Adsorptive Removal of Iron (II), Aluminium (III) and Chromium (Vi) From Aqueous Solution by Charred and Phosphorylated Sugarcane Bagasse

ADSORPTIVE REMOVAL OF IRON (II), ALUMINIUM (III) AND CHROMIUM (VI)
FROM AQUEOUS SOLUTION BY CHARRED AND PHOSPHORYLATED

SUGARCANE BAGASSE
A DISSERTATION
SUBMITTED FOR THE
PARTIAL FULFILMENT OF THE REQUIREMENTS FOR
THE MASTER OF SCIENCE DEGREE IN CHEMISTRY
BY
Salik Ram Dahal

Symbol No: 13162/ 2012
Registration No: 5-248-2595-2005
CENTRAL DEPARTMENT OF CHEMISTRY

INSTITUTE OF SCIENCE AND TECHNOLOGY
TRIBHUVAN UNIVERSITY
KRITIPUR, KATHMANDU
NEPAL
SEPETEMBER, 2013
i
ADSORPTIVE REMOVAL OF IRON (II), ALUMINIUM (III) AND CHROMIUM (VI)
FROM AQUEOUS SOLUTION BY CHARRED AND PHOSPHORYLATED
SUGARCANE BAGASSE
A DISSERTATION
SUBMITTED FOR THE
PARTIAL FULFILMENT OF THE REQUIREMENTS FOR
THE MASTER OF SCIENCE DEGREE IN CHEMISTRY
BY
Salik Ram Dahal

Symbol No: 13162/ 2012
Registration No: 5-248-2595-2005
CENTRAL DEPARTMENT OF CHEMISTRY

INSTITUTE OF SCIENCE AND TECHNOLOGY
TRIBHUVAN UNIVERSITY
KRITIPUR, KATHMANDU
NEPAL
SEPETEMBER, 2013
ii
LETTER OF ACCEPTANCE
This dissertation work entitled “ADSORPTIVE REMOVAL OF IRON (II), ALUMINIUM

(III) AND CHROMIUM (VI) FROM AQUEOUS SOLUTION BY CHARRED AND
PHOSPHORYLATED SUGARCANE BAGASSE” submitted by Mr. Salik Ram Dahal
(Roll No/ Symbol No: 13162/2012; T.U. Regd. No. Registration No: 5-248-2595-2005) under
the supervision of Associate Prof. Dr. Deba Bahadur Khadka, Central Department of
Chemistry, Tribhuvan University, Nepal, is hereby submitted for the partial fulfilment of the
Master (M. Sc.) Degree in Chemistry. This dissertation has not been submitted in any other
university or institution previously for the award of a degree.
_ _______
Supervisor
Associate Prof. Dr. Deba Bahadur Khadka
Central Department of Chemistry
Tribhuvan University
_________ _ ___ ____ _

Internal Examiner External Examiner
Tribhuvan University, Kritipur
____ _
Professor Dr. Kedar Nath Ghimire
Head of the Department
Tribhuvan University, Kritipur,
Kathmandu, Nepal
Date: September, 2013
iii
RECOMMENDATION LETTER
This is certify that the dissertation work entitled “ADSORPTIVE REMOVAL OF IRON
(II), ALUMINIUM (III) AND CHROMIUM (VI) FROM AQUEOUS SOLUTION BY
CHARRED AND PHOSPHORYLATED SUGARCANE BAGASSE” has been carried out
by Mr. Salik Ram Dahal as a partial fulfilment for the requirement of M.Sc. Degree in
Chemistry under my supervision. To the best of my knowledge, this work has not been
submitted to any other degree in this institution.
_____________ _ _______
Supervisor
Associate Prof. Dr. Deba Bahadur Khadka
Tribhuvan University, Kritipur
Kathmandu, Nepal
iv
DECLARATION
I, “Salik Ram Dahal”, hereby declare that the work presented herein is genuine work done
originally by me and has not been published or submitted elsewhere for the requirement of a
degree program. Any literature, data or works done by other are cited in this dissertation and
has been given due acknowledgement and listed in the reference section.
Salik Ram Dahal

v
ACKNOWLEDGEMENT
It is a matter of great pleasure to express my sincere gratitude to my research supervisor

Associate Prof. Dr. Deba Bahadur Khadka, Central Department of Chemistry,
Tribhuvan University for his valuable guidance, support, constant encouragement and
providing a great knowledge throughout this entire research work. His encouragements,
assistance at all times have been of immense value.
I would like to express my sincere gratitude Prof. Dr. Kedar Nath Ghimire, Head of
Department for providing this opportunity and kind co-operation during the entire work.
I would like to express my sincere gratitude Prof. Dr. Megh Raj Pokhrel, Central
Department of Chemistry, Tribhuvan University for his valuable guidance, support
constant encouragement and providing a great knowledge throughout this entire research
work. His encouragements and assistance at all times have been of immense valued.
I would like to express my sincere thanks to all the supporting staffs of the Central
Department of Chemistry & Central Library. I express my sincere thanks for my friends
for helping me in preparing this Dissertation. I would like to express my gratitude to my
family for their co-operation and support throughout the entire period of the study.
I would like to express my sincere gratitude to University Grand Commission, Nepal for
the support of this dissertation work under the scheme of Masters Thesis Support Grants
and UGC-Institutional Grants.
Salik Ram Dahal
September, 2013
6
ABBREVIATIONS
AAS = Atomic Absorption Spectroscopy

%A = Percentage Adsorption
b = Langmuir Constant in L/mg
CSB = Charred Sugarcane Bagasse
Conc. = Concentration
Cr (VI) = Hexavalent Chromium.
Ce = Equilibrium concentration of metal ion in mg/L
Ci = Initial concentration of Metal ion in mg/L
Ct = Concentration of Metal ion at time‘t’ in mg/L
DMF = Dimethyl Formamide
DPCI = 1, 5-Diphenylcarbazide.
ECR = Eriochrome Cyanine R
 = Molar Extinction Coefficient
FTIR = Fourier Transforms Infra-red Spectroscopy
GAC = Granular Activated Carbon
g = Gram
ICP = Inductively Coupled Plasma
KL = Langmuir Equilibrium Parameter
K1 = Pseudo first order rate constant in min-1
K2 = Pseudo second order rate constant in g/mg.min
1
K2 = Second order rate constant in g/mg.min
K = Adsorption capacity in L/g
L = Litre
mg = Milligram
mg/L = Milligram per litre
mL = Millilitre.
mg/g = Milligram per gram
mmol/kg = Millimole per kilogram
7
mol/kg = Mole per kilogram
n = Adsorption intensity
PCSB = Phosphorylated Charred Sugarcane Bagasse
pHe = Equilibrium pH.
ppm = Parts Per Million
pHi = Initial pH
pHe = Equilibrium pH
ppb = Parts Per Billion
qm = Maximum Adsorption Capacity in mg/g
qe = Amount Adsorbed at Equilibrium in mg/g.
qt = Amount Adsorbed at Time ‘t’ in mg/g.
RSB = Raw Sugarcane Bagasse
SB = Sugarcane Bagasse
µg/L = Microgram Per Litre
V0 = Initial adsorption rate in mg/g.min.
V = Volume of metal solution in litre
W = Weight of adsorbent used in gram
% = Percentage
8
Abstract
Adsorptive removal of heavy metal ions, mainly Fe(II), Cr(VI) and Al(III) from aqueous
solution onto chemically modified charred sugarcane bagasse (CSB) and phosphorylated
charred sugarcane bagasse (PCSB) has been investigated. Bioadsorbent was chemically
modified to introduce surface functional group. The effect of pH, contact time and effect
of metal ion concentration were studied by batch equilibration method under different
experimental conditions. The concentration of metal ion in the test solution before and
after the adsorption was determined spectrophotometerically. The optimum pH for the
adsorption of Fe(II) was found to be 2.5 whereas 1 for Cr(VI) and 3 for Al(III). And the
maximum adsorption capacity (qmax) for Fe (II) is 117.08 mg/g for CSB and 175.6 mg/g
for PCSB and for Al(III) 133.33 mg/g for CSB and 209.52 mg/g for PCSB likewise for
Cr(VI) qmax is 140 mg/g for CSB. But for Cr(VI) only charred sugarcane bagasse have
optimum capacity for sorption. As phosphoric acid modified bagasse is not effective.
Adsorption kinetic data were tested using pseudo-first order, pseudo-second order, and
second order kinetic models. The adsorption data followed pseudo-second order kinetic
model for all three metals ions which agrees that chemisorptions as the limiting
mechanism. Adsorption isotherm was better represented by Langmuir model. Hence
Sugarcane Bagasse is an abundant waste material and available almost free of cost, low
cost bio-wastes can be used for the removal of Fe(II) , Cr(VI) and Al(III) from water and
wastewater.
Key Words: Modified Charred Sugarcane Bagasse, Phosphorylated Charred Sugarcane

Bagasse, Langmuir Model, and Adsorption Isotherm.
9
CONTENTS
Letter of Acceptance
Recommendation Letter
Declaration
Acknowledgement
Abbreviations
Abstract
1 Introduction……………………………………………………………………1-14
1.1 General Introduction
1.2 Low Cost Adsorbents and Importance of Biosorption
1.3 Adsorptive Study
1.4 Structure of Lignin and Cellulose
1.5 Adsorption Isotherms
1.5.1 Langmuir Adsorption Isotherm
1.5.2 Freundlich Adsorption Isotherm
1.6 Adsorption Kinetics
1.6.1 The Pseudo First Order Kinetics Model
1.6.2 The Pseudo Second Order Kinetics Model
1.6.3 The Second Order Kinetics Model
2. Objectives of the Study…………………………………………………………15
2.1 General objectives
2.2 Specifics objectives
3. Literature Survey ………………………………………................................16-21
4. Scope and Limitations of the Study…………………………………………22
10
5. Material and Methods ………………………………………………………23-26
5.1 Instrument Used
5.1.1 Chemiline Digital pH Meter. CL-110, Electrode HI-1230
5.1.2 Spectrophotometer, WPA Linton(S-104), Cambridge, UK
5.1.3 V.D.R.L SHAKER, Accuma X India
5.2 Preparation of Reagents
5.2.1 1000 ppm Stock Iron Solution
5.2.2 Potassium Dichromate (K2Cr2O7) Stock Solution (1000 ppm).
5.2.3 Aluminium Stock Solution [KAl(SO4)2.12H20]
5.2.4 5M Sulphuric Acid Solution (approx)
5.2.5 5M Sodium Hydroxide Solution (approx)
5.2.6 5M Nitric Acid Solution (approx)
5.2.7 Preparation of 0.25% 1,5 Diphenycarbazide (DPCI) Solution
5.2.8 Buffer Solution pH 4
5.2.9 Buffer Solution of pH 7
5.2.10 Buffer Solution of pH 9.2
5.2.11 10% Hydroxyl Amine Hydrochloride Solution
5.2.12 1, 10-Phenanthroline Hydrochloride Solution
5.2.13 0.2% Eriochrome Cynine R[C23H15Na3O9S] Solution
5.2.14 Ammonium Acetate Buffer Solution
5.2.15 0.1M Nitric Acid
5.2.16 0.02N Sodium Carbonate Solution
5.2.17 0.02 N NaHCO3 Solution
5.2.18 0.02 N NaOH Solution
5.2.19 0.02 N HCl Solution
11
5.2.20 0.04 N Oxalic Acid Solution
5.2.21 0.1N HNO3 Solution (approx)
5.2.22 2M NaOH Solution (approx)
5.3 Preparation of Adsorbents from Sugarcane Bagasse………………….....26-32
5.3.1 Preparation of Raw Sugarcane Bagasse.
5.3.2 Acid Modifications
5.3.3 Phosphorylation of Charred Adsorbents
5.3.4 Effects of Chemical Modification
5.3.5 Plausible Mechanism of Adsorbents
6. Experimental …………………………………………………………………33-42
Determination of λmax and Construction of Calibration Curve
6.1 Construction of Calibration Curve for Iron
6.2 Construction of Calibration Curve for Aluminium
6.3 Construction of Calibration Curve for Chromium
6.4 Batch Adsorption Studies
6.4.1 Batch pH Studies
6.4.2 Batch Isotherm Studies
6.4.3 Batch Equilibrium Time Studies
6.4.4 Batch kinetics Studies
7. Results and Discussion ………………………………………………………43-79
7.1 Batch pH Studies of Fe(II)
7.2 Batch Equilibrium Time Studies of Fe(II)
7.3 Batch Kinetics Study of Fe(II)
7.4 Batch Isotherm Studies of Fe(II)
7.5 Effect of pH Studies of Cr(VI)
12
7.6 Batch Equilibrium Time Studies of Cr(VI)
7.7 Batch Kinetic Study of Cr(VI)
7.8 Batch Isotherm Studies of Cr(VI)
7.9 Effect of pH of Al(III)
7.10 Batch Equilibrium Time Studies of Al(III)
7.11 Batch Kinetic Study of Al(III)
7.12 The Effect of Initial Concentration of Al(III)
7.13 Batch Isotherm Study of Al(III)
8. Conclusion………………………………………………………………………80
REFERENCES…………………………………………………………………81-84
13
List of Tables
Table 6.1: Spectrophotometric Determination of max for Fe(II) .
Table 6.2: Calibration Curve for Fe(II) .
Table 6.3: Spectrophotometric Determination of λmax for Al(III).
Table 6.4: Calibration Curve for Al(III).
Table 6.5: Spectrophotometric Determination of λmax for Cr(VI).
Table 6.6: Construction of Calibration Curve for Cr(VI).
Table 7.1: Effect of pH on Adsorption of Fe(II) onto CSB.
Table 7.2: Effect of pH on Adsorption of Fe(II) onto PCSB.
Table 7.3: Effect of Contact Time for the Adsorption of Fe(II) onto SCB.
Table 7.4: Effect of Contact Time for the Adsorption of Fe (II) onto PSCB.
Table 7.5: Kinetic Study of Adsorption of Fe(II) onto SCB.
Table 7.6: Kinetic Study of Adsorption of Fe(II) onto PSCB.
Table 7.7: Different Parameters Calculated from the Kinetic Plots Adsorbents for Fe(II).
Table 2.8: Effect of Concentration on the Adsorption of Fe(II) onto CSB.
Table 2.9: Effect of Concentration on the Adsorption of Fe(II) onto PCSB.
Table 7.10: Langmuir and Freundlich Parameters and Correlation Coefficient (R2) with
Experimental qmax for the Adsorption of Fe(II) onto CSB and PCSB.
Table 7.11: Effect of pH on the Adsorption of Cr(VI) on CSB.
Table 7.12: Effect Contact Time for the Adsorption of Cr(VI) onto CSB.
Table 7.13: Different Parameters Calculated from the Kinetic Plots Adsorbents for
Cr(VI).
Table 7.14: Effect of Concentration on the Adsorption of Cr(VI) onto CSB.
Experimental qmax for the Adsorption of Cr(VI) onto CSB.
14
Table 7.16: Effect of pH on the Adsorption of Al(III) onto CSB.
Table 7.17: Effect of pH on the Adsorption of Al(III) PCSB.
Table 7.18: Effect of Contact Time of Al(III) CSB.
Table 7.19: Kinetic Study of Al(III) onto PCSB.
Table 7.20: Different Parameters Calculated from the Kinetic Plots Adsorbents for Al(III).
Table 7.21: Effect of Initial Concentration: Batch Isotherm Study of Al(III) on CSB.
Table 7.22: Effect of Initial Concentration: Batch Isotherm Study of Al(III) on PCSB.
Experimental qmax for the Adsorption of Al(III) onto CSB and PCSB.
Table 7.24: Accuracy and Precision of the Spectrophotometric Method for the
Determination of Cr(VI) DPCI.
Determination of Fe(II) by 1, 10-Phenonthroline.
Determination of Al(III) by Eriochrome Cyanine R.
Table 7.27: Comparison of Maximum Adsorption Capacity qmax between Various
Bioadsorbent.
15
List of Figures
Figure 1.1: Structure of Lignin.
Figure 1.2: Lignin Polymer Structure.
Figure 1.3: Structure of Cellulose.
Figure 5.1: Acid Modification Process.
Figure 5.2: Phosphoric Acid Modification (Phosphorylation) Process.
Figure 5.3: Modification Mechanism of Adsorbent.
Figure 5.4: Modification by Introducing Phenolic –OH Group.
Figure 5.5: Modification Mechanism of Adsorbent by Phosphoric Acid.
Figure 5.6: Complexation of Chromium (VI) with Polyphenolic/Polyhydroxyl
Functional Moiety of Modified Sugarcane Waste.
Figure 5.7: Complexation of Iron with Polyphenolic/Polyhydroxyl Functional Moiety of
Modified Sugarcane Waste.
Figure 6.1: Series Dilution.
Figure 6.2: Spectrophotometric Determinati or of Fe(II).
Figure 6.3: Calibration Curve for Fe (II).
Figure 6.4: Determination of  max for Spectrophotometric Determination of Al(III).
Figure 6.5: Calibration Curve for Al(III).
Figure 6.6: Determination of  max for Spectrophotometric Determination of Cr (VI).
Figure 6.7: Calibration Curve for Cr(VI).
Figure 7.1: Effect of pH on the Adsorption of Fe(II) onto CSB and PCSB.
16
Figure 7.2: Effect of Contact Time on Adsorption of Fe(II) onto SB.
Figure 7.3: Pseudo First Order Kinetic Plot for the Adsorption of Fe(II) onto SB.
Figure 7.4: Pseudo Second Order Kinetic Plot for the Adsorption of Fe(II) onto SB.
Figure 7.5: Second Order Kinetic Plot for the Adsorption of Fe(II) onto SB.
Figure 7.6: Adsorption Isotherm of Fe(II) on CSB.
Figure 7.7: Adsorption Isotherm of Fe(II) on PCSB.
Figure 7.8: Langmuir Adsorption Isotherm for the Adsorption of Fe(II) on CSB.
Figure 7.9: Langmuir Adsorption Isotherm for the Adsorption of Fe(II) on PCSB.
Figure 7.10: Freundlich Adsorption Isotherm for the Adsorption of Fe(II) onto CSB.
Figure 7.11: Freundlich Adsorption Isotherm for the Adsorption of Fe(II) onto PCSB.
Figure 7.12: Effect of pH on Removal of Cr(VI) by CSB.
Figure 7.13: Effect of Contact Time on Adsorption of Cr(VI) onto CSB.
Figure 7.14: Pseudo First Order Kinetic Plot for the Adsorption of Cr(VI) onto CSB.
Figure 7.15: Pseudo Second Order Plot for the Adsorption of Cr(VI) onto CSB.
Figure 7.16: Second Order Kinetic Plot for the Adsorption of Cr(VI) onto CSB.
Figure 7.17: Adsorption Isotherm for Cr(VI) onto CSB.
Figure 7.18: Langmuir Adsorption Plot for Cr(VI) onto CSB.
Figure 7.19: Freundlich Adsorption Isotherm for Cr(VI) onto CSB.
Figure 7.20: Effect of pH on the Adsorption of Al(III) onto CSB and PCSB.
Figure 7.21: Effect of Adsorption on Contact Time of Al(III)) onto CSB.
Figure 7.22: Pseudo First Order Kinetic Plot Al(III) onto SB.
Figure 7.23: Pseudo Second Order kinetic for Al(III) onto SB.
Figure 7.24: Second Order Kinetic Plot for Al(III) onto SB.
Figure 7.25: Adsorption Isotherm of Al(III) on CSB.
Figure 7.26: Adsorption Isotherm of Al(III) on PCSB.
17
Figure 7.27: Langmuir Adsorption Isotherm for Al(III) onto CSB.
Figure 7.28: Langmuir Adsorption Isotherm for Al(III) onto PCSB.
Figure 7.29: Freundlich Adsorption Isotherm for Al(III) on CSB.
Figure 7.30: Freundlich Adsorption Isotherm for Al(III) on PCSB.
1. INTRODUCTION
1.1 General Introduction
All over the globe, human communities are striving to protect the environment. Since the
dawn of civilization, a large number of pollutants are posing major environmental and
health problem to the human beings. Amongst all, environmental contamination by toxic
metals is wide spread problem, with source of pollution mainly arising from industrial
activities. Theses heavy metals pollutants are contaminating the biosphere as well as
hydrosphere.
18
Heavy metals are a group of pollutants which occurs as a natural of the earth’s crust.
Serious consequences of biological hazards caused by metal toxicity cannot be ruled out.
A high degree of industrialization and urbanization has substantially enhanced the
degradation of aquatic environments through the discharge of industrial wastes water and
domestic wastes. The tremendous increase in the use of heavy metals over the past few
decades has inevitably resulted in an increased flux of metallic substances in the aquatic
environment. 1 Heavy metals are defined as the high atomic weight metals and metalloids
generally considered to be of sufficient distribution and abundance as to be in some way
environmentally or biologically significant as a toxic substance. A heavy metal is a
member of an ill-defined subset of elements that exhibit metallic properties which mainly
includes the transition metals, some metalloids, lanthanides and actinides. Many different
definitions have been proposed. Some based on density, some on atomic number or
atomic weight, and some on chemical properties or toxicity. 2
Wastes containing different heavy metals are produced and discharged into the
environment by various industries such as mining and smelting, surface finishing
industry, energy & fuel production, fertilizer & pesticide industry and application,
metallurgy, iron and steel electroplating, electrolysis, electro-osmosis, leatherworking,
photography, electric appliance manufacturing, metal surface treating, aerospace and
3
atomic energy installation etc.
The heavy metals like Lead (Pb), Cadmium (Cd), Nickel (Ni), Chromium (Cr), Arsenic
(As), Mercury (Hg), Aluminum (Al), Iron (Fe) in waste water are hazardous to
environment.4 Unlike the organic pollutants the majority of which are susceptible to
biological degradation, heavy metals do not degrade into harmless end products so easily.
Therefore the elimination of heavy metals from water and waste water is important to
protect the public health.5 The permissible limit of Cr (VI) for drinking water is 0.1 mg/L
and that for Al (III) is 0.05 mg/L and for Fe (II) is 0.3 mg/L. In natural water chromium
may exist in water in both hexavalent and trivalent state although the trivalent form rarely
occurs in potable water. The chromium toxicity is mainly induced from its hexavalent
form, Cr (VI), comparatively to chromate and dichromate ions. It is toxic to humans,
19
animals and even to plants. It can cause lung, kidney and liver cancers, as well as gastric
damages, and are corrosive to tissue.6
Chromium is priority metals pollutant introduces into water bodies from many industrial
processes such as leather tanning, metals processing, paint manufacturing, steel
fabrication and agricultural run-off. Chromium is also used in explosive ceramic and
photography. Chromium exists in both trivalent and hexavalent states in soils and
aqueous systems. Hexavalent chromium, which is primarily present in the form of
chromate (CrO4) and dichromate (Cr2O7) ions possess significantly higher levels of
toxicity than the other valence states i.e. the trivalent form of chromium namely Cr(III)
,on the other hand is about 1000 times less toxic than Cr(VI). Furthermore, it has limited
hydroxide solubility making it relatively immobile and less available for biological
uptake. As a result Cr (VI) toxicity could be reduced them become less available when
reduced to Cr (III).7 The toxicity of Cr (VI) is well documented and it is considered a
hazard to health of man and animals. The various compounds of chromium are found to
be both corrosive to flesh and carcinogenic. The present of Cr (VI) in the aquatic
environment at high concentration is lethal to marine species.8
Aluminium occurs in natural water which is not essential for plants and animals.
Concentration exceeding 1.5mg/L is toxic. The possibility of a link between elevated
aluminium levels in brain tissue and Alzheimer’s disease has been raised.6 Al is the most
abundant metal in the earth’s crust with a mean concentration in the earth’s upper crust is
8.1%. In most natural water the concentration of Al is low due to its limited solubility. Its
solubility increases at lower pH and by complexion with fluoride or organic substances.
Al has now known essential biological role for animals or plants. For many years it was
thought to be virtually nontoxic. Recent experiments have shown otherwise. It is now
well documented that dialysis fluids containing Al are the cause of a potentially lethal
condition called dialysis encephalopathy. The condition is caused by a slow degeneration
of brain tissue brought about by Al introduced into bloodstream via the dialysis unit. Al
ingested with food is normally taken up to small extend only is rapidly excreted as long
as the kidneys working properly. Plants and tree also suffer from high levels of Al in the
20
root zone. Aquatic invertebrate seem generally not to be as sensitive to Al as fish,
although some toxic effects have been shown.9
The higher levels of iron impart taste and odor, and are responsible for the effect as the
growth of iron bacteria. The decay of such organism has a consequence bad taste and
odor. The most popular bacteria are Crenothrix, Leptothrix, Sphaerotilus and Gallionella
that transform in their own metabolism the ferrous into the ferric one.10
Iron is one of the major constituents of the lithosphere and comprises approximately 5%
of it. It is routinely detected in municipal waste effluents, particularly in cities where iron
and steel are manufactured. Iron readily complexes with sulphates in the sediments of
many surface waters. The primary concern about the presence of iron in the drinking
water is its objectionable taste. The taste of iron in drinking water can easily be detected
even at low concentration of about 1.8 mg/L. There are many problems that result from
iron toxicity. These include anorexia, oliguria, diarrhoea, hypothermia, dysphasic shock,
metabolic acidosis and even death. In addition to these, the patient may experience
vascular congestion of the gastrointestinal tract, liver, kidney, heart, brain, spleen,
adrenals and thymus. With acute iron poisoning, much of the damage to the
gastrointestinal tract and liver may result from the high localized iron concentration and
free radical production leading to hepatotoxicity via. lipid peroxidation and destruction of
hepatic mitochondria. As a result of iron storage disease, the liver becomes cirrhotic.11
Several mishaps related to heavy metal concentrations in the aquatic environment have
increased the awareness about heavy metal toxicity. Among these, Mina Mata tragedy in
Japan (1953-60) due to metallic mercury escaping from the laboratories and industries,
mainly from chlorine manufacturing. It was acquired by aquatic life and passed along
through natural food chains to humans, largely by fish. Another disease “Itai-Itai” that
occurred among the farmers who drank water-containing cadmium supplied from the
Jentsu River in Japan.12 Chromium (VI) causes many adverse effects on humans, aquatic
life and soil. Some of the effects are summarized as follows; Humans: Nausea, Vomiting,
Epiesgestric pain, Severe Diarrhea, Hemorrhage, Dermatitis by skin contact, Nasal
Mucous Membrane, Ulcer Lung Cancer and Tissue Necrosis. Aquatic life: reduction in
21
fish production at high concentrations, chromium accumulates in fish tissues and reaches
to consumers. Gold fish and trout are killed at a concentration of 180 mg/l. Land: Soil
fertility is reduced if chromium-bearing effluents are discharged on land.13
1.2 Low Cost Adsorbents and Importance of Biosorption
Unlike organic wastes, heavy metals are non-biodegradable and they can be accumulated
in living tissues, causing various diseases and disorders; therefore they must be removed
before discharge. Research interest into the production of cheaper adsorbents to replace
costly wastewater treatment methods such as chemical precipitation, ion-exchange,
electro-ﬂotation, membrane separation, reverse osmosis, electro dialysis, solvent
extraction, etc.14 are attracting attention of scientists.
Adsorption is one the physicochemical treatment processes found to be eﬀective in

removing heavy metals from aqueous solutions, adsorbent can be considered as cheap or
low-cost if it is abundant in nature, requires little processing and is a by-product of waste
material from waste industry. Plant wastes are inexpensive as they have no or very low
economic value.15
Conventional techniques, such as chemical precipitation, solvent extraction, ion

exchange, electroplating, and activated carbon adsorption and membrane separation
process have been employed to remove heavy metals from waste water.16 These methods
have become inefficient and expensive especially when the heavy metal concentration is
less than 100 ppm.17
Biosorption is a process whereby certain types of inactive, dead biomass may bind and
concentrate heavy metals from aqueous solutions.18 The use of non-expensive waste
biomass, the low cost of biomass immobilization, competitive performance, heavy metal
selectivity, no sludge generation and the possibility of biomass regeneration are some of
the advantages of biosorption over other conventional techniques.19
Heavy metal pollution of wastewater is a common environmental hazard, since the toxics
metal ions dissolved can ultimately reach the top of the food chain and thus become a risk
22
factor for human health. The use of an adsorption process in the treatment of wastewater
containing toxic metal ions is an attractive and suitable technique. 20, 21
The adsorption efficiency of the agricultural wastes can be enhanced by various methods
such as thermal activation, steam activation, chemical modification, chemical activation
and so forth.22 Biosorption is a technique of adsorptive removal and recovery of the
heavy metal ions by using biological wastes as the adsorbent. It is more economical and
provides a greater metal removal capacity even at low metal ion concentration. The two
most important advantages of using biosorbents are: they are cheap and are available in
the form of waste.23
There are different biological substrates tested in biosorption with either modified or
unmodified form such as fly ash, almond hulls, peanut hulls, cotton seed hulls, maize
bran, saw dust, different algae, crab shells, rice husk, and sugarcane bagasse. These
biomaterials have been recognized as the potential alternative to conventional
technologies for the removal of heavy metals from the waste water. Thus, it is possible to
effectively recover valuable metals and remove toxic metals from the waste water by
using low cost biomass wastes. 24
Sugarcane baggase which is the agricultural waste material produced from sugarcane
refining industry, juice ships etc. It consists of cellulose (50%), Polyoses (27%) and
Lignin (23%). Due to presence of these biological polymers sugarcane baggase is rich in
hydroxyl and phenolic groups and these groups can be modified chemically to produce
adsorbent materials with new properties, are believe to be responsible for the heavy
metals uptake from aqueous solution by adsorption.25
In Nepal, most of biomaterials like rice husk, maize bran, apple waste, pomegranate
waste, orange peel, banana peel, sugarcane bagasse, wheat straw narkat stem are easily
available as the waste materials. Sugarcane is grown in the fields of Nepal in all seasons
around and its bagasse one of the waste. In the present research work, the bagasse of
sugarcane is used and chemically modified to increase the metal uptake capacity. These
were first treated with concentrated H2SO4 and then phosphorylated to introduce the more
23
functional group as phosphoric moiety has been developed which tremendously increases
the metal binding capacity.
1.3 Adsorptive Study
The phenomenon of concentration of any substance on the surface of the solid or liquid
as compared to that present in the bulk of the materials is called adsorption.26 The
material on the surface of which adsorption takes place is known as adsorbent and the
substance undergoing adsorption is called adsorbate. Adsorption occurs by the effects of
residual force operating at the surface of adsorbent due to unsatisfied valance or bond
deficiency.27
Adsorption study can be carried out by two methods:
I) Column method II) Batch method
I) Column method
In this method, adsorbent is filled in a glass column of fixed length and diameter. The
sample solution of adjusted pH and a particular concentration is percolated into the
column at a controlled flow rate. The metal concentration before and after adsorption is
detected by AAS or spectrophotometer.28, 29
II) Batch method
In batch method, a fixed mass of adsorbent is added to a stopper bottle containing a fixed
volume of sample solution at fixed pH. The pH of aqueous solution are adjusted by series
of 1M , 2M ,3M , 4M and 5M HCl solution and 1M , 2M , 3M , 4M and 5M NaOH
solutions by hit and trial method .The stopper bottle is shaken in a mechanical shaker for
24 hours to attain adsorption equilibrium. The metal concentrations before and after
adsorption is measure by AAS or spectrophotometer.22, 28 Heavy metal adsorption onto
adsorbent is affected by different parameters such as initial concentration of metal ions
(mg/L), contact time (in minutes), amount of adsorbent used (g/L), temperature (C) and
24
pH of the solution.29, 30 To understand the mechanism and effectiveness of adsorption,
any one of the above parameter is varied by keeping the other parameters constant.29
From the metal concentration measurement before and after adsorption, amount of metal
ion adsorption onto adsorbent is determined by using following relation as. 31
Ci  Ce
 qt =  V ............................................... (I)
W
Where, Ci and Ce are initial & equilibrium metal ion concentration in mg/L respectively.
qt is the amount of metal adsorbed at time ’t’ in mg/g.
V is the volume of metal solution in L.
W is the weight of adsorbent in gm.
Metal removal percentage is calculated by using a formula:
Ci  Ce
A (%) = 100 ......................................... (II)
Ci
This is the ratio of decrease in metal ion concentration before and after adsorption to the
initial metal ion concentration.
1.4 Structure of Lignin and Cellulose
Lignin is an amorphous multifunctional phenolic network containing hydroxyl, ether and

carbonyl groups.32
25
Figure 1.1: Structure of Lignin.
Figure 1.2: Lignin Polymer Structure.
Figure 1.3: Structure of Cellulose.
26
Cellulose is made up of chains of D-glucose units, each unit joined by a glycoside linkage
to C-4 of the next. X ray analysis and electron microscopy indicate that these long chain
lie by side by side in bundles, undoubtedly held together by hydrogen bonds between the
numerous neighbouring –OH groups. These bundles are twisted together to form rope
like structure which themselves are groups to from the fibre we can see. In wood, these
cellulose ropes are embedded in lignin to give a structure that has been likened to
reinforced concrete.33
1.5 Adsorption Isotherm
The equilibrium between an adsorbate immobilized on the active sites of an adsorbent

and the adsorbate remaining in aqueous phase is usually presented by adsorption
isotherm.34
The equation parameter and underlying thermodynamic assumption of these equilibrium

models often provides some insight into both the sorption mechanism and the surface
properties and affinities of the sorbent. In order to describe the adsorption characteristic
of low- cost sorbents used in water and waste water treatment, experimental equilibrium
data are most frequently modelled by the relationship developed by Freundlich and
Langmuir.34
1.5.1 Langmuir Adsorption Isotherm
The first quantitative model of adsorption was given by Langmuir in 1916. The Langmuir
isotherm model has been successfully applied for the adsorption of solute from a liquid
solution, which involves all the energetically equivalent adsorbent sites, homogenous
surface for adsorption with the formation of monolayer coverage and adsorption is
independent of occupation of neighbouring sites.25
Langmuir adsorption isotherm is given by the following equation.
Ce
 a  bCe ........................................ (III)
X
27
Where, Ce is the concentration of adsorbate, which is in dynamic equilibrium with the
adsorbents adsorbed on charcoal, x is the amount of adsorbate adsorbed per gram
charcoal, and 'a' and 'b' are Langmuir constant.
In order to establish the maximum adsorption capacity, the Langmuir adsorption isotherm
can be rearranged and the linear form of Langmuir equation is given by.35, 36
q max  bCe
qe  .................................... (IV)
1  bCe
This equation can be further simplified as,
Ce 1 C
  e ................. …….......... (V)
qe qmb qm
Where qe is milligram of metal accumulated per (unit mass) gram of the adsorbent at
equilibrium (mg/g), Ce is the equilibrium concentration of adsorbate (mg/L), qm the
maximum adsorption capacity and b is the Langmuir adsorption equilibrium constant
(L/mg). When Ce/qe is plotted against Ce, then a straight line with a slope equal to 1/qm
1
and intercept obtained from which qm value can be calculated. The value of so
qmb
obtain provide the information of quality of adsorbent. The adsorbent with the high value
of qm is preferred since its adsorption capacity is high.37
According to (Hall et al., 1996), the essential features of the Langmuir isotherm can be
expressed in terms of a dimensionless constant separation factor or equilibrium parameter
(KL) which is defined by the following relationship.38
1
KL = ....................................... (VI)
1  bCi
Where Ci is the initial concentration of the adsorbate (mg/L) and KL is the Langmuir
equilibrium constant which is related with the affinity of binding sites. The parameters
KL indicate the shape of isotherm and nature of the adsorption process. K L >1 for
28
unfavourable, KL= 1 favourable, KL= zero for irreversible.36, 38
The KL values lies
between 0 and 1 indicate the favourable adsorption.
1.5.2 Freundlich Adsorption Isotherm
The Freundlich isotherm model is the earliest known relationship describing the sorption
equation. The fairly satisfactorily empirical isotherm can be used for non-ideal sorption
that involves heterogeneous sorption. The Linear from of Freundlich model is represented
by the following equation.35
qe = KCe1/n......................................... (VII)
In logarithmic form (the linearized from of which can be written as):
Log qe = log k + 1/n log Ce................. (VIII)
Where, ‘K’ and ‘n’ are the Freundlich constant which are considered to be the relative
indicators of adsorption capacity and adsorption intensity. The value of 1/n varies
between 0-1 indicates the favourable adsorption of heavy metal.39
1.6 Adsorption Kinetics
Adsorption kinetics study is the study of rate and mechanism of the adsorption process.
There are numerous adsorption kinetics models that are used to describe the uptake of
adsorbate by different adsorbent. The pseudo-first order rate equation (Lagergren, 1898)
the pseudo second order rate equation (Ho et al., 2000) and second order rate equation
(Ho et al., 1996) has been used widely for the description of adsorption kinetic model.
The conformity between experimental data and the model predicted values was expressed
by the correlation coefficient. This helps in determine which reaction model is suitable
for adsorption of heavy metals onto adsorbent. Kinetic of heavy metals adsorption was
modelled by the first order Lagergren equation, the pseudo-second order equation and the
second order rate equation, A relatively higher value indicates that the model successfully
describe the kinetic of adsorption.40, 41
29
1.6.1 The Pseudo First Kinetics Order Model
The pseudo First order kinetic model is employed for the reversible reaction with an
equilibrium being established between liquid and solid phases. The pseudo first order rate
equation (Lagergren, 1898) is generally expressed as follows.
dq t
 K1 (q e  q t ) .................................. (IX)
dt
Where qe and qt are amount of metal adsorbed at equilibrium and at time t, respectively
(mg/g). K1 is the rate constant of pseudo first order adsorption (L min-1).41
After integration and applying boundary conditions the linearized form of equation (X),
when t = 0 to t = t and qt = 0 to qt = qt,
K1
Log (qe-qt) = log (qe) – t.................. (X)
2. 303
The plot of log (qe-qt) verses 't' should give a straight line from which k1 and qe can be
determined from slopes and intercept of the plot respectively.
1.6.2 Pseudo Second Kinetics Order Model
Most of the sorption system followed a pseudo-second order kinetic model as reported by
Ho and Mc Kay. It is based on the sorption capacity on solid phase. The pseudo second
order adsorption Kinetic rates equation used to study the kinetic of adsorption of heavy
metals is expressed as the rate of occupation of adsorption sites is proportional to square
of the number of unoccupied sites.42 The pseudo second order adsorption Kinetic rates
equation is expressed as (Ho et al., 2000). 41
dq t
 k 2 (q e  q t ) 2 .............................. (XI)
dt
Where K2 is the pseudo second order rate constant mg-1 min-1 and qe and qt are the
amount of metal ion adsorbed at equilibrium and at time ’t’ respectively (mg/g).
30
Integrating the above equation by applying boundary condition t= 0 to t = t & qt = 0 to qt
= qt gives rearranged linear form as,
 t  1 1
   2
 (t) ..................... (XII)
 q t  k 2q e q e
If initial adsorption rate vo mgg-1 min-1 is
vo = K2qe2 ........................................... (XIII)
Then equation (xiii) becomes
 t  1 1
    (t) ....................... (XIV)
 qt  vo q e
The plot of t/qt verses t of equation (XII) should give a straight line having slope 1/qe and
1
intercept . So the pseudo second order rate constant and amount of metal ion
K 2 q e2
adsorbed at equilibrium can be calculated.41
1.6.3 The Second Kinetics Order Model
The second order adsorption kinetic rate equation is expressed as (Ho et al., 1996).
dq t
 k 2 (q e  q t ) 2 …………………….. (XV)
dt
Integrating the equation under boundary condition the linear form of second order
adsorption kinetic rate equation is.
1 1
  k12 (t) .................. (XVI)
(q e  q t ) q 3
Where, qe and qt have their respective meaning‘t’ is contact time and K21 is second order
rate constant (g/mg. min). The plot of (1/qe-qt) verses should be a straight line with slope
equal to K21 & intercept 1/qe.40
31
The validity of kinetic models can be investigated by studying the kinetic at different
time interval with different initial metal concentration. The equilibrium uptake of metal
should nearly equal to the experimental equilibrium. If it couldn’t do so, then the reaction
is not likely to be following that model, even if that particular model gives high
correlation coefficient with the experimental data. Opposing to other well establish
model, pseudo second-order model predict the behaviour over the whole range of studies
and it is in agreement with chemisorptions mechanism being the rate controlling steps
with the formation of monolayer coverage on the adsorbent surface.42
32
2. Objectives of the Study
2.1 General Objectives
The general objective of the present work is to prepare a low cost bio adsorbent from the
sugarcane bagasse and to investigate the adsorption capacity of the adsorbent in the
removal of Fe (II), Al (III) and Cr (VI).
2.2 Specific Objectives
The specific objectives of the present study can be summarized as follows:
a) To prepare an adsorbent introducing phosphoric group onto the charred sugarcane

bagasse as phosphate group has high affinity for metals ions.
b) To study the adsorption behaviour of Fe (II), Al (III) and Cr (VI) onto charred and
phosphorylated charred powder.
c) To investigate the effect of pH, initial concentration of metal ions, and contact time on
the removal of Fe (II), Al (III) and Cr (VI) from aqueous solution.
d) To find out the type of adsorption isotherm of Fe (II), Al (III) and Cr (VI) followed and
check the validity of Langmuir and Freundlich adsorption isotherms.
e) To study the kinetics of the adsorption process.
f) To determine the values of maximum adsorption capacity (qmax) of the prepared

adsorbents.
33
3. Literature Survey
The industrial activities has intensified more environmental problems as seen for
example in the deterioration of several ecosystems due to the accumulation of
dangerous pollutants. Apart from the environmental damage, human health is likely to be
affected as the presence of toxic wastes beyond a certain limit brings serious hazards to
living organisms.43
On reviewing the literatures quite large numbers of scientist and environmentalist have
investigated the possibility and efficiency of utilization of agricultural fibres as an
adsorbent for heavy metal adsorption in polluted water. Although adsorption process
have short history as compared to other water purification process. Like precipitation, ion
exchange, chelation, solvent extraction, electrolytic recovery and liquid membrane
separation method. Recently, use of biological waste materials for heavy metal removal
has been increasing because of being environment friendly, cost effective and high metal
uptake capacity.44, 45
Adsorption is gaining interest as one of the most effective processes for treatment of
industrial effluent containing toxic materials. The occurrence of non-biodegradable
wastes in streams and lakes threatens the use of water resources and various treatment
methods have been used for the removal of these wastes. Among these methods,
adsorption using commercial activated carbon has proven to be efficient, however it is
highly expensive. Hence in recent years there has been a continuous search for locally
available and cheaper adsorbent.
Adsorption was first observed by Lowitz in 1885 and was soon applied as a process for
removal of color from sugar during refining. In the 19th century, American water
treatment plants used inactivated charcoal filters for water purification. In 1929 the first
granular activated carbon (GAC) units for treatment of water supplies were constructed in
Hamm, Germany and in 1930 at Bay city, Michigan. Currently, adsorption on activated
carbon is a recognized method for the removal of heavy metals from wastewater while
the high cost of activated carbon limits its use in adsorption.46
34
(Halya et al., 2000), biosorption of Cr (VI) from aqueous solution on husk of Bengal
gram. The biosorptive capacity of Bengal gram husk was dependent on the pH of
chromium solution with pH 2 being optimal .The adsorption data fitted with Langmuir
and Freundlich isotherm models.47
(Dodrowolski et al., 2000), studied the adsorptions of Cr (VI) from aqueous solution on
activated carbon and found that the reaction rate of ions on the surface of the activated
carbon rather than diffusion was the major process influencing the equilibrium. Surface
reduction of Cr (VI) to Cr (III) appeared to be the principal mechanism for the adsorption
of chromium on the activated carbon.48
(Hamadi et al., 2001), studied the adsorption kinetics for the removal of Cr (VI) from
aqueous solution by Tyres & Sawdust. They found that the removal was favoured at low
pH, with maximum removal at pH 2. They found both sorbets were effective to remove
Cr (VI) from solution. The sorption kinetics was found to follow pseudo second-ordered
model.49
(Ghimire et al., 2002), introduced the phosphate group to orange juice residue with the
substitution of alcoholic analogue of glucose. The phosphorylated orange juice residue
was further loaded with Fe (III), for which loading capacity was 3.7 mol/kg. Maximum
adsorption capacity on iron loaded phosphorylated orange juice residue was found to be
0.94 and 0.91 mol/kg for As (V) and As (III), respectively.50
(Ghimire et al., 2003), prepared the saponified and phosphorylated orange waste for the
removal of Arsenic and Fluoride from synthetic and field water samples. They found Fe
(III) and La (III) loaded saponified orange waste effective for arsenic removal and La
(III) and Cr (VI) loaded phosphorylated orange waste better for Fluoride removal
(superior than activated alumina). The loading capacities of Fluoride on the Ce (IV)
loaded phosphorylated orange waste and La (III) loaded phosphorylated orange waste to
be 2.7 and 2.8 mol/kg, respectively.45
35
(Demirabas et al., 2004), studied the adsorption kinetics for the removal of Cr(VI) from
aqueous solution on the activated carbon prepared from cornelian cherry, apricot stone
and almond shells. They found that the maximum adsorption of Cr (VI) at pH 1 for all
types of carbons. The sorption reaction was found to be follow pseudo second order
model.42
(Ahalya et al., 2005), studied biosorption of Cr (VI) from aqueous solution by the husk
of Bengal gram. They found that the removal was favoured at pH 2. The adsorption data
fit well with the Langmuir & Freundlich isotherm model.51
(Karthikeyan et al, 2005), studied the removal of Fe (III) ion from aqueous systems using
chitin as an adsorbent. Chitin is a non-toxic and biodegradable polymer of N-acetyl
glucosamine and glucosamine residues. It is a major component of arthropod and
crustacean shells. The researchers found that the adsorption of Fe (III) by chitin was
spontaneous, endothermic and favourable.52
(Parajuli et al., 2005), prepared the cross-linked lingo-catechol gel by immobilizing

catechol onto wood lignin, followed by cross linking. They used this adsorbent for the
removal of different heavy metals. 53
(Kumar et al., 2006), studied the removal of Cd2+ by raw rice husk, epichlorohydrin
treated rice husk, NaOH treated rice husk and Na2CO3 treated rice husk. The maximum
adsorption capacities were found to be 8.58, 11.12, 20.24 & 16.18 mg/g respectively. The
data well fitted for Langmuir adsorption isotherm and pseudo second order kinetic
model.54
(Gaupta et al., 2006), studied the adsorption of Cr (VI) by low cost adsorbent prepared
from amarind seeds. They found that the adsorbent prepared from amarind seeds can be
used for removal of Cr (VI) from aqueous solution and adsorption was favourable at low
pH. Freundlich adsorption model showed good agreement with the experimental data.55
(Sankaramakrishnan et al., 2006), modified chitosan flakes with 4% w/w acetic acid, 2M
NaOH solution to make beads. Those chitosan beads and flakes were cross linked with
glutaraldehyde and the cross-linked product was xanthated with 14% NaOH and CS2.
36
Such cross-linked xanthated chitosan flake had maximum adsorption capacities of 625
mg/g for Cr (VI) while beads had qmax equal to 256.4 mg/g.56
(Biswas et al., 2007), prepared the La (III), Ca(II) and Fe(III) loaded orange waste and
studied the adsorption of phosphate from water and found maximum adsorption capacity
to be 139.4 mg/g of dry gel for all three types of adsorbents. They proposed ligand
substitution mechanism for the adsorption.27
(Arivoli et al.,2007), studied the adsorption of chromium ion from aqueous solution by
acid activated banana bark carbon and show have effect of variable parameter on
adsorption process and maximum adsorption takes place at low and high pH value and
the amount of adsorption increased with increasing ionic strength and temperature. They
calculate the different thermodynamic parameters as H, S, G0 .57
(Ghimire et al., 2008), chemically modified the sea weed Laminaria Japonica by cross
linking with epichlorohydrin. They studied the adsorption behaviour of trivalent and
divalent metal ions onto it. It was found that it exhibits excellent selectivity towards
certain heavy metals.46
(Anber et al., 2008), studied the kinetic and thermodynamic parameters of Fe (III)
adsorption on olive cake. They found optimum pH for the adsorption to be 4.5 and the
data well fitted with Freundlich adsorption isotherm model and pseudo second order
kinetic model.58
(Nameni et al., 2008), studied adsorption of hexavalent chromium from aqueous solution
by wheat bran. They studied the effect of various parameters on Cr (VI) adsorption and
found that the adsorption of chromium by wheat bran reached to equilibrium after 60
minutes and maximum chromium removal (87.8%) obtained at pH 2. The result showed
that the adsorption follow the pseudo second order kinetics.59
(Alzaydien et al., 2009), used the unmodified orange peel for the removal of Pb (II) from
waste water. He found that the maximum adsorption capacity to be 21.1 mg/g at pH 6 and
20 oC. Both Langmuir and Freundlich models fitted well to the experimental data and the
pseudo second order kinetic model was obeyed by it.60
37
(Bozic et al., 2009), studied the adsorption of iron and copper ion from synthetic
solutions using saw dust of beech linden, poplar trees. The kinetics of adsorption was
reported to be relatively fast reaching equilibrium for less than 20 min. The maximum
adsorption capacity (7-8 mg/g saw dust) was achieved at pH between 3.5 & 5 for all kind
of saw dust studied. No influence of particle size was evidenced. A degree of adsorption
higher than 80% was achieved for Cu2+ ions but it is very low for Fe2+ ions, not
exceeding 10%.34
(Abdel et al., 2009), conducted a factorial experimental design for biosorption of iron and
Zinc using Typha Domingensis phytomass. Authors have reported that this study was
manly dependent on using the statistical design of experiments over the conventional
univariate procedure for optimization of the system. The information obtained by such
design are much more than those obtained from conventional procedures with
significantly reduced number of experiments and thus save time, energy and cost. This
observation had shown that the pH is the most important factor affecting the biosorption
of Fe3+ and Zn2+ by Typha Domingensis phytomass, while the second factor is the
temperature & then the interaction between two factors.61
(Baral et al., 2010), studied hexavalent chromium removal from aqueous solution by
adsorption on sawdust. The studies were conducted by varying various parameters such
as contact time, pH, amount of adsorbent, concentration of adsorbate & temperature.
They found that the maximum removal of Cr (VI) in the pH range 4.5-6.5 & sorption
reaction was found to be follow pseudo-second order .62
(Raymundo et al., 2010), studied a methodology involving sugarcane bagasse bio

adsorbent to remove the carcinogenic Congo red dye from the aqueous solution. The
result showed high efficiency with retention of 64% in synthetic Congo red solution and
94 % in effluents enrich with Congo red at 10 of adsorbent. The equilibrium data fitted
well with Langmuir adsorption isotherm.63
(Humagai et al., 2010), studied the removal of cadmium, lead, nickel, zinc and copper
from aqueous media by using charred xanthated sugarcane bagasse which was found to
have significance adsorption capacity. The adsorption behaviour was pH dependent and
38
the velocity of sorption of the tested metal was fast reaching equilibrium within 40
minutes. The maximum loading capacity was found to be 225 for Cd (II), 318 for Pb (II),
144 for Ni (II), 164 for Zn (II) and 178 for Cu (II) mg/g respectively.64
(Halim et al., 2011), studied the adsorption of Al (III) onto Curcuma Longa
(turmeric).the optimal removal of 95.8% was achieved at the 90 minutes. A dose of 6g/L
was enough for the 93% removal of Al (III) ion. Both Langmuir and Freundlich
adsorption isotherm describe the sorption behaviour. The adsorption data follows pseudo-
second order kinetic and the adsorption behaviour was pH dependent.65
(Pandey et al., 2012), studied adsorption of Methyl Red (MR) onto chemically modified
sugarcane wastes and aminated sugarcane waste. The maximum dye removal was
observed at pH 2 onto CSW and pH 7 for ASW. The adsorption data follows pseudo-
second order kinetic model.25
Though there are several works regarding the adsorption onto either using activated
carbon or with biomaterials as such. Now a day, the great attention has been paid to
remove the heavy metals by using functionalized biopolymers. Under such
circumstances, this dissertation has explored a possibility to derive polyphenolic/
polyhydroxy functional matrix in sugarcane waste for the purpose of heavy metals
adsorption.
39
4. Scope and Limitations of the Study
This study was purely laboratory, this study is aimed at finding out how a manipulation
of the following parameters; pH, adsorbent mass, environmental conditions affect the
adsorption potentials of fibre ash on the following three heavy metals, (Al, Fe and Cr).
Temperature was not included among these parameters for technical reasons. In general,
contaminated waste waters contain more than one heavy metal. This study was done on
single metal synthetic solutions which is a limitation. The chemical used are of laboratory
grades. The metal concentration was measured by spectrophotometer which is less
sensitive than other modern methods like ICP. And the chemical available in the
laboratory were used directly for their respective concentration with careful attention as
mention in the standard text.
40
5. Material and Methods
5.1 Instruments Used
5.1.1 Chemiline Digital pH meter, Cl-110, Electrode-HI-1230.
5.1.2 Spectrophotometer, WPA Linton (S-104), Cambridge, UK.
5.2.3 V.D.R.L SHAKER, Accuma X India.
5.2. Preparation of the Reagents
5.2.1 1000 ppm Stock Iron Solution
7.016 gm Mohr’s salt [Fe(NH4)2.FeSO4.7H2O] was dissolved in 1L 0.1N nitric acid

solution and volume was made up to mark.
5.2.2 Potassium Dichromate (K2Cr2O7) Stock Solution (1000 ppm)
Stock potassium dichromate solution was prepared by dissolving 2.828 gm of potassium

dichromate crystal in 1000 ml volumetric flask in 0.1 N HNO3 solutions. 1ml of stock
potassium dichromate solution equal to 1 g HCrO4- as in the form of Cr (VI). From
stock potassium dichromate solution, working solution of lower concentration was
prepared by dilution method in 0.1N nitric acid solution.
5.2.3 Aluminium Stock Solution [K Al (SO4) 2 .12H20]
Stock aluminium solution was prepared by dissolving 17.58 gram of potash alum in 1000
ml volumetric flask in 0.1N nitric acid solution. 1 ml of stock aluminium solution 1000
equal to 1 g Al (III). From stock aluminium solution, working solution of lower
concentration was prepared by dilution method in 0.1N nitric acid solution.
5.2.4 5M Sulphuric Acid Solution (approx.)
41
5M of Sulphuric and solution was prepared by diluting 69.5 ml of concentration sulphuric
acid in 250 ml volumetric flask in distilled water.
5.2.5 5M Sodium Hydroxide Solution (approx.)
5M sodium hydroxide solution was prepared by dissolving 20 gm. of sodium hydroxide

pellets in 100 ml volumetric flask in distilled water.
5.2.6 5 M Nitric Acid Solution (approx.)
5M nitric acid was prepared by diluting the 32 ml of concentration HNO3 (15.66 M) in

100 ml volumetric flask in distilled water.
5.2.7 Preparation of 0.25% 1,5 Diphenycarbazide (DPCI) Solution
0.25 gm. of 1.5–Diphenylcarbazide crystals were transferred to a 100 ml volumetric flask

and 50 ml of pure acetone was added slowly with constant striking. Then 50 ml water
was added up to the mark. Due to the high sensitivity of this solution to light, it was
protected from direct sunlight by wrapping the bottle containing the reagent with black
paper. This prolonged the life span of the reagent. When this solution turned faint red, it
was discarded and a fresh solution was prepared.
5.2.8 Buffer Solution pH 4
Buffer tablet of pH 4 was dissolved in a 100 ml volumetric flask and made up to the mark
in distilled water.
5.2.9 Buffer Solution of pH 7
Buffer tablet of pH 7 was dissolved in 100 ml volumetric flask and made up to the mark
in distilled water.
5.2.10 Buffer Solution of pH 9.2
Buffer tablet of pH 9.2 was dissolved in a 100 ml volumetric flask and made up to the
mark in distilled water.
42
5.2.11 10% Hydroxyl Amine Hydrochloride Solution
10 ml Hydroxyl Amine Hydrochloride was taken in 100 ml volumetric flask and diluted
to mark.
5.2.12 1, 10-Phenanthroline Hydrochloride Solution
0.2 mg of 1,10-Phenanthroline Hydrochloride was taken in 100ml volumetric flasks it

was dissolved in some water by stirring and heating to about 80 degree 0C and diluted to
the mark.
5.2.13 0.2% Eriochrome Cynine R [C23H15Na3O9S] Solution
200 mg of Eriochrome Cynine R crystal were dissolved in 100 ml volumetric flask in

distilled water.
5.2.14 Ammonium Acetate Buffer Solution
250 gm. Ammonium Acetate was dissolved in 150 ml water and then 700 ml glacial
acetic was added to it.
5.2.15 0.1M Nitric Acid
12.5 ml concentration Nitric acid (16M) was diluted to 2 L using V.F.
5.2.16 0.02N Sodium Carbonate Solution
0.265 gm. Sodium carbonate was dissolved in water and the volume was made up to 250
ml.
5.2.17 0.02 N NaHCO3 Solution
0.42 gm. NaHCO3 was dissolved in water and the volume was made up to 250 ml.
43
5.2.18 0.02 N NaOH Solution
0.2 gm. NaOH was dissolved in water and the volume was made up to 250 ml.
5.2.19 0.02 N HCl Solution
0.42 ml HCl was diluted to 250 ml.
5.2.20 0.04 N Oxalic Acid Solution
0.63 gm. Oxalic acid was dissolved in water and the volume was made up to 250 ml.
5.2.21 0.1N HNO3 Solution (approx.)
0.1N Nitric acid solution was prepared by mixing 6.25 ml of concentrated Nitric acid in
1000 ml V.F. in distilled water.
5.2.22 2M NaOH Solution (approx.)
20 g of NaOH pellets was dissolved in distilled water in 250 ml V.F. and volume was
made up to the mark.
5.2 Preparation of Adsorbents From Sugarcane Bagasse
5.3.1 Preparation of Raw Sugarcane Bagasse
Sugarcane bagasse used in the study was collected from a juice shop located in Kritipur.
The collected bagasse was washed and dried in the sun for a week and it was cut into
small piece and grinded in mechanical grinder at Central Department of Chemistry,
Kritipur and sieved into mess of 125 micrometres. Thus obtained raw bagasse has lesser
efficacy for removal of heavy metal. In order to enhance metal uptake capacities of RSB,
it was then subjected to chemical modification.
5.3.2 Acid Modification
The raw sugarcane bagasse was chemically modified by using concentrated H2SO4 in
(1:2) with occasional stirring; this acid modified bagasse was allowed to stand for 24
44
hours for completion of acid modification. The excess acid was removed by washing with
water till neutrality and it was dried in sun and then in oven for 6-8 hours below 100 C.
Finally it was grinded and sieved to a particle size 125 micrometres.66
Figure 5.1: Acid Modification Process.
5.3.3. Phosphoric Acid Modification (Phosphorylation)
The acidic modified dried powder was taken about 20 gram and 250 ml DMF was taken
in three necked flask then it was shaken well, and 30 gram of urea was added and 30 ml
of phosphoric acid was added in drop wise with constant stirring (by magnetic stirrer).
Then the mixture was refluxed for 2 hour at 150C in paraffin oil bath with stirrer
continuously and at one neck thermometer is kept. Then it was cooled, after cooling, the
45
mixture was washed with 500ml, 70% propanol till clear solution is obtained, then
washing is followed by water till neutrality .The adsorbent was then (washed) with 0.1
HCl and then filtered again washed with rain water several times till neutrality. It was
dried in air (sun dried) for one day and dried in oven for 1 day at 60-70 C, then taken out
from oven and kept in air tight bottle.
Figure 5.2: Phosphoric Acid Modification (Phosphorylation) Process.
46
5.3.4 Effects of Chemical Modification
Biosorbents are the biomass materials which have different adsorption capacities. The
adsorption capacity of such adsorbent can be increased by different methods as thermal
activation, chemical modification & so on. Sugarcane bagasse consists of cellulose,
hemicelluloses, lignin, polyphenol and many other low molecular weight compounds.67
Chemical modification in generally improve the adsorption capacity of adsorbents

probably due to higher number of active binding sites after modification, better ion
exchange properties, increase in concentration and or formation of new functional groups
takes place that favours the metals uptakes. So by chemical modification of RSB, the
effective surface area of carbon increases and surface of the adsorbent get modified due
to the reduction of low molecular weight lignin and decrease in crystallinity of
hemicelluloses. This causes in increased in concentration and or formation of new
functional groups and active sites at the surface of the adsorbents.68 The treatment of
acid with biopolymers creates a suitable environment for its ring opening.34 When raw
sugarcane bagasse is treated with conc. H2SO4 the some of the glucose monomer of the
cellulose may be carbonized and of some of them may open up as follows:
CH2OH CH2OH
O Conc. H2SO 4 OH
O O
OH OH OH
Ring opening
OH OH
(Compound formed by ring opening)
Figure 5.3: Modification Mechanism of Adsorbent.34
Similarly on treating with Concentration H2SO4 the large ring of lignin is decompose into
smaller fragments to some extend but FTIR spectra shows that parent functional groups
47
do not undergoes too much change. One of the important fragments is benzene-1, 2-diol
as its phenolic –OH group can be chemically modified.69
Figure 5.4: Modification by Introducing Phenolic –OH Group.
These compounds obtained by treating with concentrated H2SO4 where surface functional
sites converted into large number of phenolic – OH group. Therefore charred adsorbents
can further be modified with phosphoric acid to introduce phosphate group into adsorbent
in order to increase the loading capacity of Fe (II) Al (III) and Cr (VI).
OH O
OH
CH2 OH
CH2 P
OH
OH O
H O O
OH H C Conc. H
H3PO4 OH H C
O H
O H
H OH
H OH
48
Figure 5.5: Modification Mechanism of Adsorbent by Phosphoric Acid .67
5.3.5 Mechanism of the Adsorption.
Plausible Adsorption Mechanism:
The plausible mechanism of Chromium (VI) adsorption can be schematically represented

as follows:
CH2OH O CH2OH
O
OH O
O + HO Cr O- O Cr + H2O + OH-
OH OH OH
O O
O
OH OH
OH - O O
HCrO 4
Cr + OH- + H2O
OH O O
Figure 5.6: Complexation of Chromium(VI) with Polyphenolic/Polyhydroxyl

Functional Moiety of Modified Sugarcane Waste.
49
OH O
H O OH
CH2 H2O
P CH2 Fe
P
H O O H2O
3+ H O H2O
OH H O + Fe O
C OH H C
O H O H
H OH
H OH
O O OH
OH O H2O
O P Fe
O P
OH Fe3+ O H2O H2O
OH O OH H2O
Fe
O P O P H2O
OH O H2O
O O
Figure 5.7: Complexation of Iron with Polyphenolic/Polyhydroxyl Functional

Moiety of Modified Sugarcane Waste.
50
6. Experimental:
Determination of λ max and Construction of Calibration Curve
First of all 1000 ppm stock solution was diluted to 500 ml in 50 ml V.F by 0.1M HNO3
by series dilution method as direct dilution leads to large dilution error.
Figure 6.1: Series Dilution.
6.1 Construction of Calibration Curve for Iron
The solution of 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm and 9ppm of Fe
(II) were prepared along with the required reagents like 6 ml buffer solution of pH 4.5,
3ml of 10%hydroxyl amine hydrochloride solution and 3 ml 20% 1, 10-phenonthroline
solution in nine 25 ml volumetric flask. The blank solution was prepared by adding all
51
reagent but with no iron solution. The solution was allowed to leave for 30 minutes to
develop the full colour. An intermediate concentration of iron solution was taken for the
determination of λ max For this the spectrophotometer was set to zero by using blank
solution.
The amount of colour developing reagent and time regents and time was also optimized
as follows:
 Amount of Hydroxyl Amine Hydrochloride Solution: 3 ml
 Amount of Ammonium Acetate Buffer : 6 ml
 Amount of Phenonthroline : 3 ml
 Time Required for Color Development : 30 min
Then, the absorption of light by the intermediate concentration of the solution at different
wavelength was measured. The spectrophotometer was set zero every times of changing
wavelength with the help of blank solution. At last, a plot of absorption of light verses
corresponding wavelength was plotted. From the graph, the value of λ max was evaluated.
Table 6.1: Spectrophotometric Determination of  max for Fe (II)

S.N. Wavelength (nm) Absorbance
1 420 0.56
2 430 0.64
3 440 0.74
4 450 0.74
5 460 0.80
6 470 0.78
7 480 0.78
8 490 0.78
9 500 0.86
10 505 1.00
11 510 1.00
12 515 0.98
13 520 0.90
14 530 0.70
15 540 0.48
16 550 0.26
17 560 0.16
52
Figure 6.2 Spectrophotometric Determination of  max for Fe (II).
After finding the value of λ max i.e. 510 nm, the spectrophotometer was set at that
wavelength (510 nm) and the absorption of solution of different concentration (1-8 mg/L)
was measured. Thus obtain plot between the absorbance and concentration of the solution
is known as calibration curve.
Table 6.2: Calibration Curve for Fe (II)
S.N. Concentration (mg/L) Absorbance

1 0.0 0.00
2 0.5 0.10
3 1.0 0.24
4 2.0 0.44
5 3.0 0.64
6 4.0 0.82
7 5.0 1.00
8 6.0 1.18
9 7.0 1.32
10 8.0 1.50
53
Figure 6.3: Calibration Curve for Fe (II).
6.2 Construction of Calibration Curve for Aluminium
Aluminium (III) solution of 1.25 ppm was prepared from series of dilution technique
from 1000 ppm stock solution of aluminium. And nine different 25ml volumetric flask
were taken and from 1.25ppm solution 0.5ml, 1ml, 2ml, 3ml, 4ml, 5ml, 6ml, 7ml, and
8ml solution were taken and 5ml of buffer of pH 6.0 were added along with 1ml of
Eriochrome Cyanine R (0.20%) as a colour developing agent were also added and the
volume was made up to the mark by adding water. The concentration of aluminium
solution in nine volumetric flask become 25ppb, 50ppb, 75ppb, 100ppb, 150ppb, 200ppb,
250ppb, 300ppb, 350ppb and 400ppb respectively. Likewise a blank solution was
prepared by using same amount of the reagent. The solutions were allowed to leave for
15 minutes for the full colour to be developed.
After 15 minutes, a solution of intermediate colour was taken and its absorption spectra
of pink -purple colour Al (III) - ECR complex was recorded at different wavelength. At
every wavelength, the spectrophotometer was set to zero with the help of blank solution.
Then, a plot of absorption verse wavelength of light was plotted. From this plot the λ max
was evaluated which was 525nm.
54
Table 6.3: Spectrophotometric Determination of λ max for Al (III)

1 400 0.08
2 425 0.12
3 450 0.14
4 475 0.16
5 500 0.18
6 525 0.22
7 530 0.20
8 540 0.18
9 550 0.14
10 560 0.10
11 570 0.06
12 580 0.04
The Determination of λmax of Al (III)

0.25
0.2 λmax = 525 nm

Absorbance
0.15
0.1
0.05
0
390 440 490 540 590
Wavelength (nm)
Figure 6.4: Spectrophotometric Determination of  max for Al (III).
The absorption of light by each of the solution was measured by fixing the
spectrophotometer was set to zero by using blank solution. At last, a plot of concentration
versus light was made which is the calibration curve for the aluminium.
55
Table 6.4: Calibration Curve for Al (III)
S.N. Concentration (ppb) Absorbance

1 0 0.00
2 25 0.02
3 50 0.08
4 100 0.22
5 150 0.30
6 200 0.42
7 250 0.50
8 275 0.56
9 300 0.64
10 350 0.74
11 400 0.86
Figure 6.5: Calibration Curve for Al(III).
6.3 Construction of Calibration Curve for Chromium
From chromium (VI) solution of 5mg/L of volume 0, 0.5 , 1 , 1.5, 2 , 2.5 , 3 , 3.5 and 4
ml were taken in a different 25ml volumetric flask and was acidified with 1 ml of 5M
H2SO4 in each volumetric flask and shaken well. Then 1ml of 0.25% DPCI solution was
added to each volumetric flask and shaken well. The volume was then made up to mark
by adding water. The absorption spectra of red-violet colour Cr (VI) - Diphenycarbazide
complex was recorded in spectrophotometer against blank reagent. Then, a plot of
56
absorption verse wavelength of light was plotted. From this plot the λ max was evaluated
which was 540 nm.
Table 6.5: Spectrophotometric Determination of λ max for Cr (VI)

1 490 0.04
2 500 0.08
3 520 0.14
4 530 0.18
5 540 0.22
6 545 0.22
7 550 0.20
8 560 0.16
9 570 0.12
10 580 0.08
11 590 0.04
12 600 0.04
The Determination of λ max for Cr (VI)

0.25
λ max =540 nm
0.2
Absorbance
0.15
0.1
0.05
0
470 490 510 530 550 570 590 610
Wavelength (nm)
Figure 6.6: Spectrophotometric Determination of  max for Cr (VI).
57
Table 6.6: Construction of Calibration Curve for Cr (VI)
S.N. Conc. (ppb) Absorbance
1 0 0.00
2 50 0.02
3 100 0.04
4 200 0.08
5 300 0.14
6 400 0.22
7 500 0.26
8 600 0.30
9 800 0.40
Figure 6.7: Calibration Curve for Chromium.
6.4 Batch Adsorption Studies
The adsorption of Fe (II), Cr (VI) and Al (III) ion were studies by carrying out batch
tests. Synthetic working solution of Fe (II), Cr (VI) and Al (III) of predetermined
concentration and adsorbent prepared from sugarcane bagasse in modified form were
58
used. The pH of the solutions and series of 1M , 2M , 3M , 4M and 5M HNO 3 solution
and series of 1M , 2M , 3M ,4M , and 5M NaOH solutions.
The working solutions of various required concentrations of Fe (II), Cr (VI) and Al (III)
were prepared by diluting 1000ml stock solution, whereas solution of concentration less
than 50mg/L working solutions of known initial concentration were added to 25mg of
raw and modified sugarcane bagasse in different 25 ml reagent bottles and the mixtures
were agitated on a mechanical shaker for 24 hours at laboratory temperature. At the end
it was used to analyse the residual concentration of metal filter paper and the filtrates
were used to analyse the residual concentration of metal ions. Concentration before and
after was determined spectrophotometerically by using 1,10-phenanthroline for Fe(II),
Diphenycarbazide method for Cr(VI) and Eriochrome Cynine R method for Al (III) ion
solution respectively.
6.4.1 Batch pH Studies
Batch pH studies were conducted by shaking 50 ppm of iron, 25 ppm of Cr (VI) and Al
(III) solution with 25 mg of adsorbent for 24 hours at laboratory temperature. The initial
pH Fe (II), Cr (VI) and Al (III) solutions were adjusted from 1.0 to 6.0 pH value using
digital pH meter. All samples were shaken in 25 ml reagent bottles using mechanical
shaker at laboratory temperature separately. The equilibrium pH of the reaction mixture
was recorded and filtrates were used for remaining Fe (II), Cr (VI) and Al (III) metal ion
concentration. The pH at which maximum adsorption of metal ion occurs was selected as
optimum pH for the further studies.
6.4.2 Batch Isotherm Studies
Adsorption isotherm studies were carried out with different initial concentration of Fe
(II), Cr (VI) and Al (III) ion ranging from 10mg/L separately with adsorbent dose of
25mg. The sample solution were taken in 25 ml regent bottles and shaken in a mechanical
shaker for 24 hours. Both charred sugarcane bagasse (CSB) and phosphorylated
sugarcane bagasse (PCSB) were used at optimum pH. The remaining metal ion
concentrations were determined after filtering the reaction mixture by using the same
59
spectrophotometer. The experiment regarding adsorption isotherm helps in determining
nature of adsorption and maximum adsorption capacity of the adsorbent used.
6.4.3 Batch Equilibrium Time Studies
The effect of contact time was studies at room temperature at optimum pH. The
equilibrium time of the adsorbent for Fe (II), Cr (VI) and Al (III) were investigated at
their respective pH values by taking 25 ml of respective concentration of Fe (II), Cr (VI)
and Al (III) solution in 25ml reagent bottles with 25mg adsorbent dose. The mixtures
were shaken in a mechanical shaker for 10, 20, 30, 40, 50, 60, 80, 100, 120 mins, 3 hrs,
4hrs, 6hrs, 10hrs, 12 hrs, and 24 hrs respectively. The metal ions concentration before
and after adsorption were determined by spectrophotometer.
6.4.4 Batch Kinetics Studies
The measurement of adsorption kinetics was carried out at optimum pH for all Fe (II), Cr
(VI) and Al (III) separately. Required metal ion solution were added in different 25ml
reagent bottles containing 25 mg of adsorbent and the mixture were shaken in a
mechanical shaker up to desired contact time. Samples were filtered through filter paper
and concentration before and after adsorption were determined spectrophotometerically.
The data thus obtained with pseudo first order, pseudo-second order and second order
kinetics.
60
7. Results and Discussion
7.1 Batch pH Studies of Fe(II)
Batch pH study was carried out with the Fe (II) solution with initial concentration, 50
mg/L to study the influence of pH on the percentage adsorption.
Table 7.1: Effect of pH on Adsorption of Fe(II) onto CSB

Volume of metal solution = 25 ml
Concentration of metal solution =50 mg/L
Amount of Adsorbent =25 mg
S.N pH pHe Ci (mg/L) Ce (mg/L % Adsorption

)
1 1.0 1.6 48.78 47.50 2.60
2 1.5 2.0 47.50 41.37 12.90
3 2.0 2.2 45.00 37.80 15.98
4 2.5 3.8 41.46 7.31 82.37
5 3.0 4.9 25.62 8.53 66.67
Table 7.2: Effect of pH on Adsorption of Fe(II) onto PCSB.

S.N pH pHe Ci (mg/L) Ce (mg/L ) % Adsorption
1 1.0 1.1 48.78 43.90 10.00
2 1.5 1.9 48.17 37.80 21.52
3 2.0 2.3 46.34 32.92 28.95
4 2.5 3.3 41.96 6.09 85.26
5 3.0 4.6 24.39 7.31 70.00
The pH of the aqueous solution is an important parameter in the removal of metal by
adsorption. The metal removal capacity generally increases with the increases in pH.
Figure shows that % adsorption of Fe (II) increased from 2.6 % to 82.37 % and 10 % to
85.26 % for CSB and PSCB respectively, on increasing pH from 1.0 to 2.5 and decreases
beyond pH 2.5. Hydrolysis possesses a greatest problem in the adsorptive removal of
iron.
61
Figure 7.1: Effect of pH on the Adsorption of Fe (II) onto CSB and PCSB.
The analysis of the data and graph revealed that the optimum pH for the adsorption of Fe
(II) was found to be 2.5 for the both adsorbent. In the case the optimum pH was found to
be 2.5. Beyond it the percentage adsorption decreases. It is because of the hydrolysis and
the adsorbent is not capable to absorb the Fe (II) from its hydrolysed product. Beyond pH
3.0, there is excessive hydrolysis of Fe (II) which decreases the Fe(II) concentration
leading precipitation.
The increase in percentage adsorption with the increase of pH indicates that the
adsorption process involves the cation exchange mechanism. There is competition
between Fe (II) and H+ ions for adsorption sites. At low pH value, there is high H+ ion
concentration than Fe(II) ions and leads to the low adsorption of Fe(II) ions. But at high
pH, the concentration of H+ ions is less and they are easily replaced by the metal ions
onto the adsorbent by the ion exchange process.
7.2 Batch Equilibrium Time Studies of Fe(II)
The adsorption of Fe (II) onto modified CSB & PCSB from 5 minutes to infinite time is
given in the graph:
62
Table 7.3: Effect of Contact Time for the Adsorption of Fe (II) onto SCB.
pH = 2.5
S.N. Time ( min ) Ci (mg/L) Ce (mg/L) qt (mg/g)
1 5 40.24 20.73 17.94
2 10 40.24 19.51 19.07
3 15 40.24 18.29 20.19
4 30 40.24 15.85 22.43
5 45 40.24 13.41 24.68
6 60 40.24 10.97 26.92
7 120 40.24 9.75 28.05
8 180 40.24 8.53 29.17
9 240 40.24 7.31 30.29
10 300 40.24 6.09 31.41
11 360 40.24 4.87 32.54
12 420 40.24 3.65 33.66
13 480 40.24 2.43 34.78
14 540 40.24 2.43 34.78
15 600 40.24 2.43 34.78
Table 7.4: Effect of Contact Time for the Adsorption of Fe(II) onto PSCB.
pH = 2.5
S.N. Time ( min ) Ci (mg/L) Ce (mg/L) qt (mg/g)
1 5 41.46 15.85 23.56
2 10 41.46 14.63 24.68
3 15 41.46 12.19 26.92
4 30 41.46 9.75 29.17
5 45 41.46 8.53 30.29
6 60 41.46 7.31 31.42
7 120 41.46 4.87 33.66
8 180 41.46 3.65 34.78
9 240 41.46 1.21 37.03
10 300 41.46 1.21 37.03
11 360 41.46 1.21 37.03
12 420 41.46 1.21 37.03
63
Figure 7.2: Effect of Contact Time on Adsorption of Fe(II) onto SB.
From figure it was found that optimum time for the adsorption of Fe(II) ions onto CSB &
PCSB and is 8 hrs and 4 hrs respectively. From this data, it can be concluded that PCSB
is better adsorbent than others as it brings equilibrium quickly.
The data indicates that initially the rate of adsorption is high but it decreases with time. It
is due to the fact that initially there is large number of surface cation exchange sites but
with the passes of time those sites are covered by metal ions. When all the active sites are
occupied by the metal ions, dynamic equilibrium is attained and the rate of adsorption
becomes zero.
7.3 Batch Kinetics Study of Fe (II)
The kinetic data for the adsorption of Fe(II) onto CSB and PCSB were analysed by using
pseudo-first order, pseudo-second order and second order kinetic models. On studying
these plots, it was found that the adsorption of Fe(II) onto all these adsorbents follow
pseudo-second order kinetic model with high correlation coefficient (R2) value.
64
Table 7.5: Kinetic Study of Adsorption of Fe(II) onto SCB.
pH= 2.5
S. Time Ci Ct qt qe-qt 1/qe-qt Log(qe-qt) t/qt

N (min) (mg/L) (mg/L) (mg/g) (mg/g) (g/mg) (mg/g) (min.g/mg)
1 5 40.24 20.73 17.94 16.84 0.06 1.22 0.27
2 10 40.24 19.51 19.07 15.71 0.06 1.18 0.52
3 15 40.24 18.29 20.19 14.59 0.07 1.15 0.74
4 30 40.24 15.85 22.43 12.35 0.08 1.09 1.33
5 45 40.24 13.41 24.68 10.10 0.09 1.00 1.82
6 60 40.24 10.97 26.92 7.86 0.12 0.92 2.22
7 120 40.24 9.75 28.05 6.73 0.14 0.85 4.27
8 24hrs 40.24 2.43 34.78 ….. … ……. …..
Table 7.6: Kinetic Study of Adsorption of Fe(II) onto PSCB.

pH = 2.5
S.N Time Ci Ct qt qe-qt 1/qe-qt Log(qe- t/qt

(min) (mg/L) (mg/L) (mg/g) (mg/g) (g/mg) qt) (min.g/mg
(mg/g) )
1 5 41.46 15.85 23.56 13.47 0.07 1.15 0.21
2 10 41.46 14.63 24.68 12.35 0.08 1.09 0.40
3 15 41.46 12.19 26.92 10.11 0.09 1.04 0.55
4 30 41.46 9.75 29.17 7.86 0.12 0.92 1.02
5 45 41.46 8.53 30.29 6.74 0.14 0.85 1.48
6 60 41.46 7.31 31.42 5.61 0.17 0.77 1.90
7 120 41.46 4.87 33.66 3.37 0.29 0.53 3.56
8 24hrs 41.46 1.21 37.03 - - - -
65
Figure 7.3: Pseudo-first Order Kinetic Plot for the Adsorption of Fe(II) onto SB.
Figure 7.4: Pseudo-second Order Kinetic Plot for the Adsorption of Fe(II) onto SB.
66
Figure 7.5: Second Order Kinetic Plot for the Adsorption of Fe(II) onto SB.
The amount of adsorption (qe) of Fe(II) onto these adsorbents obtained from experiment
is close to the qe obtained from pseudo-second order plot. So, it is concluded that the
adsorption of Fe(II) followed the pseudo-second order kinetic model.
Table 7.7: Different Parameters Calculated from the Kinetic Plots Adsorbents for Fe (II).
Adsorbent qexp Pseudo-first order Pseudo-second order Second-order

(mg/g) K1 (×10 -
qe R2
K2 (×10 -
qe Vo R2
K21 qe R2
3 3
) ) (×10-3)
CSB 34.78 7.50 15.52 0.89 5.60 29.32 4.81 0.99 0.70 16.42 0.93
PCSB 37.03 11.97 13.19 0.96 6.80 34.48 8.08 0.99 1.90 16.66 0.99
7.4 Batch Isotherm Studies of Fe (II)
The effects of concentration of metal solution on the adsorption of Fe(II) onto different
adsorbents prepared from Sugarcane Baggase are given below. The data shows that the
percentage of adsorption decreases with increase in the concentration of Fe(II) ion.
67
Table 7.8: Effect of Concentration on the Adsorption of Fe (II) onto CSB.
pH = 2.5
S.N. Ci Ce qe Ce/qe Log Ce Log qe %
(mg/L) (mg/L) (mg/g) (g/ L) (mg/L) (mg/g) Adsorption
1 9.02 0.97 8.05 0.12 0.01 0.90 89.18
2 23.17 3.65 19.51 0.18 0.56 1.29 84.21
3 46.34 8.53 37.80 0.22 0.93 1.57 81.51
4 95.12 21.95 73.16 0.30 1.34 1.86 76.92
5 185.36 87.80 97.55 0.90 1.94 1.98 52.63
6 285.36 182.92 102.43 1.78 2.26 2.01 35.89
7 370.73 263.41 107.31 2.45 2.42 2.03 28.94
8 463.40 353.65 109.75 3.22 2.54 2.04 23.68
9 570.65 453.65 117.08 3.87 2.65 2.06 20.51
Table 7.9: Effect of Concentration on the Adsorption of Fe (II) onto PCSB.

pH = 2.5

(mg/L) (mg/L) (mg/g) (g/ L) (mg/L) (mg/g) Adsorption
1 9.02 0.48 8.54 0.05 0.31 0.93 91.66
2 23.17 3.04 20.12 0.15 0.48 1.30 86.87
3 46.34 7.31 39.02 0.18 0.86 1.59 84.21
4 95.12 19.51 75.60 0.25 1.29 1.87 79.48
5 185.36 78.04 107.31 0.72 1.89 2.03 57.90
6 285.36 146.34 139.00 1.05 2.16 2.14 48.71
7 370.73 204.80 165.40 1.25 2.31 2.21 44.68
8 463.40 292.68 170.70 1.71 2.46 2.23 36.84
9 570.65 395.12 175.60 2.25 2.59 2.24 28.33
68
Figure 7.6: Adsorption Isotherm of Fe (II) on CSB.
Figure 7.7: Adsorption Isotherm of Fe(II) on PCSB.
The plots of Ce/qe versus Ce are linear with higher value of correlation coefficient (R2) for
the Langmuir isotherm than that of Freundlich isotherm which indicates the adsorption of
Fe(II) on all the adsorbents follows Langmuir adsorption isotherm more strictly than
Freundlich isotherm. The value of the slope was found to be lesser than unity implied that
significant adsorption took place at low metal ion concentration.
69
Figure 7.8: Langmuir Adsorption Isotherm for the Adsorption of Fe(II) on CSB.
Figure 7.9: Langmuir Adsorption Isotherm for the Adsorption of Fe (II) on PCSB.
70
Figure 7.10: Freundlich Adsorption Isotherm for the Adsorption of Fe(II) on CSB.
Figure 7.11: Freundlich Adsorption Isotherm for the Adsorption of Fe(II) onto PCSB.
71
The calculated values of Langmuir and Freundlich parameters from their respective plots
are given in the Table below:
Table 7.10: Langmuir and Freundlich Parameters and Correlation Coefficient (R2)
with Experimental qmax for the Adsorption of Fe(II) onto CSB and
PCSB.
S.N Adsorbents Expt. Langmuir Isotherm Freundlich Isotherm

qmax(mg/g)
qmax(mg/) b(L/mg) R2 k(mg/g) 1/n R2
1 SCB 117.08 117.64 0.05 0.99 12.09 0.40 0.90
2 PSCB 175.60 185.18 0.03 0.99 10.47 0.51 0.92
K is an indicator of adsorption capacity. Therefore from the above data, it is concluded

that the adsorption capacity of those adsorbents is in the order: CSB< PCSB. Another
important parameter is qmax which is the maximum quantity of metal ions per unit mass
of adsorbent to form a complete monolayer on the surface. Higher the value of qmax,
higher is the amount of metal ions adsorbed. Therefore, it is concluded that PCSB is the
best adsorbent than the CSB. PCSB and CSB have the qmax value of 117 mg/g and 175.6
mg/g which shows that PCSB better than CSB adsorbents.
7.5 Effect of pH Studies of Cr (VI)
Figure shows the effect of pH in the adsorption of Cr (VI) onto Acid modified sugarcane
bagasse at an initial concentration of 25 ppm at laboratory temperature. The amount of
adsorption decreases from 93.33% to 16.66 in case of charred bagasse when the pH of the
solution increased from 1 to 6.
72
This indicates that the adsorption of chromium is clearly dependent on pH. Effect of pH
on Cr(VI) removal shows that at lower pH, the Cr(VI) removal efficiency is higher and at
higher pH the removal efficiency is reduce considerably .
Table 7.11: Effect of pH on the Adsorption of Cr (VI) CSB.

Volume of metal solution: 25 mL
Concentration of Cr (VI) solution = 25 mg/L
Amount of adsorbent =25 mg.
Ci Ce qe %
pH pHe
(mg/L) (mg/L) (mg/L) Adsorption
1 1.4 18.75 1.25 17.50 93.33

2 2.3 20.00 3.75 16.25 81.25
3 3.5 20.00 8.75 11.25 56.25
4 3.9 20.00 11.25 8.75 43.75
5 5.6 17.50 12.50 5.00 28.57
6 6.2 15.00 12.50 2.50 16.66
The pH effects the solubility of metals in solution and the ions on the functional groups
of the adsorbent. Chromium adsorption was high for all the adsorbent at low pH values.
The adsorption capacity of all the adsorbent for Cr (VI) decreased with increasing pH
values. Generally Cr (VI) is better adsorbed at low pH values this is because at low pH Cr
(VI) is better adsorbed by the C=O functional group on the adsorbent since oxygen is
electronegative and can attract ions that are positively charged. Also at low pH there is
presence of a large number of H+ ions which in turn neutralizes the negatively charged
adsorbent surface by reducing the hindrance to the diffusion of dichromate ions. The
decrease in percentage adsorption of chromium at higher pH could be due to the high
number of hydroxyl which causes hindrance to the diffusion of chromate ions.70 The
following reaction mechanism for adsorption of Cr (VI) at different pH is proposed:
73
At lower pH, dominant form of Cr (VI) is 2HCrO4- while the surface of adsorbent is
charged positively. The H2CrO4 and CrO3 exist as poly-nuclear species at high chromium
concentration and at low pH value.
One of the reason for the better adsorption capacity observed at low pH values may be
attributed to larger number of H+ ions present at these pH values, which in turn
neutralizes the negatively charged hydroxyl groups –(OH) on adsorbed surface thereby
reducing hindrance to the diffusion of dichromate ions. At high pH, the reduction in
adsorption may be due to abundance of OH- ions causing increased hindrance to diffusion
of positively charged dichromate ions.
It is obvious that pH determines the extent of the Cr (VI) removal as well as providing a
favourable removal adsorbent surface charge for the adsorption to occur. At low pH,
chromium exists as HCrO4-. Also the reason of maximum adsorption at low pH is due to
the favourable complexation of the chromium with polyphenolic/ polyhydroxy functional
groups of the modified sugarcane waste. From the batch pH studies it was found that the
adsorption of Cr (VI) is found to be effective at pH 1.
At low value of solution pH 1 the increase in Cr (VI) adsorbed is due to electrostatic

attraction between positively charges surface functions charcoal1, 2 and HCrO4- indicating
anionic adsorption mechanism.
The most predominant forms of Cr (VI) in aqueous system are acidic chromates (HCrO4-)
chromates (CrO42-) and dichromate (Cr2O72-). From the stability diagram for the Cr (VI)-
H2O system, it is evident that acidic chromate ions are the dominant species at low pH
value. As pH increases, the proportion of acidic chromate ions in solution decreases,
which may be caused by a decrease in net positive centres on the adsorbent surface.
Consequently, the weakness of electrostatic forces between the adsorbed ions and
adsorbent leads to a decrease in the sorption capacity.
74
Figure 7.12: Effect of pH on Removal of Cr (VI) by CSB.
7.6 Batch Equilibrium Time Studies of Cr(VI)
Figure below shows the adsorption of Cr(VI) onto CSB from 10 minutes to 24 hrs
Adsorption of chromium onto this material is found to be constant after 240 minutes. The
metal adsorption capacity is high at initial time because of the presence of large number
of complexation sites. The sorption capacity decreases with time due to decrease in active
sites in the adsorbent and after saturation sorption becomes constant.
The adsorption capacity sharply increased with increase in time and attains equilibrium in
240 min (CSB). The removable rate of Cr(VI) increases with the increase of adsorption
time. However, it remains constant after an equilibrium time, which indicates that the
adsorption tends toward saturation. The rate of adsorption is higher in the beginning due
to larger available surface area of the biosorbents. After the capacity of adsorbent gets
exhausted, i.e. at equilibrium the rate of uptake is controlled by the rate at which the
adsorbate is transported from the exterior to the interior sites of biosorbents particles.5
The adsorption of Cr (VI) onto modified CSB from 10 minutes to infinite time is given in
the graph:
75
Table 7.12: Effect Contact Time for the Adsorption of Cr(VI) onto CSB.

Concentration of Cr (VI) solution = 25 mg/L
Amount of adsorbent =25 mg
S.N. Time Ci Ce qt (mg/g) t/ qt qe-qt Log 1/(qe-qt)

(min) (mg/L) (mg/L) min.g/mg (mg/g) (qe-qt)
1 10 22.5 15.00 7.50 1.33 12.5 1.09 0.92
2 20 22.5 13.75 8.75 2.28 11.25 1.05 0.95
3 30 22.5 12.50 10.00 3.00 10.00 1.00 1.00
4 40 22.5 11.25 11.25 3.55 8.75 0.94 1.06
5 50 22.5 10.00 12.50 4.00 7.50 0.87 1.14
6 60 22.5 8.75 13.75 4.36 6.25 0.79 1.26
7 90 22.5 7.50 15.00 6.00 5.00 0.69 1.45
8 120 22.5 6.25 16.25 7.38 3.75 0.57 1.75
9 180 22.5 3.75 18.75 10.13 1.25 0.09 11.11
10 240 22.5 2.50 20.00 12.00 - - -
11 300 22.5 2.50 20.00 15.00 - - -
12 24hrs 22.5 2.50 qe=20.0 72.00 - - -
Figure 7.13: Effect of Contact Time on Adsorption of Cr (VI) onto CSB.
76
7.7 Batch Kinetic Study of Cr (VI)
The kinetic data for the adsorption of Cr(VI) onto CSB were analysed by using pseudo-
first order, pseudo-second order and second order kinetic models. On studying these
plots, it was found that the adsorption of Cr (VI) onto all these adsorbents follow pseudo-
second order kinetic model with high correlation coefficient (R2) value. The plot a graph
t
for verses‘t’ we get a straight line with slope having positive value CSB and
qt
according to pseudo second order model. So adsorption studies of Cr(VI) on surface
modified waste follow pseudo-second order kinetic model.
Figure 7.14: Pseudo-first Order Kinetic Plot for the Adsorption of Cr(VI) onto CSB.
77
Figure 7.15: Pseudo-second Order Plot for the Adsorption of Cr(VI) onto CSB.
Figure 7.16: Second Order Kinetic Plot for the Adsorption of Cr(VI) onto CSB.
78
Table 7.13: Different Parameters Calculated from the Kinetic Plots Adsorbents for
Cr(VI).
T
Adsorben qexpt. Pseudo-first Order Pseudo-second Order Second Order
h
t (mg/ K1 qe R2 K2 qe Vo R2 K21 qe R2
e
) (×10-3) (×10- (×10-
3 3
) )
a
CSB 20.0 12.20 14.0 0.9 2.27 18.9 0.8 0.9 6.7 1.21 0.95
T
8 7 1 8
h
e
amount of adsorption qe (mg/g) of Cr(VI) on the respective adsorbent obtained from the
experiments was close to the qe value obtained from pseudo-second order kinetic model.
The best fitting of kinetic data to pseudo-second order implies that both Cr(VI)
adsorptions occur in a monolayer fashion and adsorption pattern occurs through chemical
adsorption or ion exchange.
7.8 Batch Isotherm Studies of Cr (VI)
The percentage of adsorption of Cr(VI) was studied by varying Cr(VI) concentration

from 10 to 400 mg/l keeping adsorbent dose, stirring speed, pH and contact time
constant. The higher concentration of metal ion was used to study the maximum
adsorption capacity of adsorbent.
The percentage of adsorption decreases with increase in the initial concentration of Cr

(VI) ion. But the actual amount of chromium adsorbed per unit mass of adsorbent was
increased with increased with concentration of solution. At low initial concentration of Cr
the removal efficiency is 94.73% and it goes on decreasing when concentration increases.
The adsorption increase at lower concentration range to higher concentration range and
attain the equilibrium. On increasing the initial concentration from 10 mg/l to 400 mg/l,
the amount adsorbed increase to 94.73 % from 36.84% for CSB.
79
Table 7.14: Effect of Concentration on the Adsorption of Cr(VI) onto CSB:
pH = 1

(mg/L) (mg/L) (mg/g) (g/L) (mg/L) (mg/g) Adsorption
1 9.5 0.50 9.0 0.05 0.30 0.95 94.73

2 18.0 1.50 16.5 0.09 0.17 1.21 91.66
3 27.0 3.00 24.0 0.12 0.47 1.38 88.88
4 45.0 7.50 37.5 0.20 0.87 1.57 83.33
5 67.5 18.75 48.75 0.38 1.27 1.68 72.22
6 95.0 30.00 65.0 0.46 1.47 1.81 68.42
7 135.0 45.00 90.0 0.50 1.65 1.95 66.66
8 180.0 70.0 110.0 0.63 1.84 2.04 61.11
9 237.5 112.5 125.0 0.90 2.05 2.09 52.53
10 285.0 150.0 135.0 1.11 2.17 2.13 47.36
11 315.0 175.0 140.0 1.25 2.24 2.14 44.44
12 380.0 240.0 140.0 1.71 2.30 2.14 36.84
Figure 7.17: Adsorption Isotherm for Cr(VI) onto CSB.
80
Adsorption of Cr(VI) onto CSB gives the linear relationship with Langmuir and
Freundlich isotherm. Langmuir and Freundlich parameters are determined from the slope
and intercept of their respective plots. The value of Langmuir equilibrium parameter lies
between 0 and 1 indicating that equilibrium data fits well with Langmuir adsorption
isotherm. It is also clear that the correlation coefficient (R2) in case of Langmuir
adsorption isotherm is greater than Freundlich adsorption isotherm which indicates that
adsorption process fits more closely to Langmuir adsorption isotherm model. This shows
that uptake of metal ions occur on a homogenous surface by monolayer adsorption
without any interaction between the adsorbed ions.
Figure 7.18: Langmuir Adsorption Plot for Cr(VI) onto CSB.
81
Figure 7.19: Freundlich Adsorption Isotherm for Cr(VI) onto CSB.
Table 7.15: Langmuir and Freundlich Parameters and Correlation Coefficient (R 2)

with Experimental qmax for the Adsorption of Cr(VI) onto CSB.
S.N. Adsorbent Expt. Langmuir Isotherm Freundlich Isotherm

qmax(mg/g) qmax b(L/m) R2 K 1/n R2
(mg/g) (mg/g)
1 SCB 140 153.84 0.041 0.98 11.26 0.50 0.94
7.9 Effect of pH of Al (III)
The effect of pH on the adsorption of Al (III) on CSB and PCSB at initial concentration
of 25 mg/L at laboratory temperature was studied. The batch study of Al (III) shows that
percentage adsorption increases from 9.09 % to 80.0 % for CSB and 16.12 % to 83.33%
for PCSB. The pH increased from 0.5 to 3 pH. Since at pH higher than 3.5 had shown
hydrolysis phenomena, there is rapid formation of insoluble Al(OH)3, i.e. rapid
precipitation occur so that continuous monitoring of pH is need which cannot be
achieved in normal lab setting. So the optimum pH 3 was chosen as the optimum pH for
adsorption of Al (III) for further analysis.
82
Table 7.16: Effect of pH on the Adsorption of Al (III) onto CSB.
Concentration of metal solution = 25 mg/L
pH pHe Ci (mg/L) Ce (mg/L) % Adsorption
0.5 0.9 18.45 17.65 9.09
1.0 1.2 19.64 11.30 33.33
1.5 2.6 17.85 8.33 53.33
2.0 2.5 17.04 6.54 65.62
2.5 2.8 17.26 4.16 75.86
3.0 3.2 17.85 3.57 80.00
Table 7.17: Effect of pH on the Adsorption of Al (III) PCSB.

pH pHe Ci (mg/L) Ce (mg/L) % Adsorption
0.5 1.0 18.45 15.47 16.12
1.0 1.5 20.23 11.90 41.11
1.5 1.6 17.85 7.14 60.00
2.0 2.6 18.45 5.35 70.09
2.5 2.9 18.45 3.57 80.64
3.0 3.5 17.85 2.97 83.33
The increase in percentage adsorption with increase of pH indicates that the adsorption
process involves the cation exchange mechanism. At low pH value, there is higher
concentration of the protons than the concentration of metal ions and protons tends to
attach with the adsorbent molecule. But at higher pH, the concentration of H+ ion is less
and they are easily replaced by the metal ions onto the adsorbent by the ion exchange
process. And the binding sites of adsorbent start deporting and the metal uptake become
difficult. Sometimes all metals assumed to adsorb at higher pH around 6. It is due to
complete hydrolysis i.e. no Al ion is remained in the solution.
83
Figure 7.20: Effect of pH on the Adsorption of Al (III) onto CSB and PCSB.
7.10 Batch Equilibrium Time Studies of Al (III)
The equilibrium time (optimized time for adsorption of Al (III) was found 5 hrs and 4 hrs
for CSB and PCSB respectively. The initial rate of adsorption is high. This is because
initially there is large number of cation exchange sites. The rate of adsorption decreases
with time due to the decrease in active sites in the adsorbent. When all the active sites are
occupied by metals ions. Equilibrium is attained and the rate of adsorption becomes zero.
84
Table 7.18: Effect of Contact Time of Al (III) CSB.
S.N. Time Ci Ce qt Log
(min) (mg/L) (mg/L) (mg/g) t/qt qe-qt (qe-qt) 1/(qe-qt)
1 5 19.04 16.07 2.97 1.68 13.68 1.13 0.073
2 10 19.04 15.47 3.56 2.80 13.09 1.11 0.076
3 15 19.04 14.28 4.75 3.15 11.90 1.07 0.084
4 30 19.04 12.50 6.54 4.58 10.11 1.01 0.098
5 45 19.04 11.90 7.13 6.31 9.52 0.97 0.105
6 60 19.04 10.71 8.32 7.21 8.33 0.92 0.120
7 75 19.04 10.11 8.92 8.40 7.73 0.88 0.129
8 100 19.04 8.92 10.11 9.89 6.54 0.81 0.152
9 120 19.04 7.73 11.30 10.61 5.35 0.72 0.186
10 150 19.04 5.95 13.08 11.46 3.57 0.55 0.280
11 180 19.04 4.76 14.27 12.61 2.38 0.37 0.420
12 240 19.04 3.57 15.46 15.52 1.19 0.07 0.840
13 300 19.04 2.38 16.65 18.01 …….. ….. …….
14 24 19.04 2.38 16.65 86.48 …… ….. ……
Table 7.19: Kinetic Study of Al (III) onto PCSB.

S.N. Time Ci Ce qt Log
(min) (mg/L) (mg/L) (mg/g) t/qt qe-qt (qe-qt) 1/(qe-qt)
1 5 20.23 14.88 5.35 0.93 13.10 1.11 0.07
2 10 20.23 14.28 5.95 1.68 12.500 1.09 0.08
3 15 20.23 13.69 6.54 2.29 11.91 1.07 0.08
4 30 20.23 12.50 7.73 3.88 10.72 1.03 0.09
5 45 20.23 11.30 8.93 5.03 9.52 0.97 0.10
6 60 20.23 9.52 10.71 5.60 7.74 0.88 0.12
7 75 20.23 8.33 11.90 6.30 6.55 0.81 0.15
8 100 20.23 7.14 13.09 7.63 5.36 0.72 0.18
9 120 20.23 6.54 13.69 8.76 4.76 0.67 0.21
10 150 20.23 4.16 16.07 9.33 2.38 0.37 0.42
11 180 20.23 2.97 17.26 10.42 1.19 0.07 0.84
12 240 20.23 1.78 18.45 13.00 …… …… ……
13 300 20.23 1.78 18.45 16.26 ……. …… ……
14 24 hrs 20.23 1.78 18.45 78.04 …… ……. ……
85
Figure 7.21: Effect of Adsorption on Contact Time.
7.11 Batch Kinetic Study of Al (III)
The kinetic data for the adsorption of Al (III) onto CSB & PCSB were analysed by using
pseudo-first order, pseudo-second order and second order kinetic models. On studying
these plots, it was found that the adsorption of Al (III) onto all these adsorbents follow
pseudo-second order kinetic model with high correlation coefficient (R2) value.
The amount of adsorption (qe) of Al (III) onto these adsorbents obtained from experiment
is close to the qe obtained from pseudo-second order plot. So, it is concluded that the
adsorption of Al (III) followed the pseudo-second order kinetic model. The best fitting of
kinetic data to pseudo second order implies that Al (III) adsorption occurs in monolayer
fashion and adsorption pattern occur through chemical adsorption or ion exchange.
86
Figure 7.22: Pseudo-first Order Kinetic Plot Al (III) onto SB.
Figure 7.23: Pseudo-second Order kinetic for Al (III) onto SB.
87
Figure 7.24: Second Order Kinetic Plot for Al (III) onto SB.
Different parameters were calculated from the kinetic plots of these adsorbents which are
shown in the table.
Table 7.20: Different Parameters Calculated from the Kinetic Plots Adsorbents for Al (III).
Adsorbent qexp Pseudo First Order Pseudo Second Order Second Order
(mg/g)
K1 qe R2 K2 qe Vo R2 K21 qe R2
(×10-3) (×10-3) (×10-3)
CSB 16.65 9.9 14.85 0.98 0.69 20.00 0.27 0.987 1.2 17.77 0.90
PCSB 18.45 12.4 15.41 0.95 0.91 21.50 0.42 0.980 1.9 28.24 0.80
7.12 The Effect of Initial Concentration of Al (III)
The effect of concentration on adsorption of Al (III) onto different adsorbent of SB is

shown below. The data shows that the percentage of adsorption decrease with increase in
the concentration of Al(III). The percentage Adsorption ranges from 82.95 to 35% for
CSB and 88.50 to 54.99% for PCSB. And the initial concentration ranges from 10 mg/L
88
to 400mg/L. Here the adsorption capacity of PCSB is found to be greater than CSB due
to chemical introduction of phosphates groups.
Table 7.21: Effect of Initial Concentration: Batch Isotherm Study of Al (III) on CSB.
pH = 3
S.N. Ci Ce qe (mg/g) Ce/qe Log Ce Log qe %

(mg/L) (mg/L) (L/g) (mg/L) (mg/L) Adsorption
1 8.33 1.42 6.91 0.20 0.15 0.83 82.95
2 17.14 3.33 13.81 0.24 0.52 1.14 80.57
3 26.42 5.00 21.42 0.23 0.69 1.33 81.07
4 46.42 9.52 36.90 0.25 0.97 1.56 79.49
5 69.64 16.07 53.56 0.30 1.20 1.72 76.92
6 92.85 23.80 69.05 0.34 1.37 1.83 74.36
7 142.85 50.00 92.85 0.53 1.69 1.96 64.99
8 195.23 85.71 109.52 0.78 1.93 2.03 55.92
9 232.14 113.00 119.52 0.94 2.05 2.07 51.32
10 285.71 164.00 121.71 1.34 2.21 2.08 42.59
11 333.33 200.00 133.33 1.50 2.30 2.12 39.99
12 380.95 247.64 133.33 1.85 2.39 2.12 35.00
Table 7.22: Effect of Initial Concentration: Batch Isotherm Study of Al (III) on PCSB.
pH = 3
S.N. Ci Ce qe (mg/g) Ce/qe Log Ce Log qe %

(mg/L) (mg/L) (L/g) (mg/L) (mg/L) Adsorption
1 8.33 0.95 7.37 0.12 0.02 0.86 88.56
2 17.14 2.38 14.75 0.16 0.37 1.16 86.10
3 26.42 4.28 22.13 0.19 0.63 1.34 83.77
4 46.42 8.33 38.08 0.21 0.92 1.58 82.04
5 69.64 14.28 55.35 0.25 1.15 1.74 79.48
6 92.85 21.42 71.42 0.29 1.33 1.85 76.92
7 142.85 39.28 103.56 0.37 1.59 2.01 72.49
8 195.23 57.14 138.08 0.41 1.75 2.14 70.73
9 232.14 83.30 148.80 0.55 1.92 2.17 64.10
10 285.71 107.14 178.56 0.60 2.02 2.25 62.50
11 333.33 125.00 208.33 0.60 2.09 2.31 62.49
12 380.95 171.42 209.52 0.81 2.23 2.32 54.99
89
7.13 Batch Isotherm Study of Al (III)
The maximum adsorption capacity of sugarcane bagasse for Aluminium was investigated
over the range of various Aluminium concentrations. The figure shows the plot of
adsorption capacity qe versus the equilibrium concentration Ce of aluminium ions in the
solution. The amount of Aluminium adsorbed was found to increase with increasing
aluminium concentration until the maximum adsorption capacity was achieved. From the
above data, it is concluded that the adsorption capacity of those adsorbents is in the order:
CSB< PCSB. Another important parameter is qmax which is the maximum quantity of
metal ions adsorbed per unit mass of adsorbent to form a complete monolayer on the
surface of adsorbent. Higher the value of qmax, higher is the amount of metal ions
adsorbed. Therefore, it is concluded that PCSB is the best adsorbent than the CSB. The
CSB and PCSB have qmax value of 133.33 mg/g and 209.52 mg/g respectively.
Adsorption Isotherm for Al(III) on CSB

160
140
120
100
qe (mg/g)
80
60
40
20
0
0 50 100 150 200 250 300
Ce (mg/L)
Figure 7.25: Adsorption Isotherm of Al (III) on CSB.
90
Figure 7.26: Adsorption Isotherm of Al (III) on PCSB.
Langmuir and Freundlich adsorption models can be used to describe the equilibrium
between adsorbed aluminium ions and aluminium ions in solution. The plots of Ce/qe
versus Ce are linear with higher value of correlation coefficient (R2) for the Langmuir
isotherm than that of Freundlich isotherm which indicates the adsorption of Al(III) on all
the adsorbents follows Langmuir adsorption isotherm more strictly than Freundlich
isotherm. The Langmuir model assumes monolayer coverage of adsorbent surface and no
interaction of adsorbate in the plane of the adsorbent surface. The value of the slope was
found to be lesser than unity implied that significant adsorption took place at low metal
ion concentration.
91
Figure 7.27: Langmuir Adsorption Isotherm for Al (III) onto CSB.
Figure 7.28: Langmuir Adsorption Isotherm for Al (III) onto PCSB.
92
Figure 7.29: Freundlich Adsorption Isotherm for Al (III) on CSB.
Figure 7.30: Freundlich Adsorption Isotherm for Al (III) on PCSB.
The calculated values of Langmuir and Freundlich parameters from their respective plots
are given in the table below.
93
Table 7.23: Langmuir and Freundlich Parameters and Correlation Coefficient (R 2)
with Experimental qmax for the Adsorption of Al(III) onto CSB and
PCSB.
S.N Adsorbents Expt. Langmuir Isotherm Freundlich Isotherm

qmax qmax b(L/mg) R2 k 1/n R2
(mg/g) (mg/g) (mg/g)
1 SCB 133.33 149.25 0.034 0.99 8.86 0.54 0.94
2 PSCB 209.52 263.15 0.021 0.99 8.01 0.68 0.97
Therefore, from the above data, it is concluded that the adsorption capacity of those
adsorbents is in the order: CSB< PCSB. Another important parameter is qmax which is
the maximum quantity of metal ions per unit mass of adsorbent to form a complete
monolayer on the surface. Higher the value of q max, higher is the amount of metal ions
adsorbed. Therefore, it is concluded that PCSB is the best adsorbent than the CSB. The
CSB and PCSB have qmax value of 133.33 mg/g and 209.52 mg/g respectively.
94
8. Conclusion
The result shows that charred sugarcane bagasse and phosphoric acid modified bagasse
have excellent sorption capacity for Fe (II) and Al (III) ions in aqueous solution the
sorption capacity qmax for Fe (II) is 117.08 mg/g for CSB and 175.60 mg/g for PCSB and
for Al (III) 133.33 mg/g for CSB and 209.52 mg/g for PCSB likewise for Cr (VI) q max is
140.00 mg/g for CSB. But for Cr (VI) only charred sugarcane bagasse have optimum
capacity for sorption. As phosphoric acid modified bagasse is not effective. The uptake
for above metals ions is pH dependent and the maximum biosorption capacity was
obtained at pH 2.5 for Fe(II) and 3.0 for Al(III) and 1.0 for Cr(VI). The adsorption data
followed pseudo-second order kinetic model for all three metals ions which indicates
chemisorptions as the limiting step in adsorption process. The Freundlich and Langmuir
biosorption models were used for the mathematical description of the biosorption
equilibrium of all these metal ions to biosorbents. The biosorption equilibrium data fitted
well to the Langmuir isotherm model, which suggest monolayer coverage of adsorbent
surface. This works shows that sugarcane bagasse could be used as a good adsorbent
material for these heavy metals. Hence Sugarcane Bagasse is an abundant waste material
and available almost free of cost, low cost bio-wastes can be used for the removal of
Fe(II) , Cr(VI) and Al(III) from water and wastewater. Biosorption is being demonstrated
as a useful alternative to conventional system for removal of toxic metals from industrial
effluents.
95
Determination of Cr(VI) DPCI
S.N. Concentration of Concentration Mean Standard 95%

Cr taken (mg/L) of Cr found Deviation
(mg/L) Confidence
Limit
10.0 10.20
10.0 9.80
0.20 9.90±0.318
1 10.0 9.80 9.90
10.0 9.80
20.0 19.80
20.0
2 20.20 0.20 19.90±0.318
2 20.0 19.80 19.90
20.0 19.80
3 30.0 30.40
30.0 30.00 30.10 0.20 30.10±0.318
30.0 30.00
30.0 30.00
40.0 40.20
4 40.0 39.80 39.90 0.20 39.9±0.318
40.0 39.80
40.0 39.80
Determination of Fe (II) by 1, 10-Phenonthroline
S.N. Concentration of Concentration Mean Standard 95%

Fe taken (mg/L) of Fe found Deviation
(mg/L) Confidence
Limit
25.0 22.5
25.0 25.0
1.25 24.375±1.99
1 25.0 25.0 24.375
25.0 25.0
50.0 50.0
50.0
2 50.0 1.25 49.375±1.99
2 50.0 50.0 49.375
50.0 47.5
3 75.0 75.0
75.0 75.0 74.375 1.25 74.375±1.99
75.0 72.0
75.0 75.0
100.0 100.0
4 100.0 100.0 99.375 1.25 99.375±1.99
100.0 100.0
100.0 97.5
96
Determination of Al (III) by Eriochrome Cyanine R.
S.N. Concentration Concentratio Mean Standard 95%

of Al taken n of Al Deviation
(mg/L) found Confidence
(mg/L) Limit
1.25 1.25
1.25 1.25
0.102 1.25±0.162
1 1.25 1.37 1.25
1.25 1.13
2.50 2.50
2
2.50 2.50 0.102 2.50±0.162
2 2.50 2.62 2.50
2.50 2.37
3 5.00 5.00
5.00 5.00 5.00 0.102 5.00±0.162
5.00 5.12
5.00 4.88
7.50 7.50
4 7.50 7.50 7.50 0.102 7.50±0.162
7.50 7.37
7.50 7.63
Table 7.27: Comparison of Maximum Adsorption Capacity (qmax) between

Various Bioadsorbent.
Bioadsorbent Metal Ions Maximum Referen

Adsorption ces
Capacity
(qmax)
(mg/g)
Charred Sugarcane Baggase Fe(II) 117.08
Charred Sugarcane Baggase Cr(VI) 140.00
Charred Sugarcane Baggase Al(III) 133.33 Present
Phosphorylated Charred Sugarcane Baggase Fe(II) 175.60 study
Phosphorylated Charred Sugarcane Baggase Al(III) 209.52
Charred Apple Waste Fe(II) 88.64 [71]
Charred Apple Waste Cr(VI) 85.19
Charred Apple Waste Al(III) 131.49
Phosphorylated Charred Apple Waste Fe(II) 112.04
Phosphorylated Charred Apple Waste Al(III) 139.93
97
Iron Loaded Charred Orange Waste (FeCOW) As (III) 10.00 [72]
Iron Loaded Charred Orange Waste (FeCOW) As(V) 45.0 0
Iron Loaded Charred Orange Waste (FeCOW) PO4– (phosphate) 105.00
Iron Loaded Charred Apple Waste (FeCAW) As (III) 83.333 [73]
Iron Loaded Charred Apple Waste (FeCAW) As(V) 81.25
Iron Loaded Charred Apple Waste (FeCAW) PO4– (phosphate) 100.00
Iron Loaded Charred Sugarcane Baggase(FeCSB) As (III) 25.00 [74]
Iron Loaded Charred Sugarcane Baggase(FeCSB) As(V) 52.50
Iron Loaded Charred Sugarcane Baggase(FeCSB) PO4-(phosphate) 70.00
98
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103

Adsorptive Removal of Iron (II), Aluminium (III) and Chromium (Vi) From Aqueous Solution by Charred and Phosphorylated Sugarcane Bagasse

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Adsorptive Removal of Iron (II), Aluminium (III) and Chromium (Vi) From Aqueous Solution by Charred and Phosphorylated Sugarcane Bagasse

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ADSORPTIVE REMOVAL OF IRON (II), ALUMINIUM (III) AND CHROMIUM (VI)

FROM AQUEOUS SOLUTION BY CHARRED AND PHOSPHORYLATED

Salik Ram Dahal

CENTRAL DEPARTMENT OF CHEMISTRY

Salik Ram Dahal

CENTRAL DEPARTMENT OF CHEMISTRY

This dissertation work entitled “ADSORPTIVE REMOVAL OF IRON (II), ALUMINIUM

_________ _ ___ ____ _

Date: September, 2013

Salik Ram Dahal

It is a matter of great pleasure to express my sincere gratitude to my research supervisor

Salik Ram Dahal

AAS = Atomic Absorption Spectroscopy

Key Words: Modified Charred Sugarcane Bagasse, Phosphorylated Charred Sugarcane

1.1 General Introduction

1.2 Low Cost Adsorbents and Importance of Biosorption

1.3 Adsorptive Study

1.4 Structure of Lignin and Cellulose

1.5 Adsorption Isotherms

1.5.1 Langmuir Adsorption Isotherm

1.5.2 Freundlich Adsorption Isotherm

1.6 Adsorption Kinetics

1.6.1 The Pseudo First Order Kinetics Model

1.6.2 The Pseudo Second Order Kinetics Model

1.6.3 The Second Order Kinetics Model

2. Objectives of the Study…………………………………………………………15

2.1 General objectives

2.2 Specifics objectives

3. Literature Survey ………………………………………................................16-21

4. Scope and Limitations of the Study…………………………………………22

5.1 Instrument Used

5.1.1 Chemiline Digital pH Meter. CL-110, Electrode HI-1230

5.1.2 Spectrophotometer, WPA Linton(S-104), Cambridge, UK

5.1.3 V.D.R.L SHAKER, Accuma X India

5.2 Preparation of Reagents

5.2.1 1000 ppm Stock Iron Solution

5.2.2 Potassium Dichromate (K2Cr2O7) Stock Solution (1000 ppm).

5.2.3 Aluminium Stock Solution [KAl(SO4)2.12H20]

5.2.4 5M Sulphuric Acid Solution (approx)

5.2.5 5M Sodium Hydroxide Solution (approx)

5.2.6 5M Nitric Acid Solution (approx)

5.2.7 Preparation of 0.25% 1,5 Diphenycarbazide (DPCI) Solution

5.2.8 Buffer Solution pH 4

5.2.9 Buffer Solution of pH 7

5.2.10 Buffer Solution of pH 9.2

5.2.11 10% Hydroxyl Amine Hydrochloride Solution

5.2.12 1, 10-Phenanthroline Hydrochloride Solution

5.2.13 0.2% Eriochrome Cynine R[C23H15Na3O9S] Solution

5.2.14 Ammonium Acetate Buffer Solution

5.2.15 0.1M Nitric Acid

5.2.16 0.02N Sodium Carbonate Solution

5.2.17 0.02 N NaHCO3 Solution

5.2.18 0.02 N NaOH Solution

5.2.19 0.02 N HCl Solution

5.2.21 0.1N HNO3 Solution (approx)

5.2.22 2M NaOH Solution (approx)

5.3 Preparation of Adsorbents from Sugarcane Bagasse………………….....26-32

5.3.1 Preparation of Raw Sugarcane Bagasse.

5.3.2 Acid Modifications

5.3.3 Phosphorylation of Charred Adsorbents

5.3.4 Effects of Chemical Modification

5.3.5 Plausible Mechanism of Adsorbents

Determination of λmax and Construction of Calibration Curve

6.1 Construction of Calibration Curve for Iron

6.2 Construction of Calibration Curve for Aluminium

6.3 Construction of Calibration Curve for Chromium

6.4 Batch Adsorption Studies

_________ _ _ __ _