aluminium sulfate
NaCl
Sodium chloride
n.v
Negative value
xxiv
LIST OF APPENDICES
APPENDIX
A
TITLE
National Drinking Water Quality
PAGE
134
Standards, 2000 of Malaysia for Some
Inorganic Species and Frequency of
Monitoring
B-1
EDAX Spectrum for Zeolite Na-P1
136
B-2
EDAX Spectrum for Zeolite Na-P2
137
B-3
EDAX Spectrum for Desilicated Zeolite
138
Na-P2
C
X-ray Diffractogram of Well-Mixed
139
Zeolite Na-P2
D-1
Surface Analysis of Zeolite Na-P2
140
Using Nitrogen Adsorption
D-2
E-1
Calculation of Si/Al Ratio through 29Si
NMR
Ion exchange Kinetics Data of Pb2+,
141
143
Zn2+ and Cd2+
E-2
The Effect of Initial pH on Metal Ions
148
Removal
E-3
Binary Ion Exchange Isotherm Data for
152
2+
Pb Uptake by Zeolites
E-4
Binary Ion Exchange Isotherm Data for
Zn2+ Uptake by Zeolites
154
xxv
E-5
Binary Ion Exchange Isotherm Data for
156
Cd2+ Uptake by Zeolites
E-6
Multicomponent Ion Exchange Isotherm
158
Data
F-1
Sorption Kinetics Data of Se (IV) and
160
Se (VI) by the Series of AluminiumLoaded Zeolites
F-2
Sorption Isotherm Data of Se (IV) and
164
Se (VI) by 10 Al-P
F-3
Sorption Isotherm Data of Se (IV) and
Se (VI) in NaCl Solution of Different
Ionic Strength
166