Okoye - A - I - PG - M.SC - 07 - 42985 (JURNAL PENTING 15062017) PDF

PREPARATION, CHARACTERIZATION AND
ADSORPTIVE EVALUATION OF ACTIVATED

CARBON FROM Telfairia occidentalis AND
Gambeya albida SEED SHELLS
BY
OKOYE, AMALACHUKWU I.
PG/M.Sc/07/42984
DEPARTMENT OF PURE AND INDUSTRIAL

CHEMISTRY
UNIVERSITY OF NIGERIA, NSUKKA
OCTOBER, 2010
PREPARATION, CHARACTERIZATION AND
ADSORPTIVE EVALUATION OF ACTIVATED
CARBON FROM Telfairia occidentalis AND
Gambeya albida SEED SHELLS
BY
OKOYE, AMALACHUKWU I.
PG/M.Sc./07/42984
A RESEARCH PROJECT SUBMITTED IN PARTIAL

FULFILLMENT OF THE REQUIREMENTS FOR THE
AWARD OF MASTER OF SCIENCE (M.Sc.) DEGREE IN
INDUSTRIAL CHEMISTRY IN THE DEPARTMENT OF
PURE AND INDUSTRIAL CHEMISTRY, UNIVERSITY OF
NIGERIA, NSUKKA.
OCTOBER, 2010
i
TITLE
PREPARATION, CHARACTERIZATION AND ADSORPTIVE EVALUATION OF

ACTIVATED CARBON FROM Telfairia occidentalis AND Gambeya albida SEED
SHELLS
ii
APPROVAL
OKOYE, Amalachukwu I, a postgraduate student in the Department of Pure and
Industrial Chemistry with Registration Number PG/M.Sc./07/42984 has satisfactorily
completed the requirements for research work for the degree of M.Sc. in Industrial
Chemistry.
Prof. O. D. Onukwuli Dr. P.O. Ukoha

Supervisor Head of Department
External Examiner
iii
DEDICATION
This work is dedicated to Almighty God and to my loved ones.

iv
ACKNOWLEDGEMENT
I wish to express my profound gratitude to my supervisor, Professor O.D Onukwuli, whose
guidance and advice enabled me to carry through this project. I also greatly appreciate Mr
P.M Ejikeme for his many useful suggestions during the course of this project.
My appreciation also goes to Mr F. Sale of Kogi State University, Ayingba, who ensured the
prompt analyses of my samples. I also thank the staff of Soil Science Department, UNN,
especially Miss Ngozi and Mr Attamah, who provided me with most of the equipments I
needed during the early stages of my laboratory work. Likewise, I greatly thank the staff of
National Centre for Energy Research and Development, UNN, especially Mr A.C. Ofomatah,
who provided me with most of the equipments I needed during the latter stages of the
laboratory work.
I am also very grateful to my parents and brothers whose support and encouragement
sustained me throughout my period of study. Finally, my appreciation goes to all my friends
and well-wishers and to all others who in one way or the other helped me during my period of
study.
v
ABSTRACT
Activated carbons were produced from fluted pumpkin (Telfairia occidentalis) seed shell
(TOSS) and star apple (Gambeya albida) seed shell (GASS). Phosphoric acid and ammonium
chloride were used as activating agents. Carbonization was carried out at different four
different temperatures (from 300 to 600oC) and for different lengths of time (from 60 to
120minutes). Each of the adsorbents produced was characterized and their potential for
removal of Pb2+ and Cu2+ from solution was determined. Phosphoric acid activated carbons
were found to have better adsorption properties than ammonium chloride activated carbons.
Increase in carbonization temperature and time resulted in carbons with higher adsorption
potentials. Adsorption equilibrium was attained between 130 170 minutes. Adsorption
decreased with increase in adsorption temperature and particle size and increased with
increase in initial concentration of the metal ions and adsorbent weight. Adsorption also
increased with increase in pH of the metal solutions up to a pH value of 5, beyond which the
metal ions were precipitated out of their solutions as their hydroxides. Lead was more
effectively adsorbed than copper by both adsorbents. Kinetic studies showed that the
adsorption processes were best fitted by the pseudo-second order equation except the
adsorption of 50mg/l of Cu2+ on activated carbon from Gambeya albida seed shell, which
was best fitted by the pseudo-first order equation. The rates of the adsorption processes were
controlled by film (boundary layer) diffusion. The adsorption processes were exothermic in
nature and involved monolayer coverage of the metal ions on the adsorbents.
vi
TABLE OF CONTENTS
TITLE PAGE .i
APPROVAL PAGE...ii
DEDICATION..iii
ACKNOWLEDGEMENTiv
ABSTRACT...v
TABLE OF CONTENTS..vi
LIST OF FIGURES...ix
LIST OF TABLES ...xi
CHAPTER ONE: INTRODUCTION ..1
1.1 Research Objectives ................3
CHAPTER TWO: LITERATURE REVIEW5
2.1 Historical Background of Activated Carbon5

2.2 Methods of Production of Activated Carbon.11
2.2.1 Carbonization......................................13
2.2.2 Activation....13
2.3 Characteristics of Activated Carbon ..15
2.3.1 Classifications of Activated Carbon........................16
2.3.2 Properties of Activated Carbon...18
2.3.2.1 Physical properties...19

2.3.2.2 Chemical properties..23
2.4 Adsorption Phenomenon................25
2.4.1 Adsorption Isotherm........................27
2.4.1.1Langmuir Isotherm....28
2.4.1.2 Freundlich Isotherm.........................30
2.4.1.3 Temkin Isotherm..32
2.4.2 Adsorption Kinetics.33

2.4.2.1 Bhattacharya-Venkobachar Model...33
vii
2.4.2.2 Lagergren Pseudo-first Order Model...34
2.4.2.3 Pseudo-second Order Model................................35
2.4.2.4 Elovich Model..........................36
2.4.2.5 Intra-particle and Film Diffusion Kinetics...36
2.4.3 Previous Work on Pb2+ and Cu2+ Removal from Simulated Waste
Water...38
CHAPTER THREE: EXPERIMENTAL.....43
3.1 Chemicals and Instrumentation..43
3.2 Production of Activated Carbon.....43
3.2.1 Effect of Activating Conditions..43
3.2.2 Effect of Carbonization Temperature..44
3.2.3 Effect of Carbonization Time..44
3.3 Characterization of Adsorbents..44
3.3.1 Determination of Yield and Weight Loss............44
3.3.2 Surface Area Measurement.....45
3.3.3 Determination of Ash Content....................45
3.3.4 Determination of Bulk Density...46
3.3.5 Determination of Total Pore Volume..46
3.4 Adsorption Tests46
3.4.1 Effect of Particle Size.....47
3.4.2 Effect of Solution pH.....47
3.4.3 Effect of Adsorbent Weight...48
3.4.4 Effect of Temperature.48
3.5 Kinetic Study..48
3.6 Isotherm Study...............48
CHAPTER FOUR: RESULTS AND DISCUSSION..49
4.1 Characterization of Adsorbents..............................49

viii
4.1.1 Characterization of Adsorbents Produced Using Different Activating

Agents..49
4.1.2 Characterization of Adsorbents Carbonized at Different
Temperatures..51
4.1.3 Characterization of Adsorbents Carbonized for Different Lengths of

Time....52
4.2 Effect of Process Variables on Adsorption....53
4.2.1 Effect of Activating Agent on Adsorption..53
4.2.2 Effect of Carbonization Temperature on Adsorption..55
4.2.3 Effect of Carbonization Time..57
4.3.4 Effect of Particle Size on Adsorption..59
4.2.5 Effect of Solution pH on Adsorption .61
4.2.4 Effect of Adsorbent Weight on Adsorption ..62
4.2.7 Effect of Adsorption Temperature on Amount of Metals Adsorbed.64
4.2.8 Effect of Contact Time and Initial Metal Ion Concentration on

Adsorption...65
4.3 Kinetic Studies...69
4.3.1 Kinetic analysis of Pb2+ adsorption on TOSS carbon.69
4.3.2 Kinetic analysis of Cu2+ adsorption on TOSS carbon.73
4.3.3 Kinetic analysis of Pb2+ adsorption on GASS carbon.78
4.3.4 Kinetic analysis of Cu2+ adsorption on GASS carbon82
4.4 Isotherm Studies.86
4.4.1 Isotherm study of Pb2+ adsorption on TOSS carbon..86
4.4.2 Isotherm study of Cu2+ adsorption on TOSS carbon..90
4.4.3 Isotherm study of Pb2+ adsorption on GASS carbon..93
4.4.4 Isotherm study of Cu2+ adsorption on GASS carbon..96
CHAPTER FIVE: CONCLUSION..99
REFERENCES...101
ix
LIST OF FIGURES
Figure 2.1: Activated carbon particle...18
Figure 4.1: Effect of Carbonization Temperature on Amount of Metal Adsorbed..55
Figure 4.2: Effect of Carbonization Time at 500oC for TOSS and 600oC for GASS on
Amount of Metal Adsorbed57
Figure 4.3: Effect of Particle Size on Amount of Metals Adsorbed59

Figure 4.4: Effect of Solution pH on Amount of Metals Adsorbed.61
Figure 4.5: Effect of Adsorbent Weight on Amount of Metals Adsorbed...63
Figure 4.6: Effect of Adsorption Temperature on Amount of Metals Adsorbed ....64
Figure 4.7: Effects of Contact Time and Initial Concentration of Pb2+ on its Amount
Adsorbed using TOSS carbon....66
Figure 4.8: Effects of Contact Time and Initial Concentration of Cu2+ on its Amount
Adsorbed using TOSS carbon66
Adsorbed using GASS carbon....67
Figure 4.10: Effects of Contact Time and Initial Concentration of Cu2 on its Amount
Adsorbed using GASS carbon..67
Figure 4.11: Bhattacharya-Venkobachar Plot for Pb2+ Adsorption on TOSS Carbon.69
Figure 4.12: Pseudo First Order Plot for Pb2+ Adsorption on TOSS Carbon...70
Figure 4.13: Elovich Plot for Pb2+ Adsorption on TOSS Carbon70

Figure 4.14: Pseudo Second Order Plot for Pb2+ Adsorption on TOSS Carbon..71
Figure 4.15: Weber and Morris Plot for Pb2+ Adsorption on TOSS Carbon71
Figure 4.16: Bhattacharya-Venkobachar Plot for Cu2+ Adsorption on TOSS Carbon.....74
Figure 4.17: Pseudo First Order Plot for Cu2+ Adsorption on TOSS Carbon..74
Figure 4.18: Elovich Plot for Cu2+ Adsorption on TOSS Carbon...75
Figure 4.19: Pseudo Second Order Plot for Cu2+ Adsorption on TOSS Carbon..75
Figure 4.20: Weber and Morris Plot for Cu2+ Adsorption on TOSS Carbon ..76
Figure 4.21: Bhattacharya-Venkobachar Plot for Pb2+ Adsorption on GASS Carbon.78
Figure 4.22: Pseudo First Order Plot for Pb2+ Adsorption on GASS Carbon..79
Figure 4.23: Elovich Plot for Pb2+ Adsorption on GASS Carbon...79

Figure 4.24: Pseudo Second Order Plot for Pb2+ Adsorption on GASS Carbon..80
x
Figure 4.25: Weber and Morris Plot for Pb2+ Adsorption on GASS Carbon...80
Figure 4.26: Bhattacharya-Venkobachar Plot for Cu2+ Adsorption on GASS Carbon82
Figure 4.27: Pseudo First Order Plot for Cu2+ Adsorption on GASS Carbon.83
Figure 4.28: Elovich Plot for Cu2+ Adsorption on GASS Carbon..83

Figure 4.29: Pseudo Second Order Plot for Cu2+ Adsorption on GASS Carbon.84
Figure 4.30: Weber and Morris Plot for Cu2+ Adsorption on GASS Carbon..84
Figure 4.31: Langmuir Isotherm for Pb2+ adsorption on TOSS Carbon..87
Figure 4.32: Freundlich Isotherm for Pb2+ adsorption on TOSS Carbon.88
Figure 4.33: Temkin Isotherm for Pb2+ adsorption on TOSS Carbon..88
Figure 4.34: Langmuir Isotherm for Cu2+ adsorption on TOSS Carbon..90
Figure 4.35: Freundlich Isotherm for Cu2+ adsorption on TOSS Carbon91
Figure 4.36: Temkin Isotherm for Cu2+ adsorption on TOSS Carbon.91
Figure 4.37: Langmuir Isotherm for Pb2+ adsorption on GASS Carbon..93
Figure 4.38: Freundlich Isotherm for Pb2+ adsorption on GASS Carbon94
Figure 4.39: Temkin Isotherm for Pb2+ adsorption on GASS Carbon.94
Figure 4.40: Langmuir Isotherm for Cu2+ adsorption on GASS Carbon.96
Figure 4.41: Freundlich Isotherm for Cu2+ adsorption on GASS Carbon97
Figure 4.42: Temkin Isotherm for Cu2+ adsorption on GASS Carbon.97
xi
LIST OF TABLES
Table 2.1: Pore Classifications by Pore Width21
Table 2.2: Amount of Water Soluble Inorganic Substances in Carbon...24
Table 4.1: Effect of Activating Agent on Properties of Gambeya albida Seed Shell......49
Table 4.2: Effect of Activating Agent on Properties of Telfairia occidentalis Seed Shell..50
Table 4.3: Effect of Carbonization Temperature on Properties of Adsorbents Produced
Using H3PO4 as Activating Agent ......51
Table 4.4: Effect of Carbonization Time on Properties of Adsorbents Produced Using

H3PO4 as Activating Agent at 500oC for TOSS and 600oC for GASS ......53
Table 4.5: Effect of Activating Agent on Adsorption Parameters using Gambeya albida
Seed Shell Processed at 600oC53
Table 4.6: Effect of Activating Agent on Adsorption Parameters using Telfairia

occidentalis Seed Shell Processed at 500oC ...54
Table 4.7: Effect of Carbonization Temperature on Adsorption of Pb2+.....55

Table 4.8: Effect of Carbonization Temperature on Adsorption of Cu2+.56
Table 4.9: Effect of Carbonization Time at 500oC for TOSS and 600oC for GASS on
Adsorption of Pb2+...58
Table 4.10: Table 4.10: Effect of Carbonization Time at 500oC for TOSS and 600oC for
GASS on Adsorption of Cu2+...58
Table 4.11: Effect of Particle Size on Adsorption of Pb2+...60
Table 4.12: Effect of Particle Size on Adsorption of Cu2+...60
Table 4.13: Effect of Solution pH on Adsorption of Pb2+....61
Table 4.14: Effects of Solution pH on Adsorption of Cu2+..62
Table 4.15: Effects of Adsorbent Weight on Adsorption of Pb2+....63
Table 4.16: Effect of Adsorbent Weight on Adsorption of Cu2+.63

Table 4.17: Effect of Temperature on Adsorption of Pb2+...65
Table 4.18: Effect of Temperature on Adsorption of Cu2+..65
Table 4.19: The Kinetic Parameters for Pb2+ Adsorption on TOSS Carbon....72
Table 4.20: Intra-particle and Film Diffusion Constants for Pb2+ Adsorption on TOSS
Carbon...73
Table 4.21: The Kinetic Parameters for Cu2+ Adsorption on TOSS Carbon...77
xii
Table 4.22: Intra-particle and Film Diffusion Constants for Cu2+ Adsorption on TOSS
Carbon...78
Table 4.23: The Kinetic Parameters for Pb2+ Adsorption on GASS Carbon....81
Table 4.24: Intra-particle and Film Diffusion Constants for Pb2+ Adsorption on GASS
Carbon...82
Table 4.25: The Kinetic Parameters for Cu2+ Adsorption on GASS Carbon...85
Table 4.26: Intra-particle and Film Diffusion Constants for Cu2+ Adsorption on GASS
Carbon...86
Table 4.27: Isotherm Data for Pb2+ Adsorption on TOSS Carbon..87
Table 4.28: The Isotherm Parameters for Pb2+ Adsorption on TOSS Carbon.89
Table 4.29: Isotherm Data for Cu2+ Adsorption on TOSS Carbon..90
Table 4.30: The Isotherm Parameters for Cu2+ Adsorption on TOSS Carbon.....92
Table 4.31: Isotherm Data for Pb2+ Adsorption on GASS Carbon..93
Table 4.32: The Isotherm Parameters for Pb2+ Adsorption on GASS Carbon.95
Table 4.33: Isotherm Data for Cu2+ Adsorption on GASS Carbon..96
Table 4.34: The Isotherm Parameters for Cu2+ Adsorption on GASS Carbon.98
Table A.1: Effects of Contact Time using Telfairia occidentalis Seed Shell Activated
Carbon with 50mg/l of Pb2+.111
Carbon with 100mg/l of Pb2+...111
Carbon with 150mg/l of Pb2+...112
Carbon with 200mg/l of Pb2+..112
Carbon with 50mg/l of Cu2+.113
Carbon with 100mg/l of Cu2+...113
Table A.9: Effects of Contact Time using Gambeya albida Seed Shell Activated
xiii
Carbon with 50mg/l Pb2+....115

Carbon with 100mg/l Pb2+..115
Carbon with 50mg/l Cu2+...117
Carbon with 100mg/l Cu2+.117
1
CHAPTER ONE
INTRODUCTION
In recent years, increasing awareness of water pollution and its harmful effects has incited
diverse efforts towards pollution abatement. The rate at which effluents are discharged into
the environment and water bodies, have been on the increase due to rapid growth of cities in
the world. Generally, water bodies are major sites of heavy metal deposits due to the fact that
streams and rivers flow through agricultural areas where pesticides and fungicides may have
been used, through industrial districts where there may have been many metals wastes
deposits or direct discharge of effluents into these water bodies. The primary sources of
heavy metals pollution in coastal lagoons are input from rivers, sediments and atmosphere,
which can affect aquaculture profitability in certain areas1. The anthropogenic sources of
heavy metals include wastes from the electroplating and metal finishing industries,
metallurgical industries, tannery operations, chemical manufacturing, mine drainage, battery
manufacturing, leather and tanning industries, fertilizer industries, pigment manufacturing
industries, leachates from land fills and contaminated ground water from hazardous waste
sites2. Heavy metals are also emitted from resource recovery plants in relatively high levels
on fly ash particles3. Metal ions in water can also occur naturally from leaching of ore
deposits. The presence of heavy metal contaminants in the treated or untreated waste water
from the industries either producing or using these metal bearing products introduces these
metals into water bodies4.
These metal pollutants are conservative contaminants that are not easily degradable
chemically or biologically. They are therefore permanent chemical overload in the
environment5. When these metals are present in significant quantities in the environment they
constitute source of pollution and pollutants and pose threat to the environment, human,
2
animal and aquatic lives, even though in small quantities they can be beneficial in the
sustenance of life. The toxicity of metal ions is owing to their ability to bind with protein
molecules and prevent replication of DNA and thus subsequent cell division6.
Lead is one of these heavy metals with high toxicity when in excess. In children, lead causes
a decrease in intelligent quotient (IQ) score, retardation of physical growth, hearing
impairment, impaired learning as well as decreased attention and classroom performance. In
individuals of all ages, lead can cause anaemia, kidney malfunction, brain diseases and
impaired function of peripheral nervous system, high blood pressure, reproduction
abnormality, developmental defects, abnormal vitamin D metabolism, colic-like abnormal
pains, dementia, madness and, in some situations, death7. Lead as Pb2+ ion has a large affinity
for the thio (-SH) and phosphate ion (PO4) containing enzymes, ligands and bio molecules,
thereby, inhibiting the biosynthesis of haeme units, affecting membrane permeability of
kidney, liver, and brain cells. These result in either reduced functions or complete breakdown
of these organs8. Lead forms complexes with oxo-groups in enzymes to affect virtually all
steps in the process of heamoglobin synthesis and porphyrin metabolism9.
Copper is another heavy metal with high toxicity when in excess. It has been reported as one
of the most widely used heavy metal and is mainly employed in electrical and electroplating
industries10. It is, also, an essential trace element for human beings. However, it can cause
harmful and acute effects. The major effects of excessive large doses of copper in the human
body include high blood pressure, severe mucosal irritation, widespread capillary damage,
anemia, hepatic damage and necrotic changes in the liver and kidney11.
The bioaccumulation of these metal pollutants has increased the interest of researchers in
developing suitable remediation strategies12. Presently, the majority of heavy metals in
wastewater are removed by means of precipitation by adding calcium hydroxide, in which

3
large amounts of nontoxic metal compounds such as calcium sulfate are also precipitated
together with heavy metals as a precipitated sludge, which are dumped in the landfill sites. It
is not only difficult to meet stringent environmental regulation by means of precipitation
technique, but also unavailability of landfill sites due to the occupation by large amounts of
polluted sludge. Adsorptive recovery and removal using ion exchange chelating resin are also
used. However this approach is expensive taking account of the post-treatment of spent resin,
and, in addition, it also poses other environmental problems if such synthetic plastic materials
are incinerated13. Oxidation, reduction, sedimentation, lime softening, sorptive floatation,
reverse osmosis, electrodialysis, ultrafiltration, phytoremediation, etc. have also been
employed. These methods also have disadvantages like high cost, not being readily available,
introducing novel chemicals into the environment and not being environmentally friendly14.
The need to develop an alternative, more environmentally friendly and cost effective method
therefore became imperative. Adsorption is one of the easiest, safest and most cost-effective
methods for the removal of these metals15. The major advantage of an adsorption system for
water pollution control are less investment in terms of both initial cost and land, simple
design and easy operation and no effect of toxic substances compared to conventional
biological treatment processes16. Activated carbon can be used to remove heavy metal
pollutants from wastewater due to its good adsorption properties17.
1.1 Research Objectives
The objectives of this work are:
To determine the optimum production conditions of low cost activated carbon from
fluted pumpkin (Telfairia occidentalis) and star apple (Gambeya albida) seed shells.
To characterize the activated carbons produced.

4
To determine their potentials for the removal of Pb2+ and Cu2+ from simulated waste
water.
To test the data obtained from the work on various kinetic models, and
To also determine the isotherm behaviour of the adsorption processes.

5
CHAPTER TWO
LITERATURE REVIEW
2.1 Historical Background of Activated Carbon
The use of activated carbon in the form of carbonized wood began many centuries ago.
During the 1500s BC, it was used by the Egyptians as a purifying agent and also as an
adsorbent for medicinal purposes in which it was used to adsorb odour from rotten wounds18.
In 1773, Scheele recognized the specific adsorptive powers charcoal had with various gases19.
In 1777, Fontanna disclosed an experiment in which glowing charcoal was plunged under
mercury and allowed to rise into an inverted tube containing a gas, whereupon much of the
gas disappeared20. In 1785, Lowitz21 observed the ability of charcoal to decolorize many
liquids. In 1794, natural forms of activated carbon, such as charred animal bones (called bone
black), were used for the refinement of sugar22.
Since the 1800s, production of activated carbon moved from woody precursors and bones to
various other precursors in search of more effective adsorbents. In 1822, Bussy applied heat
to a mixture of potash and blood which resulted in carbon with much more decolourizing
effect than bone char and was called blood char23. In 1856, Stenhouse, prepared a
decolorizing char by heating a mixture of flour, tar, and magnesium carbonate and in 1863,
Lee prepared a deodorizing carbon by the action of superheated steam and air on peat20.
Commercial production of activated carbon started first in Europe in 1909 with the
production of a powdered carbon called Eponite24. The manufacture of higher quality gas-
adsorbent carbons was given new encouragement in the period of World War I, during which
they were used in gas masks for protection against poisonous gases25. In 1929, Spadling26
demonstrated that activated carbon could correct taste conditions in municipal waste supplies
6
at a very moderate cost. In 1963, activated charcoal became more widely accepted in the
management of ingested toxins27. In 1970, Smisek Cerny28 discussed the general principles of
production of low cost chemically activated carbon from several materials such as sawdust,
rice husk, etc. using activating agents like ZnCl2, potassium sulphide, H2SO4 and phosphoric
acid.
Since the 1980s, attention has shifted to the production of activated carbon from low cost
materials. Agricultural by-products and wastes have been seen to help achieve this goal. In
1986, Laine et al29 prepared activated carbon from coconut shell by impregnation with
phosphoric acid in a one-step carbonization process. They studied the effect of carbonization
temperature on the surface area of the produced carbons and found that the optimum
temperature for a high surface area was 450C.
Ozer et al30 in 1996 prepared activated carbon by carbonizing sugar beet pulp in a constant
flow rate of carbon dioxide at different temperatures and for different lengths of time. They
found that percentage yield of activated carbon decreased while percentage ash content and
pH increased with increase in carbonization temperature from 350oC to 750oC and with
increase in carbonization time from 15 to 120minutes. The produced carbons were tested for
adsorption of Cd2+ and the most effective activated carbon for the adsorption process was the
one produced by carbonization at 700oC for 120minutes. They also found the optimum pH
for the adsorption process to be 7 and adsorption equilibrium was attained after a contact time
of 120minutes. They carried out isotherm studies of the adsorption process and found that the
adsorption of Cd2+ was better described by Langmuir isotherm than Freundlich isotherm.
In 1999, Guo and Lua31 prepared activated carbon from oil-palm stone by pre-treatment with
H2SO4 and KOH and carried out textural and chemical characterisations of the prepared
carbons. They carried out adsorption of SO2 and NH3 on the produced carbons and found that
7
the activated carbons pre-treated with KOH adsorbed more SO2 but less NH3 than those pre-
treated with H2SO4. From chemical characterisation of the prepared carbons, they found that
the samples pre-treated with H2SO4 presented acidic groups such as phenols and carboxylic
acids, whereas those pre-treated with KOH showed alkaline groups, which they suggested to
be pyrones (cyclic ketone) and other keto-derivatives of pyran. They concluded that the
activated carbons prepared from oil-palm stones by impregnation with KOH and H2SO4 are
suitable for use as gas-phase adsorbents for the removal of acidic and alkaline gases,
respectively.
In 2004, Girgis et al32 prepared activated carbon from sugar cane bagasse by impregnation
with 50% inorganic acids and carbonization at 500oC for three hours. They found the
produced carbons to show the sequence H3PO4 > H2SO4 > HCl > HNO3, with respect to
efficiency of activation. They studied the effect of carbonization temperature on the
properties of the carbons using phosphoric acid as activating agent. Their results show that
the surface area and total pore volume increased with increase in carbonization temperature
from 300oC to 500oC. They also found that increase in the period of carbonization led to a
small decrease in both surface area and pore volume.
Gaikwad33 in 2004 prepared activated charcoal from coconut shell and the produced carbon
was found to have a surface area of 630.80m2/g and porosity of 0.5ml/g. The carbon was
tested for adsorption of Cd(II) ion from aqueous solution and they found that adsorption
increased with increase in pH up to a value of 6, after which it decreased with further increase
in pH. Adsorption equilibrium was attained after 80minutes.
In 2005, Tawalbeh et al34 prepared activated carbon from jojoba seed residue by chemical
activation in a static bed reactor using zinc chloride, potassium chloride and phosphoric acid
as activating agents. They found that the activated carbon produced by activation with zinc
8
chloride had higher iodine number (adsorptive capacity) than the potassium chloride and
phosphoric acid activated carbons. They also studied the effect of carbonization temperature
and time on the production of carbons from the jojoba seed residue. Their results show that
percentage yield of activated carbon decreased while iodine number increased with increase
in carbonization temperature and time. They concluded that for the production of activated
carbon from jojoba seed residue by chemical activation using a static bed reactor, the
optimum carbonization temperature and time are 600oC and 90minutes, respectively.
Arivoli et al35 in 2007 prepared activated carbon from banana bark by chemical activation
using concentrated sulphuric acid as activating agent and carbonizing in a furnace at 400oC
for twelve hours. The produced activated carbon was tested for its efficiency in removing
chromium ion. The effects of agitation time, initial chromium ion concentration, carbon dose,
pH and temperature on the adsorption of the metal ion were studied. Their results show that
percent adsorption decreased while the actual amount of chromium ion adsorbed per unit
mass of activated carbon increased with increase in initial chromium ion concentration from
5mg/L to 20mg/L. Both percent adsorption and actual amount of chromium ion adsorbed per
unit mass of activated carbon increased with increase in temperature from 30oC to 60oC.
Percent adsorption also increased with increase in activated carbon dosage from 0.5mg/L to
5mg/L and with increase in pH up to pH value of 7, beyond which the percent adsorption
decreased with further increase in pH. The adsorption followed first order kinetic model and
the rate was mainly controlled by intra-particle diffusion. The adsorption capacity obtained
from the Langmuir isotherm plots at initial pH of 7.0 were 11.51, 11.69, 12.00 and 12.57
mg/g at 30, 40, 50 and 60oC, respectively.
In 2008, Mopoung and Nogklai36 studied the chemical compositions and surface properties of
activated charcoal from longan seed. They investigated the influences of phosphoric acid
9
activation before and after carbonization. Carbonization temperatures in the study were
ranged from 400 - 800C. They found that higher carbonization temperatures resulted in a
high amount of organic carbon and ashes, while the volatile matters were reversely lowered.
They also found that for the studied range of carbonization temperatures, the activated longan
seed possessed higher iodine number in comparison to the unactivated but carbonized longan
seed. Also, the longan seed activated charcoal produced by activation prior to carbonization
had a greater iodine number than the one produced by carbonization prior to activation. The
highest iodine number was obtained from longan seed produced by activation prior to
carbonization at 500C.
Lori et al37 in 2008 prepared activated carbon from bagasse, sorghum and millet straws by
chemical activation using ortho phosphoric acid as activating agent. They found that the
adsorption capacities of the activated carbons for large molecular weight compounds such as
methylene blue were 502, 662 and 390mg/g for bagasse, sorghum and millet straws,
respectively. They also found that the iodine numbers, which indicate the adsorptive
capacities for low molecular weight substances were 626, 667 and 593mg/g for bagasse,
sorghum and millet straws, respectively.
Woody pod of oil bean (Penthaclethra mycrophylla) was used by Ejikeme and Ochonogor38
to prepare activated carbon in 2008. The activated carbon was prepared by chemical
activation using zinc chloride as activating agent and carbonizing in a muffle furnace at
600oC for one hour. The prepared activated carbon was tested for adsorption of basic violet 1.
They found that adsorption increased with increase in the concentration of the dye solution
from 0.0093 to 0.0372g/L. They also found that the adsorption followed first order kinetics
and that Langmuir isotherm described the adsorption process better than the Freundlich
isotherm.
10
Soleimani and Kaghazchi39, in 2008, prepared activated carbon from apricot stones by
impregnation with phosphoric acid and carbonization in programmable electrical furnace
with heating rate of 5K/min to a final carbonization temperature of 673K. The activated
carbon had BET surface area of 1387m2/g, pore volume of 0.954ml/g, bulk density of
0.452g/m3 and percentage ash content of 0.2. They tested the potential of the activated carbon
to adsorb gold ions from aqueous solution and found that adsorption increased with decrease
in carbon particle size from 12 16 to 35 50 mesh size and with increase in carbon dose
from 1 to 20kg/m3. They found the optimum pH for the gold adsorption to be 10.5 at which
98.15% of gold ions were adsorbed onto the activated carbon after three hours.
Arivoli and Thenkuzhali40, in 2008, prepared activated carbon from phoenix sylvestric leaves
by chemical activation using concentrated sulphuric acid as activating agent and carbonizing
in a furnace at 800oC for twelve hours. They studied the effects of agitation time, initial dye
concentration, carbon dose, pH and temperature on the adsorption of Rhodamine B on the
produced carbon. They found that percent adsorption decreased while the actual amount of
chromium ion adsorbed per unit mass of carbon increased with increase in initial chromium
ion concentration from 10 to 60mg/L. The percent adsorption also decreased with increase in
pH up to pH value of 8, beyond which the percent adsorption increased with further increase
in pH. Both percent adsorption and actual amount of chromium ion adsorbed per unit mass of
carbon increased with increase in temperature from 30 to 60oC. The percent adsorption also
increased with increase in carbon dosage from 0.5 to 5mg/l. The adsorption followed first
order kinetic model and the rate was mainly controlled by intra-particle diffusion. The
adsorption capacity obtained from the Langmuir isotherm plots at initial pH of 7.0 were
51.546, 47.236, 44.072 and 41.841 mg/g at 30, 40, 50 and 60oC, respectively.
11
Al-Qodah and Shawabkah41, in 2009, produced activated carbon from activated sludge using
sulphuric acid as a chemical activation agent. The produced activated carbon had specific
surface area of 580m2/g. They tested its adsorption behavior with pesticides in aqueous
solution. They studied the adsorption isotherm at solution pH of 3 using Langmuir,
Freundlich and Brunauer, Emmett and Teller (BET) models and found that the adsorption
isotherm data were closely fitted to the BET adsorption model indicating multilayer pesticide
adsorption. The estimated maximum adsorption capacity was 110 mg/g and the value
decreased with increase in the pH of the solution.
2.2 Methods of Production of Activated Carbon
Activated carbon can be produced from most carbon containing materials. Various natural
and synthetic materials have been used as raw materials for the manufacture of activated
carbons. Young fossil materials such as wood, peat and wastes of vegetable origin, which
include sawdust, nutshells and fruit stones were preferred in early production procedures
since the chars from them can be easily activated yielding reasonably high quality activated
carbon. However, presently, there is an increasing use of various kinds of natural coal which
are readily available and relatively cheap, though this still ranks second to the use of wood
and other plant materials42. Various wastes, such as sulphite liquors, waste lignin and wastes
from processing of petroleum and lubricating oil industries have also been used as raw
materials for the production of activated carbon. Commercially, the most frequently used
raw materials are peat, coal, lignite, wood and coconut shells.
In general, the raw materials to make activated carbon must accomplish a sort of
requirements like high carbon content, low mineral content, easily activation, low
degradation during storage, and, of course, low cost43. The phase of application of an
activated carbon also determines the type of raw material to be employed in the production of
12
the carbon. For vapour phase applications, carbon from lignin and wood, which are low
density materials and have high volatile content are not very suitable because they have large
pore volume but low density. However, the quality of the carbon can be improved by
densification, reconstitution or compression during carbonization. Carbons from fruit pits,
semi-hard coals, coconut shells and other nut shells, which have higher density than wood
and possess high volatile contents, are hard and granular with large micropore volumes and
are therefore quite suitable for solution as well as vapour phase application44.
The processing technique to be used for the production of activated carbon depends on the
nature and type of raw material available as well as the desired physical form of the activated
carbon. The production of activated carbon involves two major steps; carbonization and
activation. These processes are carried out after the raw material has been prepared and put in
a form that will be easy to handle.
Preparation of Raw Materials
The following processes are carried out on the raw material to put it in a form suitable for
carbonization.
(i) Sizing This involves breaking down of the raw material into lumps or granules of
appropriate sizes, which can be handled effectively in subsequent operations.
(ii) Sieving This is done using wire gauze in the case of materials with fibre or fluffy
particles in order to remove these particles and leave the desired material for
carbonization. Winnowing could also be carried out alongside the sieving.
(iii) Reconstitution This involves pulverization of the raw material followed by
agglomeration by extrusion or briquetting. It is usually done on low-density
materials in order to improve their quality.

13
2.2.1 Carbonization
Carbonization is the thermal separation of carbonaceous materials, elimination of organic
materials and production of porous fixed carbon45. This process is usually carried out in a
muffle furnace or in rotary kilns at elevated temperatures. It involves thermal decomposition
of the raw material as it is heated under a time schedule to remove the volatile or non-carbon
entities leaving basically carbon possessing a partially developed or rudimentary pore
structure. Usually, basic microstructure of carbon is formed at 500, although there may be
blockages of the micropores by pyrolytic products, which can only volatilize at higher
temperatures. According to Hassler46, temperatures below 600 are suitable for the
production of chars that are to be activated with steam but this is not an invariable rule.
Carbonization product is non-active material as a result of its small surface area47.
2.2.2 Activation
This is the process of transforming inert carbon into highly adsorbent material by conferring
on it a porous material structure and large specific surface area48. The objective is to enhance
the volume and enlarge the pores which were created during the carbonization process, and
also to create new pores. Activation is of two main types, namely physical and chemical
activation.
Physical Activation
Physical activation involves the treatment of carbonized materials with oxidizing gases at
elevated temperatures between 700-1000oC. Common gases used include CO2, steam, and
O2. The reaction between steam and charcoal takes place at all the internal surfaces of the
carbon structure, removing carbon from the pore wall and thereby enlarging them49. This
creates more sites for adsorption with the liberation of gases such as H2, CO2 and CO. The
14
active oxygen in the activating agent basically burns away the more reactive portions of the
carbon skeleton as CO and CO2. The extent of this depends on the nature of the gas employed
and the temperature of activation.
The endothermic gasification reactions of carbon with steam and CO2 with their respective
heats of reaction (Hr) are shown in equations (2.1) and (2.2).
C(s) + H2O(g) CO(g) + H2(g) + 117 kJ/(g.mol (2.1)
C(s) + CO2(g) 2CO(g) + 159 kJ/(g.mol) (2.2)
The reaction of steam with carbon also produces a side reaction whereby the carbon surface
catalyzes an exothermic reaction of CO and steam to yield CO2 and H2 as shown in equation
(2.3) 50.
CO(s) + H2O(g) CO2(g) + H2(g) + 42 kJ/(g.mol) (2.3)
This reaction retards activation, since the H2(g) becomes strongly adsorbed at active sites on
the carbon surface. In general, steam is preferred to CO2 as an activation gas because the
51
water molecule has a smaller van der Waals radius than CO2 (~3.8 vs. ~4.8) . This
leads to a faster diffusion of steam in the porous matrix of the carbon and a subsequent faster
reaction rate. The reaction of solid carbon and CO2 (equation 2.2) can be retarded by the
addition of CO(g) to drive the thermodynamic equilibrium to the left, which may improve
microporous structure through a decreased gasification rate.
The process of steam activation produces a carbonaceous substance with many small pores
and thus a very large internal surface area. This carbon is then crushed, if desired, to yield a
pulverized product.
15
Chemical Activation
Chemical activation is typically employed when wood products are used as raw material and
it involves impregnation of the feedstock with chemicals either before or after pyrolysis
(carbonization). Typical chemicals used as activating agents in chemical activation include
phosphoric acid (H3PO4), ammonium chloride (NH4Cl), sulfuric acid (H2SO4), potassium
sulfide (K2S), carbonates of alkali metals, and metal chlorides. The common property of
chemical activation compounds is to dehydrate the carbonaceous material which usually
enhances pyrolytic decomposition and inhibits formation of tar. This process has an
advantage over physical activation processes since it normally occurs at temperatures lower
than those used in the latter52. This may also benefit the development of a microporous
structure. The mechanism of chemical activation is not fully understood. According to Byrne
and Marsh53, during chemical activation, the chemistry of pyrolysis is changed and a
different, macromolecular network is established with enhanced porosity. However, the
chemical detail of this remains unexplored. Distribution of pore sizes in the product depends
on the degree of impregnation. Therefore, it is of productive and economic interest to use the
ratio of activating agent to raw material that gives the best results.
The obtained carbon is then washed to neutral pH and then dried and preserved.
2.3 Characteristics of Activated Carbon
Activated carbon represents substances with high carbon content which have undergone the
process of activation. It also refers to carbons in which the adsorptive powers have been
supposedly increased by man-made operations. According to Soleimani and Kaghazchi39,
activated carbon is the trade name for a carbonaceous adsorbent that has high porous
structure and a large surface area. A generalized definition is that activated carbons are non-
hazardous, processed, carbonaceous products having a high degree of porosity and an

16
extended inter-particulate surface area54. Hence, they are able to adsorb a wide variety of
substances and are good adsorbents.
Structurally, activated carbon is an amorphous form of carbon. This implies that it has no
regular atomic structure unlike the other allotropes (forms) of elemental carbon (diamond,
fullerenes or nanotubes). Activated carbon is hydrophobic and non-polar.
2.3.1 Classifications of Activated Carbon
Activated carbons are complex products which are difficult to classify on the basis of their
behaviour, surface characteristics and preparation methods. However, some broad
classification is made for general purpose based on their physical characteristics.
Powdered activated carbon (PAC)
PAC material is defined as fine activated carbon material. PAC is made up of crushed or
ground carbon particles. They are so finely powdered that most of them can easily pass
through a designated mesh size. Due to their small size they form large internal surface
having small diffusion distance (barrier to adsorption) and large pore diameters. Hence, their
rate of adsorption is high and mass transfer problems are very low. PAC is not commonly
used in a dedicated vessel, owing to the high head loss that would occur. PAC is generally
added directly to other process units, such as raw water intakes, rapid mix basins, clarifiers,
and gravity filters. In general, PAC is used to adsorb materials from liquids.
Granulated activated carbon (GAC)
GAC is usually prepared from coal, petroleum, heavy oils, rubber, and the pyrolysis of waste
rubber tyres55. They come in both granular and extruded form. Granulated activated carbon
forms are of larger particle size than the powdered activated carbon forms. Granulated
carbons are mainly used for treating water. Their main function includes deodorization and
17
separation of components of flow system. They are generally used for the removal of
hazardous and/or pollutant chemicals from wastewater and for purification of water, air and
other materials56. Hard granules and relatively dust free pellets are usually used for adsorbing
gaseous materials in packed beds.
Pelleted activated carbon
They are granulated in smaller size and come in extruded and cylindrical shape with
diameters from 0.8 to 5 mm. These are mainly used for gas phase applications because of
their low pressure drop, high mechanical strength and low dust content.
Spherical activated carbon
These are usually small and spherical and have high mechanical strength and excellent SO2
and NO2 adsorption capacity.
Impregnated carbon
These are porous carbons which have been impregnated with other substances. They are
usually prepared for specific applications in air pollution control especially in museums and
galleries. Silver loaded activated carbon is used as an adsorbent for purification of domestic
water. Drinking water can be obtained from natural water by treating the natural water with a
mixture of activated carbon and flocculating agent [Al(OH)3]. Impregnated carbons are also
used for the adsorption of H2S and mercaptans.
Polymers coated carbon
These are porous carbons produced by coating with a biocompatible polymer to give a
smooth and permeable coat without blocking the pores. The resulting carbon is useful for
18
hemo-perfusion which is a treatment technique in which large volumes of the patient's blood
are passed over an adsorbent substance in order to remove toxic substances from the blood.
Specialties
Activated carbon is also available in special forms such as cloths and fibres.
2.3.2 Properties of Activated Carbon
An activated carbon particle can be depicted as in Figure 2.1.
Large and
small
i
Pores available to both

Carb small
on and largeavailable
moleculeonly to
Pores
adsorption
small
molecule adsorption
Figure 2.1: Activated carbon particle. (Adapted from New Concepts in Water
Purification57.)
Activated carbon is not a pure carbon. It contains other elements in various proportions
depending on the source material and on the mechanism of its production. Such other
elements, which are chemically combined with the carbon atoms, include hydrogen, oxygen,
nitrogen, sulphur, etc. The adsorptive and catalytic powers of the activated carbons are traced
to the presence of these elements in the carbon. The morphology of an activated carbon as
observed by an electron microscopy is greatly determined by the raw material that was used
for its production. This is as a result of the fact that the nature of the starting material is
directly reflected in the final product. The properties of commercially available activated
19
carbons are responsible for their use as either gas-phase or liquid-phase adsorbents. These
properties are grouped into two broad classes; physical and chemical properties
2.3.2.1 Physical properties
Forms
Activated carbons are available in different forms such as symmetrical pellets, irregularly
shaped granules, powder and specialties like pre-formed shapes, example, wool and slurry for
coating supports. The major forms of activated carbon are the powdered form, the granular
form and the pellets. These forms of activated carbon have been described in section 2.3.1.
Particle size
This property is important due to the fact that adsorption rate varies inversely with particle
size. Mathematically,
r (1/s) (2.4)
where r is the rate of adsorption and s is the particle size. This means that, an increase in
particle size will lead to a decrease in adsorption rate while a decrease in particle size will
favour high adsorption rate. The finer the particles size of an activated carbon, the better the
access to the surface area and the faster the rate of adsorption kinetics. In vapour phase
systems, this needs to be considered against pressure drop which will affect energy cost.
Careful consideration of particle size distribution can provide significant operating benefits.
Abrasion resistance
Abrasion resistance refers to a carbons ability to withstand degradation during handling and
is expressed in terms of abrasion number or handling number. It is an important indicator of
an activated carbons ability to maintain its physical integrity and withstand frictional forces
20
imposed by backwashing and other factors. During handling and use, the harder the activated
carbon, the less it will crumble into fine particles which can escape from the system leading
to losses. It is estimated by comparing the screen analysis of a carbon before and after
subjection to abrasion and shows the mechanical strength of the activated carbon.
There are large differences in the hardness of activated carbons, depending on the raw
material and activating level. For adsorption of liquids or solids dissolved in liquid, the
activated carbon needs mechanical strength enough to support the adhering solutes as they
are being adsorbed. For adsorption of gases under high pressure, activated carbon of high
mechanical strength is also required due to the fact that high force is associated with
increased pressure for a given surface area since pressure is directly proportional to force58.
This can be expressed mathematically as equation (2.5) or (2.6).
Pressure = (Force/Unit area) (2.5)
Force = Pressure x Unit area (2.6)
This means that for a constant unit area (surface area of the adsorbent), a rise in the pressure
of the adsorbate results in a corresponding rise in the force exerted by the adsorbate on the
activated carbon.
Bulk density
Apparent or bulk density is a measure of the weight of material that can be contained in a
given volume under specified conditions9. It is determined by measuring the volume of a
weighed sample of activated carbon after tapping till no further reduction in volume occurs.
The volume used in this determination includes, in addition to the volume of the skeletal
solid, the volume of the voids among the particles and the volume of the pores within the
particles. Bulk density of carbon determines how much of it can be contained in a given
21
container. Bulk density is affected by the raw material used and the degree of activation. The
density does not affect the effectiveness of the activated carbon measured in adsorption per
unit weight, but will have an effect on adsorption per unit volume. Higher density provides
greater volume activity.
Surface area
Activated carbons have very large surface area, typically ranging from 500 1400m2g-1 59.
This is an important property of activated carbon as it greatly affects the adsorptive properties
of the carbon. Increase in surface area enhances the adsorptive capabilities of activated
carbon by exposing a wide surface for physical as well as chemical adsorptions.
Pore structure
The amount and distribution of pores in an adsorbent play key roles in determining how well
adsorbates are adsorbed. Practically, the type of raw material and the method of activation are
important parameters which may influence the type of porosity60. The pore structure of an
activated carbon limits the size of the molecules that can be adsorbed on it. Individual pores
can vary greatly in size and shape for different adsorbents and even within the same
adsorbent. Pores are usually characterized in terms of their width, meaning the diameter of a
cylindrical pore or the distance between two sides of a slit-shaped pore. The pore
classification adopted by the International Union of Pure and Applied Chemistry61 is shown
in Table 2.1.
Table 2.1: Pore Classifications by Pore Width
Pore Classification Pore Width

Micropores Less than ~ 20 (2nm)
Mesopores Between ~20 and ~500 (2 and 50nm)
Macropores More than ~500 (50nm)
22
The basis for the pore classifications presented in Table 2.1 is that each size range
corresponds to different adsorption effects, as observed in an adsorption isotherm. Physical
adsorption of molecules from gas or liquid onto activated carbon takes place in the pores and
usually involves 3 steps:
(1) Macro transport: The movement of adsorbate material through the macropore system
of the activated carbon
(2) Micro transport: The movement of adsorbate material through the mesopore and
micropore system of the activated carbon.
(3) Sorption: The physical attachment of adsorbate material in the mesopores and
micropores on the surface of activated carbon.
Pore size is a determinant of efficient adsorption. Within the pores exists an adsorption
energy potential which emanates from each pore wall. In the case of physical adsorption,
these forces closely resemble dispersion (or van der Waals forces). If large enough, this
energy of adsorption is able to capture adsorbate molecules as they enter the pore, adhering
the molecules to the pore wall62. If the proximity of the pore walls causes overlap of the
adsorption fields, as in the case of micropores, the result is an increase in the potential for
adsorption. So, although some activated carbons may have lower surface areas and total pore
volumes, their smaller pore sizes increases their potential for adsorption. This makes small
pores prime candidates for removal of low adsorbate concentrations, where the driving force
for diffusional transport of the molecule to the surface is minimal63.
The presence of micropores increase the adsorption potentials of carbons over those of non-
porous and mesoporous materials. These micropores are responsible for the large surface area
of activated carbon particles created during the activation process. It is in the micropores that
adsorption largely takes place. The interaction potential in micropores is much greater than
that in larger pores due to the closeness of the pore walls, resulting in an enhanced adsorption
23
potential. An adsorbate molecule within a micropore is held there by adsorption forces
originating from approximately the ten nearest surface atoms. The forces on adsorbate
molecules depend on the distance between adsorbate and adsorbent atoms (pore size) 64. The
macropores and large mesopores play an extensive role in the molecular transport process by
providing a passage-way to the internal part of the activated carbon into the micropores. They
do not contribute substantially to the particle surface area unlike the micropores. Capillary
condensation takes place within mesopores, resulting in a hysteresis loop in the adsorption
isotherm. In macropores, the pores are so wide that it is almost impossible to map out the
isotherm in detail, especially for gaseous adsorbate in which case pressures of the adsorbate
would become so close to unity. The more widely the pore sizes are distributed, the more
enhanced the adsorptive capacity of the carbon.
2.3.2.2 Chemical properties
pH
The pH of an activated carbon is a measure of the surface acidity/basicity of the carbon. This
is the pH of a suspension of the activated carbon in distilled water. The numerical values of
the pH are affected by the experimental conditions when carrying out the experiment. A
carbon pH of 6-8 is acceptable for most application such as sugar decolorization, water
treatment, etc65. The pH of many of the commercial carbons is due to inorganic components
originating from the raw material used or added during the manufacturing process. After
activation (with acid) and carbonization, activated carbons are usually washed to bring them
to neutral pH.
Moisture content
This is determined by drying an isolated portion of an activated carbon in an oven at 105
110oC until constant weight is attained. This property is important in adsorptive capacity test.
24
Inorganic constituents
Activated carbons contain different inorganic substances, which originate from the raw
materials used and also from the ingredients added during the processing of the carbon.
However, the total amount of these inorganic constituents varies from one grade of activated
carbon to another. The inorganic constituents include:
(1) Ash
This is the form in which the inorganic constituents of carbon exist after the carbon has
undergone complete combustion at controlled temperature. Ash in an activated carbon is an
impurity and is not desired. It reduces the overall activity of the activated carbon and reduces
the efficiency of re-activation. The metals (Fe2O3) can leach out of activated carbon resulting
in discoloration. Acid/water soluble ash content is more significant than total ash content. In
some carbons, not all inorganic constituents remain as ash after combustion of the carbons.
Therefore, in such carbons, the amount of inorganic substances that can be eluted from them
is less than the water soluble inorganic substances found in their ash. This is illustrated in
Table 2.2.
Table 2.2: Amount of Water Soluble Inorganic Substances in Carbon*
Carbon Found in ash from 100g carbon Eluted from 100g original carbon
Grade (g) (g)
EE 0.75 0.50
FF 0.80 0.41
GG 1.52 1.55
MM 2.50 1.20
NN 3.50 2.05
*obtained from reference 24.

25
(2) Inorganic constituents as ion exchangers
Some types of activated carbon usually contain a normally soluble inorganic compound
bonded to the carbon in the form of an ion exchanger, usually an anion exchanger. These ion
exchangers attract free ions in solution or suspension. The capability of an activated carbon to
exchange a particular type of ion often depends on the way the carbon is treated.
2.4 Adsorption Phenomena
Adsorption is the occupation of the surface and pores (if any) of a substance (solid, liquid or
gas) by molecules of another substance as a result of some attractive forces between the
adsorbing surface and the substance adsorbed. This becomes feasible only when the
substance to be adsorbed is in contact with the adsorbing surface. The adsorbing surface is
called the adsorbent while the adsorbed substance is called the adsorbate. The chemical
equilibrium which represents the adsorption of molecules on a surface is as follows:
A + B AB (2.7)
where, A is the adsorbate, B is the adsorbent and AB is the product of the adsorption process.
For adsorption of compounds on activated carbon, which is a reversible reaction, molecules
continue to accumulate on the surface of the carbon until the rate of the forward reaction
(adsorption process) is equal to the rate of the backward reaction (desorption process). At this
point, equilibrium state is attained and no further accumulation of the adsorbate on the
adsorbent surface occurs. Hence, adsorption stops. This equilibrium state enables relationship
known as adsorption isotherm66.

26
Based on the energy associated with adsorption and the type of bond responsible for the
adherence of the adsorbate on the adsorbent, adsorption process can be classified into
physical and chemical adsorption.
Physical Adsorption (Physisorption)
This is a weak form of interaction between an adsorbent and adsorbate molecules. The forces
involved are similar to van der Waals forces and the heat evolved during the exothermic
adsorption reaction is low (usually of the same magnitude as the enthalpy of condensation, <
42KJ/mol). This amount of energy can be adsorbed as vibrations of the lattice and dissipated
as thermal motion. Because of the energy requirements for the process, equilibrium between
the solid surface and the gas molecules is usually easily attained and is readily reversible. The
amount of physisorption decreases rapidly as temperature is raised and is generally very
small above the critical temperature of the adsorbed specie. Due to the weak force involved in
physisorption, the activation energy is low, not more than 42kJ/mol. The rate of physisorption
is very high but the process is non-specific.
Generally, the process of physical adsorption begins as an adsorbate molecule is transported
from the bulk adsorbate phase to the surface of the adsorbent. Next, the molecule then
diffuses into the pore and then physically bonds with the surface. Heat is usually evolved,
making adsorption an exothermic process. In the first step, the bulk adsorbate stream must be
intimately mixed with the adsorbent to promote good contact between the two components.
In the second and third stages, the concentration gradient between the amount of adsorbate
present in the bulk adsorbate stream and that within the micropore provides the driving force
for adsorption.
27
Chemical Adsorption (Chemisorption)
This type of adsorption is one in which chemical bond is formed between the adsorbate and
the adsorbent. The chemical bond involved is usually covalent bond and the adsorbent tends
to find sites that will maximize its co-ordination number with the substrate. Chemisorption is
specific and involves forces which are stronger than those associated with physisorption.
Hence, the heat of adsorption in this case is high and is of the same order as heat of reaction.
This process requires generally high temperature and is often irreversible. Unlike
physisorption, in which multilayer coverage is possible, chemisorption does not exceed
monolayer coverage. This is because the valence force holding the molecules on the
adsorbent surface diminishes rapidly with distance. Generally, chemical adsorption is linked
to the porosity and surface chemistry of the carbon, since chemisorption is associated with
the number of active sites and carbon surface.
Chemisorption is of two kinds; activated and non-activated chemisorptions. In activated
chemisorptions, high activation energy is involved and the rate varies with temperature
according to the finite activation energy (between 8.4 83.7kJ/mol) in the Arrhenius
equation (equation 2.8) 67.
k = Ae(-E/RT) (2.8)
where k is the rate of reaction, A is a proportionality constant, E is the activation energy, R is
the universal gas constant and T is the absolute temperature. In non-activated chemisorption,
the process occurs very rapidly, hence, the activation energy is low, usually close to zero.
2.4.1 Adsorption Isotherm
Adsorption isotherm is a set of data which represents constant temperature measurements of
the quantities adsorbed by a unit weight of adsorbent in equilibrium with each of a number of
28
different activities (concentration for liquids and partial pressure for gases) of the mobile
phase or an analytical expression representing such data. In a closed system, the adsorption of
an adsorbate onto a solid can be measured by monitoring the decrease in adsorbate activity
within a known volume or by measuring the mass gain of the adsorbent due to the adsorbing
molecules. The amount of an adsorbate adsorbed in moles per gram solid is a function of the
activity of the adsorbate, the temperature of the system, the pH of the solution, the amount of
contact between the adsorbate and the adsorbent, dose rate of the adsorbent, particle size of
the adsorbent and the presence of other substances that could be adsorbed.
The models used to describe the isotherm function of adsorption include the Langmuir
isotherm, Freundlich isotherm, and Temkin isotherm.
2.4.1.1 Langmuir Isotherm
The Langmuir isotherm is based on four hypotheses68:
1. The adsorption takes place on the free sites of the adsorbent.
2. One adsorption site can adsorb one molecule; at most monolayer coverage is present.
3. The adsorption sites have the same energy (homogeneous surface), no interaction is
between the adsorbed molecules. It means that the adsorption energy is independent
on coverage.
4. There is adsorption equilibrium between the phases.
Langmuir suggested that adsorption takes place as follows:
ka
A+S AS (2.9)
kd
29
where, A is an adsorbate molecule, S is an adsorption site, ka corresponds to the rate constant
for the adsorption process and kd corresponds to the rate constant for the desorption process.
At equilibrium, the rate of adsorption is equal to the rate of desorption. On a uniform catalyst
surface, the equilibrium condition for a gaseous adsorbate is represented by the following
equation:
kaP(1 ) = kd (2.10)
where, P is the pressure of the adsorbate, A, and is the fractional surface coverage. The
required relationship for Langmuir isotherm becomes:
= (KP)/(1 + KP) (2.11)
where,
K = (kakd) = koe(qRT) (2.12)
ko is a constant and q is the heat of adsorption.
The applicability of the Langmuir isotherm to any gas adsorption process can be tested by the
use of equation (2.13), which is a rearranged form of equation (2.11).
(P/) = (1/K) + P (2.13)
Thus, a plot of (P/) against P should yield a straight line graph whose slope is 1 and the
intercept is 1K. Also, K, which is the adsorption equilibrium constant, should increase with
temperature.
For liquid adsorbates, however, the Langmuir isotherm is usually expressed as follows:
30
qe = (qmaxCe)(KL + Ce) (2.14)
where, qe is the equilibrium value of adsorbate adsorbed per unit weight of adsorbent (mg/g),
qmax is the maximum amount of adsorption corresponding to monomolecular layer coverage
(mg/g), Ce is the equilibrium concentration of the adsorbate, kL is the Langmuirs constant and
69
is related to the measure of affinity of the adsorbate for the adsorbent (l/mg) . For
correlation purposes, the equation is rearranged as follows:
Ceqe = (1kL.qmax) + (1qmax).Ce (2.15)
A linearized plot of Ceqe against Ce yields a straight line graph which has an intercept and
slope which correspond to (1kL.qmax) and (1qmax), respectively, from which the qmax and kL
can be calculated.
To confirm the favourability of an adsorption process to Langmuir isotherm, the essential
features of the isotherm can be expressed in terms of a dimensionless constant known as the
separation factor or equation parameter, RL, which can be calculated by the following
equation.
RL = 1(1 + kL.Co) (2.16)
where, Co is the initial adsorbate concentration. The value of RL indicates whether the
isotherm is irreversible (RL=0), favourable (0 < RL < 1), linear (RL=1) or unfavourable (RL >
70
1) .
2.4.1.2 Freundlich Isotherm
The Freundlich equation assumes that different sites with several adsorption energies are
involved in the process of adsorption71. It therefore incorporates surface heterogeneity of

31
active sites. The Freundlich isotherm can be derived by applying the Langmuir model and
assuming that the heat of adsorption, H, is exponentially dependent on the fractional surface
coverage, 72. This is expressed in the following equation.
= (aoP)(-RTHm) = (aoP)RTqm = ggm (2.17)
where,
qm = -Hm (2.18)
ao = kakd (2.19)
P is the pressure of the adsorbate, R is the universal constant, T is the temperature, g is the
amount of adsorbate adsorbed by adsorbent, gm is the amount of adsorbate adsorbed when the
surface of the adsorbent is completely covered with a monolayer, ka is the rate of adsorption
and kd is the rate of desorption.
For purposes of data analysis, the isotherm can be arranged as follows:
ln g = [ln gm + (RTqm) ln ao] + (RTqm) ln P (2.20)
The terms in the brackets are constants at constant temperature. A plot of ln g against ln P
yields a straight line whose slope is (RTqm), from which qm can be calculated.
For liquid adsorbates, the Freundlich relationship is shown as follows:
qe = kF.Ce1/n (2.21)
where, 1/n is a heterogeneity factor, which is a measure of intensity of sorption or affinity of
the adsorbate for the adsorbent73; kF is the Freundlich constant.
The Freundlich equation can be linearized as shown in equation (2.22).

32
log qe = log kF + 1/n log C (2.22)
The constants, kF and n, are determined by plotting log C on the abscissa and log qe on the
ordinate. A best fit of the experimental data provides values for kF and n based on the y-
intercept and the slope, respectively. The Freundlich equation is useful in cases where the
actual identity of the adsorbate is not known74.
2.4.1.3 Temkin Isotherm
The Temkin isotherm assumes that the fall in the heat of sorption is linear rather than
logarithmic, as implied in the Freundlich equation75. The isotherm can be derived by
assuming that for adsorption at a single site, the appropriate Langmuir isotherm is as shown
in the following equation76.
/(1 - ) = (kakd).P exp (-HRT) (2.23)
This gives the Temkin isotherm to be as shown in equation (1.24) for gaseous adsorbates.
ln /(1 - ) = ln P + (Ho)RT + ln Ao (2.24)
where,
Ao = ao exp (qRT) (2.25)
is a positive constant.
If the variation of ln /(1 - ) is taken to be negligible, then equation (2.24) becomes:
ln P + (Ho)RT + ln Ao = 0 (2.26)
This can be rearranged in the form of equation (2.27).

33
= (RTqo) ln (AoP) = ggm (2.27)
where,
qo = -Ho (2.28)
Ho is the heat of adsorption at zero coverage.
For correlation purposes, the isotherm is expressed as follows:
g = (gm RTqo) [ln ao + (qoRT)] + (gm RTqo) ln P (2.29)
A plot of g versus ln P gives a straight line graph whose slope is (gm RTqo), from which qo
can be calculated.
For liquid adsorbates, the Temkin isotherm model is as follows.
qe = (RT)bT ln kT + (RT)bT ln Ce (2.30)
where, bT indicates the adsorption potential of the adsorbent and kT is the Temkin constant77.
A plot of qe versus ln Ce gives a straight line graph if this model is favoured. kT can be
calculated from the intercept of the plot while bT can be calculated from the slope.
2.4.2 Adsorption Kinetics
Various kinetic models are used in determining the mechanism of an adsorption process and
the potential rate controlling steps. Some of these models are discussed in the following
sections.
2.4.2.1 Bhattacharya-Venkobachar Model
The Bhattacharya-Venkobachar equation is as follows:

34
log [1 - (U)T] = (kB2.303) t (2.31)
where
(U)T = (Co Ct)/ (Co Ce) (2.32)
KB is the Bhattacharya-Venkobachars constant (min-1); Co is the initial concentration (mgl);
Ct is the concentration at time, t (mgl) and Ce is the concentration at equilibrium (mgl). A
plot of log [1- (U)T] versus t should yield a straight line, if the sorption process obeys this
model. From the slope of the plot, KB can be determined. The Bhattacharya-Venkobachar
equation is based on the assumption that the adsorption process is controlled by intra-particle
diffusion78.
2.4.2.2 Lagergren Pseudo First Order Model
The Lagergren pseudo first order equation is generally expressed as follows:
dqtdt = k1 (qe - qt) (2.33)
where, qe and qt are the adsorption capacity at equilibrium and at time t, respectively (mg.g-1)
and k1 is the rate constant of pseudo first order adsorption (min-1). The integrated rate law,
after applying the initial condition of qt = 0 at t = 0, is as follows79:
log (qe - qt) = log (qe) - (k1t)2.303 (2.34)
A plot of log (qe - qt) versus t should give a straight line, if the sorption is controlled by this
model. k1 and qe can be determined from the slope and intercept of the plot, respectively. The
experimental qe should tally with the estimated one. Generally, higher values of k1 suggest
greater adsorption80.
35
The assumption with this model is that the rate of adsorption is proportional to the difference
between the adsorption capacity (qe) at equilibrium and the capacity at any time t79.
According to Sa and Aktay81, if the experimental results do not follow equation (2.34), then
k1(qe qt) does not represent the number of available adsorption sites and log qe is not equal
to the intercept of the plot of log (qe qt) against t.
2.4.2.3 Pseudo-second Order Model
The pseudo second order adsorption kinetic rate equation as expressed by Ho, Y.S82 is shown
in equation (2.35).
dqtdt = k2 (qe - qt)2 (2.35)
where, k2 is the rate constant of pseudo second order adsorption (g.mg-1.min-1). From the
boundary conditions t = 0 to t = t and qt = 0 to qt = qt, the integrated form of equation (2.35)
becomes equation (2.36).
1(qe - qt) = 1qe + k2t (2.36)
This is the integrated rate law for a pseudo second order reaction. Equation (2.36) can be
rearranged to obtain equation (2.37), which has a linear form.
tqt = 1(k2qe2) + tqe (2.37)
A plot of tqt versus t should give a straight line if this model is obeyed by the sorption
process. From the slope and intercept of the plots, qe and k2 are determined, respectively. The
experimental qe should tally with the estimated one. Decrease in the values of k2 suggests
increased adsorption83.
36
The main assumptions of the pseudo-second order kinetic model is that rate limiting step is
chemical sorption involving bond formation through sharing or exchange of electrons
between the adsorbate and adsorbent. It also assumes that sorption follows the Langmuir
equation84.
2.4.2.4 Elovich Model
The Elovich equation is generally expressed as shown in equation (2.38).
dqtdt = exp (-qt) (2.38)
where, is the initial adsorption rate (mg.g-1.min-1) and is desorption rate constant (mg.g-
1
.min-1) during any one experiment. To simplify the Elovich equation, Chien and Clayton85,
assumed t t and by applying the boundary conditions qt = 0 at t = 0 and qt = qt at t = t,
equation (2.38) becomes equation (2.39).
qt = (1) ln () + (1/) ln (t) (2.39)
Thus, a plot of qt vs. ln (t) should yield a linear relationship with a slope of (1) and an
intercept of (1) ln () if the sorption process fits the Elovich equation. can be calculated
from the slope of the plot while can be calculated from the intercept. Conformation to
Elovich model suggests that the rate of the adsorption process is influenced by diffusion of
ions to the binding sites on the adsorbent surface86. It is also proposed that the Elovich
equation is obeyed by adsorption processes that obey the Temkin equation87.
2.4.2.5 Intra-particle and film diffusion kinetics
The basic assumption with intra-particle diffusion model is that film diffusion is negligible
and intra-particle diffusion is the only rate-controlling step88. According to Weber and
37
Morris89, if the rate limiting step is the intra-particle diffusion, then the amount adsorbed at
any time t should be directly proportional to the square root of contact time, t, and shall pass
through the origin. This is defined mathematically as follows:
qt = kid t0.5 (2.40)
where qt (mg.g-1) is the amount adsorbed at time t (min) and kid (mg. g-1.min-0.5) is the intra-
particle rate constant. The logarithmic form of equation (2.40) is equation (2.41).
log qt = log kid + 0.5 log t (2.41)
The plot of log qt against 0.5 log t should yield a straight line with a positive intercept for
intra-particle diffusion controlled adsorption process. kid is determined from the intercept of
the plot. Higher values of Kid illustrate an enhancement in the rate of adsorption. To confirm
that an adsorption process is controlled by intra-particle diffusion, the intra-particle diffusion
coefficient, DP, is usually calculated using the following equation:
DP = (0.03r02)t0.5 (2.42)
where r0 (cm) is the average radius of the adsorbent particle and t0.5 (min) is the time
required to complete the half of the adsorption. If the calculated intra-particle diffusion
coefficient (DP) value is in the range of 10-11 to 10-13 cm2.s-1, then the intra-particle diffusion
controls the rate limiting step and, if the calculated film diffusion co-efficient (DF) value is in
the range of 10-6 to 10-8 cm2.s-1, then the rate limiting step is controlled by film (boundary
layer) diffusion. The DF values are calculated as follows:
DF = (0.23r0CS)(CLt0.5) (2.43)
38
where r0 and t0.5 have the same meaning as before, is the film thickness (10-3cm), CS and CL
are the concentrations of adsorbate in solid and liquid phase at time t, respectively90.
2.4.3 Previous Works on Pb2+ and Cu2+ Removal from Simulated Waste Water
Some investigators have studied the removal of Pb2+ and Cu2+ from simulated waste water
using activated carbon from agricultural wastes. Low et al91, in 1995, prepared activated
carbon from banana pith and tested its adsorption of Cu2+ from electroplating wastes. They
found that the adsorption process obeyed the Langmuir isotherm and the monolayer
adsorption capacity of the activated carbon for Cu2+ was 13.50mg/g.
Marshall and Champagne92 also produced activated carbon in 1995 from cotton seed hull, and
the activated carbon was tested for the adsorption of Cu2+ from simulated waste water. They
found that adsorption of the copper ion increased with increase in initial copper ion
concentration and at 100 mg/L up to 95.6% of the copper ion was adsorbed. They also found
that the adsorption process could be described by the Langmuir isotherm. The monolayer
adsorption capacity was found to be 19.1mg/g.
In 1999, Teker et al93 investigated the removal of copper (II) ions from aqueous solutions by
adsorption on activated carbon prepared from rice hulls. They studied the effect of metal
solution pH, activated carbon dosage, contact time, initial metal concentration and solution
temperature. They found that percent adsorption increased with increase in pH up to 5 and
remained at the same value with further increase in the pH up to a pH value of 9. Percent
adsorption also increased with increase in contact time up to 60 minutes and with increase in
carbon dosage up to 0.02g/ml and decreased with increase in metal concentration from 10 to
100ppm and with increase in solution temperature from 293 to 313K. The adsorption data
obtained correlated well with the Freundlich and Langmuir adsorption models. The
39
adsorption capacity of the activated carbon for the uptake of Cu (II) was 6.14 x 105mol/g
and 5.10 x 105 mol/g at 293K and 313K, respectively.
In 2000, Hasar and Cuci94 prepared activated carbon from almond husk by activating with
and without sulphuric acid at different temperatures. They investigated the ability of the
activated carbons to remove some metal ions, including Cu2+ from aqueous solution by
adsorption. They studied the effect of certain conditions such as carbonization temperature of
the husk, concentration of metal ions, contact time, and adsorbent weight. They found that
metal uptake increased with increase in carbonization temperature up to 700oC, and then
decreased at higher temperatures. Metal uptake also increased with increase in adsorbent
weight up to 5g and with increase in metal concentration up to 100mg/l. Adsorption
equilibrium was attained after 180minutes of contact. At these optimal conditions, they found
the removal of Cu2+ to be 94.7%. They also found that the adsorption process obeyed the
Freundlich isotherm.
In 2003, Bansode et al95 prepared granular activated carbons from pecan shell by activation
with phosphoric acid, CO2 and steam. The carbons were used for adsorption of Cu2+ and Pb2+
from simulated waste water. The results obtained from their study showed that phosphoric
acid-activated pecan shell carbon adsorbed more lead ion than any of the other carbons,
especially at carbon doses of 0.21.0% while steam-activated pecan shell carbon adsorbed
more copper ion than the other carbons. Their results therefore showed that carbon dioxide-
activated pecan shell carbon was a poor metal ion adsorbent. They found that the adsorption
processes obeyed the Langmuir isotherm and the monolayer adsorption capacities were found
to be 6.84, 0.001 and 18.10mg/g, for the phosphoric acid, CO2 and steam activated carbons,
respectively.
40
Abdulkarim, M. and Al-Rub, F.A.96 in 2004 converted date pits into activated carbon by air
and phosphoric acid activation. The air and phosphoric acid activated carbons showed surface
areas of 864.8m2/g and 502.2m2/g, respectively, and micropore volumes of 0.298cm3/g and
0.126cm3/g, respectively. The activated carbons were tested for adsorption of lead ion and the
ion uptake was found to increase with increase in initial lead ion concentration and solution
pH up to pH value of 5.2. Equilibrium studies showed that the adsorption of lead ions on both
adsorbents could be described by the Langmuir and Freundlich isotherm models. Kinetic
studies showed that the adsorption followed pseudo-second-order kinetics.
In 2006, Kongsuwan et al97 employed Eucalyptus camaldulensis dehn bark as a raw material
for the production of activated carbon by chemical activation using phosphoric acid as
activating agent. Carbonization was carried out in a muffle furnace at 500C for one hour.
The yield of activated carbon was found to be 31.9% and the activated carbon had a bulk
density of 0.251g/cm3, ash content of 4.88% and BET specific surface area of 1239m2/g. The
activated carbon was utilized as adsorbent for treating synthetic wastewater containing Cu(II)
and Pb(II). The adsorption of both metals was found to increase with increase in pH from 1 to
5, beyond which the metals were precipitated out of their solutions as their hydroxides.
Hence, they concluded that the optimum pH for the adsorption of both metals is 5. Their
results also show that the amount of both metals adsorbed increased with increase in metal
concentration from 0.1 to 10 mM. The adsorption reached equilibrium within 45 minutes for
the whole range of initial heavy metal concentrations. The adsorption data were found to
match well with pseudo second-order kinetic model. The adsorption isotherm obeyed
Langmuir isotherm better than Freundlich isotherm. The maximum adsorption capacities of
the activated carbon for Cu(II) and Pb(II) were 4.5 and 5.4 mmol/g, respectively.
41
Gueu et al98, in 2007, produced activated carbons from coconut and seed hull of palm tree by
chemical activation using concentred orthophosphoric acid. Carbonization was done at 400C
for sixteen hours. The activated carbons were tested for adsorption of Pb2+ from simulated
waste water. Their results showed that the adsorption capacities of the activated carbons
increased with increase in the initial lead concentration from 100 to 500mg/L and with
increase in temperature from 30 to 60C. The adsorption processes followed pseudo first
order kinetics and were well described by both Langmuir and Freundlich isotherms. The
equilibrium adsorption capacities were determined at 60C, pH of 4 and initial Pb2+
concentration of 100 mg/L using the Langmuir isotherm and were found to be 4.38 and
3.77mg/g for coconut and seed hull of palm tree activated carbons, respectively.
In 2008, Aziza et al99 produced powdered activated carbons from bumper sawdust (softwood)
and disk sawdust (hard wood) by chemical activation using calcium chloride as activating
agent. Carbonization was done in a furnace at 450oC for 90minutes. They compared the
properties of untreated, carbonized, carbonized then activated, and activated then carbonized
raw materials and found that the sequence of their iodine adsorption number, porosity and
bulk density was untreated < carbonized < carbonized then activated < activated then
carbonized bumper sawdust. For the disk sawdust, there was no consistent trend for the three
properties. However, they took the activation before carbonization method as the optimum
method for the production of activated carbon from both raw materials. They found that the
activated carbon from bumper sawdust had higher iodine adsorption number (2.1648),
porosity (0.9671) and bulk density (0.59g/cm3) than disk sawdust which had iodine
adsorption number of 2.1539, porosity of 0.9560 and bulk density 0.44g/cm3. The activated
carbon from both raw materials were tested for adsorption of Pb (II) from effluent water and
the activated carbon from bumper sawdust was found to adsorb more metal than the activated
carbon from disk sawdust.

42
In 2009, Kannan and Veemaraj100 produced activated carbon from bamboo dust by
carbonization in a muffle furnace at 600oC followed by activation with nitric acid. The
activated carbon was tested for removal of lead (II) ions. Percentage removal of the ions
decreased with increase in initial concentration from 100 to 1000ppm and increased with
increase in contact time up to 50minutes and with increase in dose of adsorbent from 10 to
28g/l. Percentage removal also increased with increase in pH up to a pH of 7.2, after which it
decreased with further increase in pH. Amount of lead (II) ions adsorbed increased with
decrease in particle size of the adsorbent. The adsorption process obeyed the first order
kinetics with intra-particle diffusion as one of the rate determining steps. The adsorption
process was better described by the Langmuir isotherm than the Freundlich isotherm. The
carbon was found to have a monolayer adsorption capacity of 2.151mg/g.
Some of the reported values for monolayer adsorption capacities are rather low. Hence, there
is still the need to discover other low cost raw materials that could yield carbons with much
higher adsorption capacities.

43
CHAPTER THREE
EXPERIMENTAL
3.1 Chemicals and Instrumentation
All the chemicals used were of analytical grade. Stock solutions (1000mg/l) were prepared
from CuSO4.5H2O for copper and from Pb(NO3)2 for lead using de-ionized water. All
working solutions were prepared by proper dilution of the stock solution with de-ionized
water. 0.1M NaOH and 0.1M HCl stock solutions were used to adjust the solution pH.
Jenway 3510 pH meter was used for measurement of solution pH throughout the study. The
concentration of the solution before and after sorption was measured using atomic absorption
spectrometer (Buck Scientific, Model 210 VGP). Vecstar programmable muffle furnace
(model LF 3) was used for carbonization of samples. Air drying oven (# BTOV 1423) was
used for drying of samples. AR 3130 weighing balance was used for weighing of samples.
3.2 Production of Activated Carbon
The raw materials, Telfairia occidentalis seed shell (TOSS) and Gambeya albida seed shell
(GASS), were obtained from Nsukka environment. They were thoroughly cleaned to remove
extraneous materials, dried and ground to smaller particle sizes. They were then sieved using
conventional sieves to get the desired particle sizes. The portions taken were those that
passed through 1.75mm and retained in 1mm sieve mesh size and those that passed through
1mm and retained in 0.5mm sieve mesh size.
3.2.1 Effect of Activating Conditions
To determine the effect of activating conditions on the resulting carbon, the sieved material
with size 0.5mm - 1mm was used. 60% by weight H3PO4 and 60% by weight NH4Cl
44
solutions were used as the activating agents. The raw materials were impregnated with the
activating agents in 1:1 wt. ratio for 24 hours, after which they were drained and dried in an
oven at 80C. They were then put in crucibles and placed in a muffle furnace set at 300C for
carbonization. TOSS was left for 60 minutes while GASS was left for 90 minutes since it is
harder. The resulting carbons were washed with distilled water until the pH of the leachate
was up to 6. They were then dried in an oven at 105C for 4 hours. For GASS, the raw GASS
was used as the blank while for TOSS, a third sample was carbonized without prior activation
and was used as the blank.
3.2.2 Effect of Carbonization Temperature
To determine the effect of carbonization temperature on resulting carbons, the portion of the
samples with particle size of 0.5mm - 1mm was activated with phosphoric acid and then
divided into four portions. These portions were carbonized (for 60minutes for TOSS and
90minutes for GASS) at 300C, 400C, 500C and 600C.
3.2.3 Effect of Carbonization Time
To determine the effect of carbonization time on the resulting carbons, the portion of the
samples with particle size of 1mm 1.75mm was used. The samples were activated with
phosphoric acid and then divided into five different portions, each. The portions were
carbonized (at 500C for TOSS and 600C for GASS) for 60, 90, 120, 150 and 180 minutes.
3.3 Characterization of Adsorbents
3.3.1 Determination of %Yield and %Weight Loss
The yield of activated carbon was defined as the ratio of the weight of the activated carbon
product to that of the original raw material (both weights were on a dry basis).
45
That is,
%Yield = (W1W0) x 100 (3.1)
where W0(g) is the original weight of the precursor on a dry basis and W1(g) is the weight of
the carbon after carbonization, washing, and drying.
The weight loss was calculated according to equation (3.2).
%Weight loss = [(W0 W1) W0] x 100 (3.2)
3.3.2 Surface Area Measurement
The surface area of each adsorbent was determined according to the method of Al-Qodah and
Shawarbkah41. In the process, 1.5g of activated carbon was agitated in 100ml of HCl that had
been diluted to pH of 3. Then 30g of NaCl was added while stirring the suspension. The
volume was then made up to 150ml with de-ionized water resulting in the change of the pH
to 4.0. 0.10N NaOH was used to raise the pH from 4 to 9 and the volume of NaOH used, V,
recorded. The surface area was then calculated using the following equation:
S = 32V 25 (3.3)
where, S is the surface area (m2/g).
3.3.3 Determination of % Ash Content
The ash content of each adsorbent was determined using a standard method according to
101
ASTM D 2866-94 . In the process, a weighed sample of each adsorbent was pre-dried at
150C, and then burnt in a muffle furnace at 650C for 4 hours in the presence of air. The %
ash content was calculated from the combustion residue as follows.
% Ash content = Wash/Wads x 100 (3.4)

46
where, Wash is the weight of dry ash (g) and Wads is the weight of dry adsorbent (g). This test
was repeated until constant ash content was obtained.
3.3.4 Determination of Bulk Density
The apparent or bulk density of each adsorbent was determined by the tapping procedure102.
A known weight of each sample, after being dried at 105C, was parked into a 10ml capacity
graduated cylinder. The bottom of the cylinder was tapped gently on the laboratory bench top
several times until there was no further diminution of the sample level. The bulk density was
then calculated using the following equation.
Bulk density (g/ml) = Wmat/Vmat (3.5)
where, Wmat is the weight of dry material (g) and Vmat is the volume of dry material (ml).
3.3.5 Determination of Total Pore Volume
The total pore volume of each adsorbent was determined by boiling a weighed sample of the
adsorbents immersed in water. After the air in the samples had been displaced, the samples
were superficially dried and weighed. The increase in weight divided by the density of water
gave the pore volume.
3.4 Adsorption Tests
Batch adsorption process was employed for the adsorption tests. 0.5g of adsorbent was added
to 100ml of 200mgl metal solution at pH 2.5 and agitated using a magnetic stirrer set at
400rpm for 4hours at room temperature. The adsorbents were removed by filtration using
ash-less and fine crystalline filter paper Whatman No. 42. The filtrates were then digested by
the hot plate method103. To carry out this digestion, 1ml of concentrated HNO3 was added to
47
25ml of the filtrate in a beaker and then heated to 85C and maintained at that temperature till
the sample volume reduced to 45% by evaporation. Then the beaker was cooled slightly and
0.5ml of concentrated HCl was added. The digestate was then taken up to 25ml with de-
ionized water and subsequently analyzed for the residual metal concentration by atomic
absorption spectrometry.
The sorption capacity and percentage quantity adsorbed were calculated from equation (3.6)
and equation (3.7), respectively.
qt = [(Co Ct) x V] / (1000 x m) (3.6)
%q = [(Co Ct) Co] x 100 (3.7)
where qt is the amount of metal adsorbed (mg/g) at time, t, V is the volume of the solution
(ml), m is the weight of adsorbent (g), C0 and Ct are the metal concentration (mg/L) at the
initial time and at a time t, respectively.
For the adsorption tests, except the effect of production conditions, only TOSS carbonized at
500C for 60minutes and GASS carbonized at 600C for 120minutes were used.
3.4.1 Effect of Particle Size
To determine the effect of particle size, the adsorption tests were carried out using the
following particle sizes of the adsorbents:
1 1.75mm, 0.5 1mm, 0.25 0.5mm, and 0.125 0.25mm.
3.4.2 Effect of pH
To determine the effect of pH, the adsorption tests were carried out using metal solutions
adjusted to pH values of 2,3,4,5 and 6 using 0.1M NaOH and 0.1M HCl stock solutions.
48
3.4.3 Effect of Adsorbent Weight
In order to determine the effect of adsorbent weight, the adsorption tests were carried out
using the following weights of the adsorbent:
0.063g, 0.125g, 0.25g, 0.5g, and 1g.
3.4.4 Effect of Adsorption Temperature
In order to determine the effect of adsorption temperature on the adsorption processes, the
adsorption experiments were carried out at the following temperatures:
20oC, 30oC, 40oC and 50oC
3.5 Kinetic Study
The kinetic experiments for adsorption processes were also carried out by the batch process at
pH 2.5. In the process, 2.0g of adsorbent was added to 400 ml of adsorbate solutions of
concentration 50, 100, 200 and 400mg/l and mixed at a constant agitation speed of 400rpm.
25ml sample solution was withdrawn each time from the reaction mixture at a fixed time
interval, filtered, digested and analyzed for residual metal concentration as stated in section
3.4.
3.6 Isotherm Study
An aliquot (100ml) of adsorbates solution of concentration 50, 100, 150 and 200mg/L was
agitated with 0.5 g of adsorbent at 400rpm for 4 hours and filtered. The filtrates were then
digested and analyzed for residual metal concentrations as stated in section 3.4.
49
CHAPTER FOUR
RESULTS AND DISCUSSIONS
The results of the experimental investigation are presented and discussed in this chapter
under the following headings:
1. Characterization of Adsorbents
2. Effect of Process Variables on Adsorption
3. Kinetic Studies
4. Isotherm Studies
4.1 Characterization of Adsorbents
The properties of the adsorbents determined include the percentage yield, percentage weight
loss, surface area, total pore volume, bulk density and percentage ash content.
4.1.1 Characterization of Adsorbents Produced Using Different Activating Agents
Table 4.1 shows the effect of different activating agents on these properties for Gambeya
albida seed shell (GASS) adsorbents.
Table 4.1: Effect of Activating Agent on Properties of Gambeya albida Seed Shell
Parameter H3PO4 NH4Cl Raw material

Activation Activation
% Yield 70.68 77.92 -
% Weight loss 29.32 22.08 -
Surface area (cm2/g) 612.2 516.5 9.3
Total pore volume (cm3/g) 2.17 1.82 1.62
Bulk density (g/cm3) 0.492 0.556 0.621
% Ash content 1.50 0.60 0.35
50
It can be seen from the table that activation of the raw GASS resulted in increased surface
area, total pore volume and % ash content as well as decreased bulk density of the adsorbents.
The increase in total pore volume and surface area could both be attributed to the destruction
of the aliphatic and aromatic species present in the raw materials by the activating agents
leading to swift removal of volatile matters during the activation process97. These volatile
matters include considerable organic by-products and minerals present in the activated carbon
surface. The reduction of the volatile matter in the activated carbons creates a high
percentage of calculated ash since the ash is non-volatile14. The increase in pore volume of
the carbons causes a less weight of the carbon to occupy more space thereby leading to
decrease in bulk density.
The changes in the measured parameters were found to be higher on activation with
phosphoric acid. Also, the activation with phosphoric acid led to higher % weight loss and
lower % yield than activation with ammonium chloride. These suggest that activation with
phosphoric acid probably involved stronger reactions, such as oxidation of the raw materials,
thereby leading to higher changes in the measured parameters.
Table 4.2 shows the effect of different activating agents on the properties of Telfairia
occidentalis seed shell (TOSS) adsorbents.
Table 4.2: Effect of Activating Agent on Properties of Telfairia occidentalis Seed Shell
Parameter H3PO4 NH4Cl Carbonized

Activation Activation Raw material
% Yield 50.23 67.00 70.94
% Weight loss 49.77 33.00 29.06
2
Surface area (cm /g) 791.0 691.8 251.0
Total pore volume (cm3/g) 2.27 1.77 0.89
Bulk density (g/cm3) 0.370 0.437 0.512
% Ash content 1.70 0.89 0.50
51
It can be seen from the table that activation of the raw material followed by carbonization
results in carbons with higher adsorption potentials than carbonization without prior
activation. This is shown by the fact that the activated TOSS had higher surface area and total
pore volume than the non-activated, carbonized TOSS. This can be attributed to the fact that
there is higher burn-off of volatile matters from the raw materials during carbonization with
activating agents present. This is because the activating agents dehydrate the raw materials36.
The activated carbons, however, had higher % weight loss and % ash content as well as lower
% yield and bulk density.
The changes in the measured properties were also found to be higher on activation with
phosphoric acid than with ammonium chloride. This could also be as a result of the
occurrence of stronger reactions in the case of phosphoric acid.
4.1.2 Characterization of Adsorbents Carbonized at Different Temperatures
Table 4.3 shows the effect of carbonization temperature on the properties of the adsorbents
produced using H3PO4 as activating agent.
Table 4.3: Effect of Carbonization Temperature on Properties of Adsorbents Produced

Using H3PO4 as Activating Agent
Parameter 300C 400C 500C 600C

TOSS GASS TOSS GASS TOSS GASS TOSS GASS
% Yield 50.23 70.68 46.90 67.12 42.77 62.64 38.84 58.12
% Weight loss 49.77 29.32 53.10 32.88 57.23 37.36 61.16 41.88
Surface area (cm2/g) 785.0 712.2 829.8 763.4 953.0 868.2 998.6 900.2
Total pore volume 2.27 2.17 2.50 2.37 2.93 2.48 3.38 2.52
(cm3/g)
Bulk density 0.370 0.492 0.357 0.485 0.324 0.468 0.290 0.452
(g/cm3)
% Ash content 1.70 1.50 3.85 1.95 5.30 2.25 6.20 2.45
52
From the table, it can be seen that the bulk density and % yield of the adsorbents decrease
while surface area, total pore volume, % weight loss and % ash content increase with increase
in carbonization temperature from 300oC to 600oC for both raw materials. This trend could be
attributed to the increase in thermal decomposition of the raw materials as the carbonization
temperature increases104 resulting in increased removal of volatile materials. Since % yield
decreases with increase in carbonization temperature, production losses should therefore be
considered in choosing the carbonization temperature for production of activated carbon.
4.1.3 Characterization of Adsorbents Carbonized for Different Lengths of Time
Table 4.4 shows the effect of carbonization time on the properties of the adsorbents produced
using H3PO4 as activating agent at 500oC and 600oC for TOSS and GASS, respectively.
Table 4.4: Effect of Carbonization Time on Properties of Adsorbents Produced Using

H3PO4 as Activating Agent at 500oC for TOSS and 600oC for GASS
Parameter 60 90 120 150 180

(mins) (mins) (mins) (mins) (mins)
TOSS GAS TOSS GAS TOSS GAS TOSS GAS TOSS GASS
S S S S
% Yield 48.06 64.91 45.75 60.01 40.17 55.82 37.75 51.86 35.58 44.37
% Weight loss 51.94 35.09 54.25 39.99 59.83 44.18 62.23 48.14 64.43 55.63
Surface area 874.6 837.0 919.4 886.8 937.4 906.2 963.0 941.8 1006.6 984.6
(cm2/g)
Total pore 2.77 2.65 3.10 2.97 3.52 3.23 3.72 3.45 3.92 3.54
volume (cm3/g)
Bulk density 0.286 0.465 0.270 0.423 0.263 0.386 0.256 0.357 0.250 0.343
(g/cm3)
% Ash content 3.40 2.45 4.60 3.95 5.15 4.90 5.60 5.30 6.35 5.50
From the table, it can be seen that the bulk density and % yield of the adsorbents decrease
while surface area, total pore volume, % weight loss and % ash content increase with increase
in carbonization time from 60 minutes to 180 minutes for both raw materials. This trend
53
could be attributed to the increase in removal of volatile matter as a result of increase in
thermal decomposition of the raw material as the carbonization time increases30. Since %
yield decreases with increase in carbonization time, it is therefore necessary to consider
production losses in choosing the carbonization time for production of activated carbon.
From Tables 4.1 to 4.4, it can be seen that the TOSS carbons had higher surface area, total
pore volume, percentage weight loss and ash content as well as lower bulk density and
percentage yield than the GASS carbons produced under the same experimental conditions.
This may be attributed to higher thermal decomposition of TOSS than GASS.
4.2 Effect of Process Variables on Adsorption
4.2.1 Effect of Activating Agent on Adsorption
Table 4.5 shows the effect of activating agent on GASS with respect to the quantity of Pb2+
and Cu2+ adsorbed by each of the GASS adsorbents.
Table 4.5: Effect of Activating Agent on Adsorption Parameters using Gambeya albida
Seed Shell Processed at 600oC*
Sample Ce C o Ce q %q
(mg/l) (mg/l) (mg/g)
Pb2+ Cu2+ Pb2+ Cu2+ Pb2+ Cu2+ Pb2+ Cu2+
H3PO4 147.00 159.75 53.00 40.50 10.60 8.05 26.50 20.13
Activation
NH4Cl 166.00 168.75 34.00 31.25 6.80 6.25 17.00 15.63
Activation
Raw Material 188.00 190.25 12.00 9.75 2.40 1.95 6.00 4.88
* Co (mg/l) = 200; V (ml) = 100; m (g) = 0.5; Ce = equilibrium concentration of the

adsorbate; Co = initial concentration of the adsorbate; q = amount of metal ion adsorbed; % q
= percent of original concentration of metal ion adsorbed; V = volume of the solution; m =
mass of adsorbent
54
The results show that the activated carbons adsorbed higher quantities of the metals than the
raw (unreacted) GASS. Similar behaviour was observed by Aziza et al99 for the adsorption of
Pb2+ on activated carbon from bumper sawdust and raw bumper sawdust. The results also
show that activation with phosphoric acid led to higher adsorption potential of the resulting
carbon than activation with ammonium chloride. For example, the phosphoric acid activated
carbon adsorbed 10.60mg/g of Pb2+ while the ammonium chloride activated carbon adsorbed
only 5.40mg/g.
Table 4.6 shows the effect of activating agent on TOSS with respect to the adsorption of Pb2+
and Cu2+.
Table 4.6: Effect of Activating Agent on Adsorption Parameters using Telfairia

occidentalis Seed Shell Processed at 500oC
Sample Ce C o Ce q %q
Pb2+ Cu2+ Pb 2+
Cu2+ Pb2+ Cu2+ Pb2+ Cu2+
H3PO4 109.25 110.75 90.75 89.25 18.15 17.85 45.38 44.63
Activation
NH4Cl 164.50 173.00 35.50 27.00 7.10 5.40 17.75 13.50
Activation
Raw Material 185.00 190.00 15.00 10.00 3.00 2.00 7.50 5.00
(Carbonized)
The results show that activation of the sample prior to carbonization led to higher adsorption
potential than carbonization without prior activation. Similar behaviour was also observed by
Aziza et al99 for the adsorption of Pb2+ on activated carbon from bumper sawdust and raw
bumper sawdust. The results also show that activation with phosphoric acid led to higher
adsorption potential than activation with ammonium chloride. As a result of this, activation
with phosphoric acid was employed in the further production of the carbons used for the rest
of this research.
55
4.2.2 Effect of Carbonization Temperature on Adsorption
Figure 4.1 shows the effect of carbonization temperature of the samples on their adsorption of
Pb2+ and Cu2+. The results are also presented in tabular form in Tables 4.7 and 4.8 for Pb2+
and Cu2+ adsorption, respectively.
Figure 4.1: Effect of Carbonization Temperature on Amount of Metal Adsorbed
Table 4.7: Effect of Carbonization Temperature on Adsorption of Pb2+
T Ce Co Ce q %q
o
( C) (mg/l) (mg/l) (mg/g)
300 109.25 147.00 90.75 53.00 18.15 10.60 26.50 44.63
400 92.25 120.50 107.75 79.50 21.55 15.90 38.25 48.38
500 74.50 95.50 125.50 104.50 26.00 20.90 52.25 57.25
600 68.25 71.50 131.75 128.50 26.35 25.70 64.25 61.25
56
Table 4.8: Effect of Carbonization Temperature on Adsorption of Cu2+
T Ce Co Ce q %q
o
( C) (mg/l) (mg/l) (mg/g)
300 110.75 159.75 89.25 40.25 17.85 8.05 44.63 20.13
400 103.25 155.00 96.75 45.00 19.35 9.00 48.38 22.50
500 85.50 146.75 114.50 53.25 22.90 10.65 57.25 26.63
600 77.50 138.25 122.50 61.75 24.50 12.35 61.25 30.88
From the results, it can be seen that for both raw materials, adsorption increased as carbons
produced at higher temperatures were used. This is as a result of possession of higher
adsorption properties by carbons produced at higher temperatures. Similar trend was
observed by Ozer et al30 for the adsorption of cadmium on activated carbon from sugar beet
pulp in which case removal percentage of cadmium increased from 35.0 to 99.0% with
increase in carbonization temperature from 350oC to 700oC. From Figure 4.1, it can also be
seen that Pb2+ was more preferentially adsorbed than Cu2+ by both adsorbents. Similar
behaviour was observed by Kongsuwan et al97 for the adsorption of Pb2+ and Cu2+ on
Eucalytus camaldulensis dehn bark. The differential removal of the two ions may be
described as being due to the difference in their ionic radius. It has been shown that the
smaller the ionic radius or area, the greater is its tendency to be hydrolyzed leading to
reduced sorption105. The differential removal was found to be higher when carbons produced
at temperatures above 300oC were used.
The results also show that the TOSS carbons adsorbed more of each metal than the GASS
carbons carbonized at the same temperature. This can be attributed to the possession of
higher adsorption properties (surface area and total pore volume) by TOSS carbons than
GASS carbons carbonized at the same temperature as shown in Table 4.3. However,
57
carbonization at 600oC resulted in marginal increase in the amount of lead adsorbed by
TOSS. As a result of this and also taking production losses (in terms of % weight loss) into
consideration, 500oC was used for the further production of carbons from TOSS for the rest
of the research while 600oC was used for GASS.
4.2.3 Effect of Carbonization Time
Figure 4.2 shows the effect of carbonization time at 500oC and 600oC for TOSS and GASS,
respectively on their adsorption of Pb2+ and Cu2+. The results are also presented in tabular
form in Tables 4.9 and 4.10 for Pb2+ and Cu2+ adsorption, respectively.
Figure 4.2: Effect of Carbonization Time at 500oC for TOSS and 600oC for GASS on
Amount of Metal Adsorbed

58
Adsorption of Pb2+
Time Ce Co Ce q %q
(mins) (mg/l) (mg/l) (mg/g)
60 136.00 146.00 64.00 54.00 12.80 10.80 32.00 27.00
90 118.25 117.50 81.75 82.50 16.35 16.50 40.88 41.25
120 98.25 104.25 101.75 95.75 20.35 19.15 50.88 47.88
150 83.50 102.25 116.50 97.75 23.30 19.55 58.25 51.13
180 76.25 85.50 123.75 114.50 24.75 22.90 61.88 57.25
Adsorption of Cu2+
Time Ce Co Ce q %q
(mins) (mg/l) (mg/l) (mg/g)
60 151.50 167.25 48.50 32.75 9.70 6.55 27.00 24.25
90 117.50 143.25 82.50 56.75 16.50 11.35 41.25 41.25
120 107.00 126.50 93.00 73.50 18.60 14.70 47.88 46.50
150 100.25 102.75 99.75 97.25 19.95 19.45 51.13 49.88
180 95.50 98.50 104.50 101.50 20.90 20.30 57.25 52.25
From the results, it can be seen that for both raw materials, adsorption increased as carbons
produced by carbonization for longer period of time were used. This is as a result of
possession of higher adsorption properties by carbons produced by longer carbonization.
Similar trend was observed by Ozer et al30 for the adsorption of cadmium on activated carbon
from sugar beet pulp in which case removal percentage of cadmium increased from 10.0 to
58.0% with increase in carbonization time from 15 to 120 minutes. The results also show that
Pb2+ was also more preferentially adsorbed than Cu2+ by both adsorbents.
From the results, it can also be seen that the TOSS carbons adsorbed more of each metal than
the GASS carbons carbonized for the same length of time. This is can be attributed to the
59
possession of higher adsorption properties (surface area and total pore volume) by TOSS
carbons than GASS carbons carbonized for the same length of time as was shown in Table
4.4. However, carbonization for 150 and 180minutes resulted in marginal increase in the
amount of metal adsorbed by the carbons from both raw materials. As a result of this and also
taking production losses (in terms of % weight loss) into consideration, carbonization was
done for 60minutes and 120minutes for TOSS and GASS, respectively in the further
production of carbons for the rest of this research.
4.2.4 Effect of Particle Size on Adsorption
Figure 4.3 shows the effect of particle size of the carbons on their adsorption of Pb2+ and
Cu2+. The results are also presented in tabular form in Tables 4.11 and 4.12 for Pb2+ and Cu2+
adsorption, respectively.
Figure 4.3: Effect of Particle Size on Amount of Metals Adsorbed

60
Table 4.11: Effect of Particle Size on Adsorption of Pb2+
Particle Size Ce C o Ce q %q
(mm)
1 1.75 136.00 104.25 64.00 95.75 12.80 19.15 32.00 47.88
0.5 1 130.50 82.25 69.50 117.75 13.90 23.55 34.75 58.88
0.25 0.5 125.50 64.00 74.50 136.00 14.90 27.20 37.25 68.00
0.125 0.25 120.00 48.75 80.00 151.25 16.00 30.25 40.00 75.63
Table 4.12: Effect of Particle Size on Adsorption of Cu2+
Particle Size Ce C o Ce q %q
(mm)
1 1.75 151.50 126.50 48.50 73.50 9.70 14.70 24.25 36.75
0.5 1 141.25 95.75 58.75 104.25 11.75 20.85 29.38 52.13
0.25 0.5 132.00 77.75 68.00 122.25 13.60 24.45 34.00 61.13
0.125 0.25 125.00 63.25 75.00 136.75 15.00 27.35 37.50 68.38
As shown in the results, adsorption decreased linearly with increase in particle size of the
carbons. This is as a result of increase in surface area as the particle size decreases34 resulting
in higher adsorption since more adsorbate particles can adhere to the sorbent surface. Similar
trend was observed by Soleimani and Kaghazchi39 for the adsorption of gold on activated
carbon from apricot stones during which percentage metal adsorption decreased from 80% to
67% with increase in particle size from 35 50 mesh to 12 16 mesh. The increase in
adsorption with decrease in particle size was more for the GASS carbon. The results also
show that the GASS carbon adsorbed more of both metals than the TOSS carbon. This could
be attributed to the fact that GASS carbonized at 600oC for 120minutes possessed better
adsorption properties (higher surface area and pore volume) than TOSS carbonized at 500oC
for 60minutes as shown in Table 4.4.

61
4.2.5 Effect of Solution pH on Adsorption
Figure 4.4 shows the effect of pH of the metal solutions on the adsorption of the metals by
the carbons. The results are also presented in tabular form in Tables 4.13 and 4.14 for Pb2+
and Cu2+ adsorption, respectively.
Figure 4.4: Effect of Solution pH on Amount of Metals Adsorbed
Table 4.13: Effect of Solution pH on Adsorption of Pb2+
pH Ce C o Ce q %q
2 155.75 122.75 44.25 77.25 8.85 15.45 22.13 38.63
3 105.50 80.75 94.50 119.25 18.91 23.85 47.25 59.63
4 55.25 58.00 144.75 142.00 28.95 28.40 72.38 71.00
5 33.50 27.50 166.50 172.50 33.30 34.50 83.25 86.25
6 21.50 21.24 178.50 178.76 35.70 35.75 89.25 89.38
62
Table 4.14: Effects of Solution pH on Adsorption of Cu2+
pH Ce C o Ce q %q
2 196.00 156.00 4.00 44.00 0.80 8.80 2.00 22.00
3 151.50 113.25 48.50 86.75 9.70 17.35 24.25 43.38
4 110.00 80.00 90.00 120.00 18.00 24.00 45.00 60.00
5 83.25 56.50 116.75 143.50 23.35 28.70 58.38 71.75
6 39.58 33.00 160.50 167.00 32.10 33.40 80.21 83.50
From the results, it can be observed that adsorption increased with increasing pH up to pH
value of 5. This trend can be explained by the fact that at low pH (1 3), the metal ions had
to compete with H+ ions for adsorption sites on the adsorbent surface. As the pH increased,
this competition weakened and more metal ions were able to replace H+ ions bound to the
adsorbent surface79. Similar trend was observed by Kongsuwan et al97 for the adsorption of
Pb2+ and Cu2+ on Eucalytus camaldulensis dehn bark. However, from pH value of 6, the
metal ions were precipitated out of their solutions as their hydroxides. Similar behaviour was
observed by Dahiya et al106. This condition has been described as undesirable during sorption
experiments as it can lead to a misunderstanding of adsorption capacity97. The results also
show that the GASS carbon adsorbed more of each metal than the TOSS carbon.
4.2.6 Effect of Adsorbent Weight on Adsorption
Figure 4.5 shows the effect of the weight of the adsorbents used on the adsorption of the
metals from their solutions. The results are also presented in tabular form in Tables 4.15 and
4.16 for Pb2+ and Cu2+ adsorption, respectively.

63
Figure 4.5: Effect of Adsorbent Weight on Amount of Metals Adsorbed
Table 4.15: Effects of Adsorbent Weight on Adsorption of Pb2+
m Ce C o Ce q %q
(g) (mg/l) (mg/l) (mg/g)
0.063 182.00 155.74 18.00 44.26 28.57 70.25 9.00 22.13
0.125 172.00 142.25 28.00 57.75 22.40 46.20 14.00 28.88
0.25 161.00 120.00 39.00 80.00 15.60 32.00 19.50 40.00
0.5 136.00 104.25 64.00 95.75 12.80 19.15 32.00 47.88
1 96.25 30.98 103.75 169.02 10.38 16.90 51.88 84.51
Table 4.16: Effect of Adsorbent Weight on Adsorption of Cu2+
m Ce C o Ce q %q
(g) (mg/l) (mg/l) (mg/g)
0.063 184.50 174.00 15.50 26.00 24.60 41.27 7.75 13.00
0.125 176.00 166.00 24.00 34.00 19.20 27.20 12.00 17.00
0.25 170.00 152.00 30.00 48.00 12.00 19.20 15.00 24.00
0.5 151.50 126.50 48.50 73.50 9.70 14.70 24.25 36.75
1 123.50 86.25 69.00 113.75 6.90 11.38 34.25 56.88
64
From the figure, it can be seen that the percentage quantity adsorbed (%q) increased linearly
with increase in adsorbent weight. This is as a result of the fact that the quantity of sites for
adsorption increases with increase in adsorbent weight106. Similar trend was observed by
Dave et al107 for the adsorption of Cu2+ on commercial activated carbon. However, from the
tabular results, it can be seen that the quantity of the metals adsorbed per gram of adsorbent
(q) decreases with increase in the weight of adsorbent used. This is as a result of the fact that
the adsorbate ions concentration decreases per active site available for adsorption on the
adsorbent106. The results also show that the GASS carbon adsorbed more of both metals than
the TOSS carbon.
4.2.7 Effect of Adsorption Temperature on Amount of Metals Adsorbed
Figure 4.6 shows the effect of adsorption temperature on the adsorption of the metals by the
carbons. The results are also presented in tabular form in Tables 4.17 and 4.18 for Pb2+ and
Cu2+ adsorption, respectively.
Figure 4.6: Effect of Adsorption Temperature on Amount of Metals Adsorbed

65
Table 4.17: Effect of Adsorption Temperature on Adsorption of Pb2+
T Ce C o Ce q %q
(C ) (mg/l) (mg/l) (mg/g)
20 118.25 92.25 81.75 107.75 16.35 21.55 40.88 53.88
30 136.00 104.25 64.00 95.75 12.80 19.15 32.00 47.88
40 157.50 117.00 42.50 83.00 8.50 16.60 21.25 41.50
50 171.00 137.75 29.00 62.25 5.80 12.45 14.50 31.13
Table 4.18: Effect of Adsorption Temperature on Adsorption of Cu2+
T Ce C o Ce q %q
(C ) (mg/l) (mg/l) (mg/g)
20 127.75 109.75 72.25 90.25 14.45 18.05 36.13 45.13
30 153.50 126.50 46.50 73.50 9.30 14.70 23.25 36.75
40 169.00 146.50 31.00 53.50 6.20 10.70 15.50 26.75
50 192.50 159.00 7.50 41.00 1.50 8.20 3.75 20.50
It is observed from the results that the adsorption decreased as temperature increased. This is
in agreement with the results obtained by Teker et al93 for the adsorption of Cu2+ and Cd2+ on
activated carbon from rice hulls. This decrease in adsorption capacity with increase in
temperature indicates that the adsorption processes were exothermic in nature109. The results
also show that the GASS carbon adsorbed more of both metals than the TOSS carbon.
4.2.8 Effect of Contact Time and Initial Metal Ion Concentration on Adsorption
Figures 4.7 and 4.8 show the effects of contact time and initial metal ion concentration on the
adsorption of Pb2+ and Cu2+, respectively, using TOSS carbon while Figures 4.9 and 4.10
show the effects using GASS carbon. The results are also presented in tabular form in
Appendix A.1 A.16.

66
Adsorbed using TOSS carbon.
Figure 4.8: Effects of Contact Time and Initial Concentration of Cu2+ on its Amount
Adsorbed using TOSS carbon.
67
Adsorbed using GASS carbon.
Figure 4.10: Effects of Contact Time and Initial Concentration of Cu2 on its Amount
Adsorbed using GASS carbon.
68
Generally, there was an initial rapid sorption for about 50 minutes of agitation after which the
rate of sorption became slower. After 130 210 minutes of agitation, equilibrium was
attained. This can be explained by the fact that within the first 50 minutes, the adsorbent still
had a vast number of unoccupied sites unto which the adsorbate particles could adsorb. As a
result, there was a high probability of adsorption for every migrating/diffusing molecule of
adsorbate. The adsorbate particles adsorbed within the first 50 minutes leading to a decrease
in the number of unoccupied sites, which made the adsorption to become slower since the
adsorbent surface was approaching saturation110. After 130 210 minutes, the adsorbent sites
were completely occupied by the adsorbate particles. At this stage, the system attained
equilibrium at which the rate of adsorption became equal to the rate of desorption. Similar
trend has been observed by various researchers such as Kongsuwan et al97 for the adsorption
of Pb2+ and Cu2+ on Eucalytus camaldulensis dehn bark carbon and Kang et al17 for the
adsorption of Cu2+ and Cd2+ on pretreated activated carbons.
The adsorption processes could be well described using the explanation regarding the
dispersion force between metal ions and surface of activated carbon. As the positively
charged ion approached the surface of the activated carbon, the surface of the carbon was
slightly induced to exhibit negatively charged property and the attraction between the two
dipoles which was likely to lower the potential energy between them occurred and eventually
brought about adsorption97. The rapid initial sorption was likely due to extra-cellular binding
and the slower sorption likely resulted from intracellular binding111. The plots of metal uptake
as a function of time (Figures 4.7 4.10) are single, smooth and continuous, leading to
saturation. This suggests possible monolayer coverage of the metal ions on the surface of the
adsorbent71.
69
From the figures, it can also be seen that the adsorption is highly dependent on initial metal
concentration. The amount of metal adsorbed per unit weight of carbon increased with
increase in initial metal concentration of solution. Similar trend was observed by Kilic et al112
and was attributed to the increase in driving force for adsorption with increase in initial metal
concentrations. Also, according to Aksu and Akpinar113, increases in initial metal ion
concentrations are effective to break the resistance originating from mass transfer, resulting
in increased adsorption.
4.3 Kinetic Studies
In order to investigate the kinetics of the adsorption processes, the data shown in Figures 4.7
4.10 were analyzed using various kinetic model equations, which are, the Bhattacharya-
Venkobachar, pseudo-first order, Elovich and pseudo-second order kinetic model equations.
The mathematical linear forms of the equations were used.
4.3.1 Kinetic analysis of Pb2+ adsorption on TOSS carbon
Figure 4.11 shows the Bhattacharya-Venkobachar plot for the adsorption of different
concentrations of Pb2+ on TOSS carbon.
Figure 4.11: Bhattacharya-Venkobachar Plot for Pb2+ Adsorption on TOSS Carbon

70
Figure 4.12 shows the pseudo-first order plot for the adsorption of different concentrations of
Pb2+ on TOSS carbon.
Figure 4.12: Pseudo First Order Plot for Pb2+ Adsorption on TOSS Carbon
Figure 4.13 shows the Elovich plot for the adsorption of different concentrations of Pb2+ on
TOSS carbon.
Figure 4.13: Elovich Plot for Pb2+ Adsorption on TOSS Carbon

71
Figure 4.14 shows the pseudo-second order plot for the adsorption of different concentrations
of Pb2+ on TOSS carbon.
Figure 4.14: Pseudo Second Order Plot for Pb2+ Adsorption on TOSS Carbon
of Pb2+ on TOSS carbon.
Figure 4.15: Weber and Morris Plot for Pb2+ Adsorption on TOSS Carbon
72
The associated kinetic parameters for each of the kinetic models for the different metal
concentrations have been evaluated from the slopes and intercepts of the respective linear
plots and are shown in Table 4.19.
Table 4.19: The Kinetic Parameters for Pb2+ Adsorption on TOSS Carbon
Kinetic model Parameter Solute Concentration (mg/l)

50 100 150 200
Bhattacharya- KB (min-1) -0.035 -0.028 -0.030 -0.030
Venkobachar R2 0.995 0.943 0.989 0.979
Pseudo-first K1 (min-1) -0.035 -0.028 -0.030 -0.032
order qe (mg/g) 7.194 6.668 9.183 12.134
2
R 0.995 0.948 0.989 0.981
Elovich (mg.g . min )
-1 -1 0.945 1.144 1.242 1.540
(mg.g-1. min-1) 0.490 0.462 0.379 0.318
R2 0.982 0.977 0.988 0.964
-1 -1
Pseudo-second K2 (g.mg .min ) 0.0075 0.0066 0.0049 0.0037
order qe (mg/g) 8.475 9.524 11.628 14.286
R2 0.997 0.999 0.998 0.996
Weber and Kid (mg.g-1.min-0.5) 0.933 1.169 1.442 1.828
Morris R2 0.950 0.926 0.942 0.979
A comparison of the various kinetic plots based on their linear regression coefficient (R2)
values shows that pseudo-second order model best described the adsorption at all the
considered concentrations. Therefore, the adsorption of Pb2+ on TOSS carbon can best be
described using the pseudo-second order model. The pseudo-second order rate constants (k2)
decreased while the equilibrium capacity values (qe) increased with increase in concentration
of the adsorbates. Estimated values of equilibrium capacity fell within the range of
experimental data. The decrease of the pseudo-second order rate constant (k2) with increasing
concentration confirmed that the adsorption processes became faster with increasing the
solute concentration in solution. This behavior was reported by Debnath and Ghosh83.
73
Table 4.20 shows the calculated intra-particle and film diffusion constants for the adsorption
of the different concentrations of Pb2+ on TOSS carbon.
Table 4.20: Intra-particle (DP) and Film Diffusion Constants (DF) for Pb2+ Adsorption
on TOSS Carbon
Constant Solute Concentration (mg/l)

50 100 150 200
2 -1 -4 -4 -3
DP (cm .s ) 9.66x10 9.33x10 1.32x10 5.57x10-4
DF (cm2.s-1) 6.89x10-6 2.92x10-6 3.14x10-6 1.20x10-6
The calculated intra-particle diffusion coefficients, DP, for the adsorption of the different
metal concentrations were in the range of 10-3 to 10-4cm2.s-1. DP-values in the range of 10-11 to
10-13 cm2.s-1 suggest that intra-particle diffusion is the rate limiting step83. However, the
calculated values are up to six orders greater than 10-11cm2.s-1. This shows that intra-particle
diffusion is not the rate limiting step for Pb2+ adsorption on TOSS carbon.
From the table, the calculated DF-values are found to be in the order of 10-6 cm2.s-1 for all the
considered Pb2+ concentrations. DF-value in the range of 10-6 to 10-8 cm2.s-1 shows that the
rate limiting step is controlled by film (boundary layer) diffusion90. Therefore, the rate of
adsorption of Pb2+ on TOSS carbon is controlled by film (boundary-layer) diffusion.
4.3.2 Kinetic analysis of Cu2+ adsorption on TOSS carbon
concentrations of Cu2+ on TOSS carbon.

74
Figure 4.16: Bhattacharya-Venkobachar Plot for Cu2+ Adsorption on TOSS Carbon
Cu2+ on TOSS carbon.
Figure 4.17: Pseudo First Order Plot for Cu2+ Adsorption on TOSS Carbon
75
Figure 4.18 shows the Elovich plot for the adsorption of different concentrations of Cu2+ on
TOSS carbon.
Figure 4.18: Elovich Plot for Cu2+ Adsorption on TOSS Carbon
of Cu2+ on TOSS carbon.
Figure 4.19: Pseudo Second Order Plot for Cu2+ Adsorption on TOSS Carbon
76
Figure 4.20 shows the Weber and Morris plot for the adsorption of different concentrations of
Cu2+ on TOSS carbon.
Figure 4.20: Weber and Morris Plot for Cu2+ Adsorption on TOSS Carbon
plots and are shown in Table 4.21

77
Table 4.21: The Kinetic Parameters for Cu2+ Adsorption on TOSS Carbon

50 100 150 200
Venkobachar R2 0.990 0.918 0.991 0.960
order qe (mg/g) 5.636 7.568 7.568 9.616
2
R 0.989 0.929 0.988 0.963
Elovich (mg.g-1. min-1) 0.297 0.614 0.657 0.659
(mg.g-1. min-1) 0.590 0.564 0.506 0.412
R2 0.994 0.994 0.994 0.983
-1 -1
order qe (mg/g) 7.299 8.197 10.000 12.346
R2 0.998 0.997 0.996 0.993
Morris R2 0.953 0.953 0.956 0.967
A comparison of the various kinetic plots based on the linear regression coefficient (R2)
values shows that pseudo-second order model best described the adsorption at all the
considered concentrations. Therefore, the adsorption of Cu2+ on TOSS carbon can also be
best described using the pseudo-second order model. The equilibrium capacity values (qe)
increased with increase in concentration of the adsorbates and the estimated values fell within
the range of experimental data. The pseudo-second order rate constants (k2) decreased with
increase in concentration showing that the adsorption of Cu2+ on TOSS became faster with
increasing the Cu2+ concentration in solution.
of the different concentrations of Cu2+ on TOSS carbon.

78
Table 4.22: Intra-particle and Film Diffusion Constants for Cu2+ Adsorption on TOSS
Carbon

50 100 150 200
2 -1 -5 -5 -5
DP (cm .s ) 2.70x10 2.82x10 2.25x10 1.88x10-5
DF (cm2.s-1) 2.91x10-6 1.44x10-6 9.55x10-7 6.52x10-7
concentrations were all of the order of 10-5cm2.s-1. This shows that intra-particle diffusion is
not the rate limiting step for Cu2+ adsorption on TOSS carbon. The DF-values are in the range
of 10-6 to 10-7cm2.s-1 for the considered Cu2+ concentrations. Therefore, the rate of adsorption
of Cu2+ on TOSS carbon is controlled by film (boundary-layer) diffusion.
4.3.3 Kinetic analysis of Pb2+ adsorption on GASS carbon
concentrations of Pb2+ on GASS carbon.
Figure 4.21: Bhattacharya-Venkobachar Plot for Pb2+ Adsorption on GASS Carbon

79
Pb2+ on GASS carbon.
Figure 4.22: Pseudo First Order Plot for Pb2+ Adsorption on GASS Carbon
Figure 4.23 shows the Elovich plot for the adsorption of different concentrations of Pb2+ on
GASS carbon.
Figure 4.23: Elovich Plot for Pb2+ Adsorption on GASS Carbon

80
of Pb2+ on GASS carbon.
Figure 4.24: Pseudo Second Order Plot for Pb2+ Adsorption on GASS Carbon
of Pb2+ on GASS carbon.
Figure 4.25: Weber and Morris Plot for Pb2+ Adsorption on GASS Carbon
81
Table 4.23: The Kinetic Parameters for Pb2+ Adsorption on GASS Carbon

50 100 150 200
Venkobachar R2 0.985 0.992 0.990 0.933
order qe (mg/g) 7.768 10.967 13.527 19.756
2
R 0.986 0.993 0.990 0.940
Elovich (mg.g-1. min-1) 0.725 0.876 1.192 1.955
(mg.g-1. min-1) 0.518 0.365 0.290 0.215
R2 0.996 0.993 0.995 0.998
-1 -1
order qe (mg/g) 8.803 12.453 17.007 22.026
R2 0.999 0.998 0.998 0.999
Morris R2 0.936 0.952 0.961 0.932
values shows that pseudo-second order model best described the adsorption at the different
concentrations. Therefore, the adsorption of Pb2+ on GASS carbon can best be described
using the pseudo-second order model. The equilibrium capacity values (qe) increased with
increase in concentration of the adsorbates and the estimated values fell within the range of
experimental data. The pseudo-second order rate constants (k2) decreased with increase in
concentration showing that the adsorption of Pb2+ on GASS became faster with increase in
the Pb2+ concentration in solution.

82
of the different concentrations of Pb2+ on GASS carbon.
Table 4.24: Intra-particle and Film Diffusion Constants for Pb2+ Adsorption on GASS
Carbon

50 100 150 200
DP (cm2.s-1) 2.26x10-5 2.68x10-5 2.50x10-5 2.83x10-5
DF (cm2.s-1) 3.40x10-6 2.31x10-6 1.92x10-6 2.16x10-6
metal concentrations were all of the order of 10-5cm2.s-1. This shows that intra-particle
diffusion is not the rate limiting step for Pb2+ adsorption on GASS carbon. The DF-values are
all of the order of 10-6cm2.s-1 for the considered Cu2+ concentrations. Therefore, the rate of
adsorption of Cu2+ on GASS carbon is controlled by film (boundary-layer) diffusion.
4.3.4 Kinetic analysis of Cu2+ adsorption on GASS carbon
concentrations of Cu2+ on GASS carbon.
Figure 4.26: Bhattacharya-Venkobachar Plot for Cu2+ Adsorption on GASS Carbon

83
Cu2+ on GASS carbon.
Figure 4.27: Pseudo First Order Plot for Cu2+ Adsorption on GASS Carbon
Figure 4.28 shows the Elovich plot for the adsorption of different concentrations of Cu2+ on
GASS carbon.
Figure 4.28: Elovich Plot for Cu2+ Adsorption on GASS Carbon

84
of Cu2+ on GASS carbon.
Figure 4.29: Pseudo Second Order Plot for Cu2+ Adsorption on GASS Carbon
Figure 4.30 shows the Weber and Morris plot for the adsorption of different concentrations of
Cu2+ on GASS carbon.
Figure 4.30: Weber and Morris Plot for Cu2+ Adsorption on GASS Carbon
85
Table 4.25: The Kinetic Parameters for Cu2+ Adsorption on GASS Carbon

50 100 150 200
Venkobachar R2 0.999 0.988 0.986 0.980
order qe (mg/g) 7.345 9.840 11.588 15.240
2
R 0.999 0.990 0.988 0.982
Elovich (mg.g-1. min-1) 0.649 0.759 0.909 1.301
(mg.g-1. min-1) 0.489 0.396 0.331 0.246
R2 0.993 0.989 0.991 0.995
-1 -1
order qe (mg/g) 8.772 11.628 14.085 18.182
R2 0.997 0.997 0.998 0.995
Morris R2 0.961 0.970 0.971 0.951
values shows that for 50mg/l of Cu2+, the Bhattacharya-Venkobachar and the Pseudo-first
order models gave similar and best fit. At higher concentrations of Cu2+, the adsorption was
best described by the pseudo-second order model. For 200mg/l of Cu2+ the Elovich model
also gave a very good correlation. The pseudo-second order rate constants (k2) decreased with
increase in concentration showing that the adsorption of Cu2+ on GASS became faster with
increasing the Cu2+ concentration in solution.

86
of the different concentrations of Cu2+ on GASS carbon.
Table 4.26: Intra-particle and Film Diffusion Constants for Cu2+ Adsorption on GASS
Carbon

50 100 150 200
DP (cm2.s-1) 3.53x10-5 2.72x10-5 2.56x10-5 2.53x10-5
DF (cm2.s-1) 6.32x10-7 8.61x10-7 6.19x10-7 5.68x10-7
concentrations were all of the order of 10-5cm2.s-1. This shows that intra-particle diffusion is
not the rate limiting step for Cu2+ adsorption on GASS carbon. The DF-values are all of the
order of 10-7cm2.s-1 for the considered Cu2+ concentrations. Therefore, the rate of adsorption
of Cu2+ on GASS carbon is controlled by film (boundary-layer) diffusion.
4.4 Isotherm Studies
The isotherm data obtained for the adsorption processes were analysed using the Langmuir,
Freundlich and Temkin isotherms.
4.4.1 Isotherm study of Pb2+ adsorption on TOSS carbon
The isotherm data obtained for the adsorption of Pb2+ on TOSS carbon are shown in Table
4.27.
87
Table 4.27: Isotherm Data for Pb2+ Adsorption on TOSS Carbon
Co Ce q Ce/q log Ce log q ln Ce

50 13.75 7.25 1.90 1.14 0.86 2.62
100 59.25 8.15 7.27 1.77 0.91 4.08
150 101.75 9.65 10.54 2.01 0.98 4.62
200 136.00 12.80 10.63 2.13 1.11 4.91
From these data, the Langmuir, Freundlich and Temkin isotherms for the adsorption process
were obtained and are shown in Figures 4.31, 4.32 and 4.33, respectively.
Figure 4.31: Langmuir Isotherm for Pb2+ adsorption on TOSS Carbon

88
Figure 4.32: Freundlich Isotherm for Pb2+ adsorption on TOSS Carbon
Figure 4.33: Temkin Isotherm for Pb2+ adsorption on TOSS Carbon

89
The isotherm parameters obtained from these plots are presented in Table 4.28.
Table 4.28: The Isotherm Parameters for Pb2+ Adsorption on TOSS Carbon
Isotherm model Parameter Value
Langmuir Isotherm KL (l.mg-1) 0.040

qm (mg.g-1) 13.70
RL 0.111
R2 0.900
Freundlich Isotherm KF (mg/g) 1.614
n 1.678
R2 0.721
Temkin Isotherm KT 0.766
bT (kJmol-1) 1.285
R2 0.672
A comparison of the isotherms based on their linear regression coefficient (R2) values shows
that the Langmuir isotherm gave the best fit for the adsorption process with R2 value of 0.900.
The calculated separation factor (RL) has a value of 0.111. This value is greater than zero and
less than one. This shows that the Langmuir isotherm is favourable for the description of the
adsorption process70. Hence, the adsorption of Pb2+ on TOSS carbon can be said to take place
by monolayer coverage of the metal ions on the adsorbent surfaces. This behaviour was
reported by Pandey et al114. The monolayer adsorption capacity was found to be 13.70mg/g
which is higher than the values obtained for activated carbon from some other raw materials
such as bamboo dust (with value of 2.151mg/g) 100, coconut (with value of 4.38mg/g) 98 and
seed hull of palm tree (with value of 3.77mg/g) 98.

90
4.4.2 Isotherm study of Cu2+ adsorption on TOSS carbon
The isotherm data obtained for the adsorption of Cu2+ on TOSS carbon are shown in Table
4.29.
Table 4.29: Isotherm Data for Cu2+ Adsorption on TOSS Carbon

50 20.75 5.85 3.55 1.32 0.77 3.03
100 67.25 6.55 10.27 1.83 0.82 4.21
150 105.75 8.85 11.95 2.02 0.95 4.66
200 151.50 9.70 15.62 2.18 0.99 5.02
Figure 4.34: Langmuir Isotherm for Cu2+ adsorption on TOSS Carbon

91
Figure 4.35: Freundlich Isotherm for Cu2+ adsorption on TOSS Carbon
Figure 4.36: Temkin Isotherm for Cu2+ adsorption on TOSS Carbon

92
Table 4.30: The Isotherm Parameters for Cu2+ Adsorption on TOSS Carbon

qm (mg.g-1) 11.36
RL 0.135
R2 0.949
n 3.891
2
R 0.850
Temkin Isotherm KT -0.199
bT (kJmol-1) 1.313
R2 0.823
The calculated separation factor (RL) has a value of 0.135 showing that the Langmuir
isotherm is favourable for the description of the adsorption process. Hence, the adsorption of
Cu2+ on TOSS carbon can be said to take place by monolayer coverage of the Cu2+ ions on
the carbon surface. The monolayer adsorption capacity was found to be 11.36mg/g. This
value is higher than the values obtained for some other activated carbons such as the
activated carbon produced from pecan shell by phosphoric acid activation and the one
produced by CO2 activation which had monolayer adsorption capacity of 6.84 and
0.001mg/g, respectively95.
93
4.4.3 Isotherm study of Pb2+ adsorption on GASS carbon
The isotherm data obtained for the adsorption of Pb2+ on GASS carbon are shown in Table
4.31.
Table 4.31: Isotherm Data for Pb2+ Adsorption on GASS Carbon

50 10.50 7.90 1.33 1.02 0.9 2.35
100 48.50 10.30 4.70 1.69 1.01 3.88
150 77.00 14.60 5.27 1.89 1.16 4.34
200 104.25 19.15 6.66 2.06 1.23 4.65
Figure 4.37: Langmuir Isotherm for Pb2+ adsorption on GASS Carbon

94
Figure 4.38: Freundlich Isotherm for Pb2+ adsorption on GASS Carbon
Figure 4.39: Temkin Isotherm for Pb2+ adsorption on GASS Carbon

95
Table 4.32: The Isotherm Parameters for Pb2+ Adsorption on GASS Carbon

qm (mg.g-1) 18.52
RL 0.009
R2 0.935
n 3.257
2
R 0.891
bT (kJmol-1) 0.593
R2 0.765
Pb2+ on GASS carbon can be said to take place by monolayer coverage of the Pb2+ ions on
the carbon surface. The monolayer adsorption capacity was found to be 16.67mg/g and is also
higher than the values obtained for activated carbon from bamboo dust (with value of
2.151mg/g) 100, coconut (with value of 4.38mg/g) 98 and seed hull of palm tree (with value of
3.77mg/g) 98.
96
4.4.4 Isotherm study of Cu2+ adsorption on GASS carbon
The isotherm data obtained for the adsorption of Cu2+ on GASS carbon are shown in Table
4.33.
Table 4.33: Isotherm Data for Cu2+ Adsorption on GASS Carbon

50 20.75 5.85 3.55 1.32 0.77 3.03
100 67.25 6.55 10.27 1.83 0.82 4.21
150 105.75 8.85 11.95 2.02 0.95 4.66
200 151.50 9.70 15.62 2.18 0.99 5.02
Figure 4.40: Langmuir Isotherm for Cu2+ adsorption on GASS Carbon

97
Figure 4.41: Freundlich Isotherm for Cu2+ adsorption on GASS Carbon
Figure 4.42: Temkin Isotherm for Cu2+ adsorption on GASS Carbon

98
Table 4.34: The Isotherm Parameters for Cu2+ Adsorption on GASS Carbon

qm (mg.g-1) 16.67
RL 0.116
R2 0.935
n 3.774
2
R 0.897
bT (kJmol-1) 0.903
R2 0.838
Cu2+ on GASS carbon can be said to take place by monolayer coverage of the Cu2+ ions on
the carbon surface. The monolayer adsorption capacity was found to be 18.52mg/g and is
higher than the values obtained for activated carbons from some other raw materials such as
pecan shell (with value of 6.84mg/g) 95 and banana pith (with value of 13.50mg/g)91.
99
CHAPTER FIVE
CONCLUSION
The results obtained from this work show the possibility of production of activated carbons
with good properties from fluted pumpkin (Telfairia occidentalis) and star apple (Gambeya
albida) seed shells. Activation of the raw materials with phosphoric acid led to carbons with
higher adsorption potentials than activation with ammonium chloride. Increase in
carbonization temperature and time yielded carbons with higher adsorption capacities.
Activated carbons produced from fluted pumpkin seed shell have better adsorption properties
than those produced from star apple seed shell under the same production conditions, as
shown by the adsorption results obtained during variation of production conditions. However,
if cost of production, in terms of weight loss of raw materials, is considered, and the
carbonization is done at 600oC for 120minutes for star apple seed shell and 500oC for
60minutes for fluted pumpkin seed shell, as was done during the variation of adsorption
conditions, then, the carbon from the star apple seed shell would have higher adsorption
potential than the one from fluted pumpkin seed shell.
Adsorption equilibrium was attained between 130 170 minutes for all the adsorption
processes. Lead was more effectively adsorbed than copper by both adsorbents. Adsorption
decreased with increase in adsorption temperature and particle size and increased with
increase in initial metal ion concentration and adsorbent weight in all the cases considered.
Adsorption also increased with increase in pH of the metal solutions up to a pH value of 5,
beyond which the metal ions were precipitated out of their solutions as their hydroxides
Almost all of the adsorption processes were best fitted by the pseudo-second order equation.
The only exception was the adsorption of 50mg/l of Cu2+ on star apple activated carbon,
100
which was best fitted by the pseudo-first order equation. The rates of the adsorption processes
were controlled by film (boundary layer) diffusion. The adsorption processes were
exothermic in nature and involved monolayer coverage of the metal ions on the adsorbents.
The adsorption data obtained in this work show that activated carbon from Telfairia
occidentalis and Gambeya albida seed shells can be used as adsorbents for low cost treatment
of industrial effluents, particularly for the removal of Pb2+ and Cu2+ ions. Future work is
therefore recommended using these seed shells to investigate their potentials for removal of
other pollutants.
101
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APPENDIX
111
Carbon with 50mg/l of Pb2+.
t Ct qt tqt log log 0.5log t log qt ln t

(mins) (mg/l) (mg/g) (qe qt) [1 (U)T]
0 50.00 0.00 - 0.89 - - - -
5 41.25 1.75 2.86 0.78 -0.11 0.35 0.24 1.61
10 33.75 3.25 3.08 0.66 -0.23 0.50 0.51 2.30
20 30.00 4.00 5.00 0.58 -0.31 0.65 0.60 3.00
30 22.00 5.60 5.36 0.34 -0.55 0.74 0.75 3.40
50 17.00 6.60 7.58 0.08 -0.81 0.85 0.82 3.91
70 13.50 7.30 9.59 -0.30 -1.19 0.92 0.86 4.25
100 12.00 7.60 13.16 -0.70 -1.59 1.00 0.88 4.61
130 11.00 7.80 16.67 - - - - 4.87
170 11.00 7.80 21.79 - - - - 5.14
210 11.00 7.80 26.92 - - - - 5.35
240 11.00 7.80 30.77 - - - - 5.52

0 100.00 0.00 - 0.94 - - - -
5 90.25 1.95 2.56 0.83 -0.11 0.35 0.29 1.61
10 83.00 3.40 2.94 0.73 -0.21 0.50 0.53 2.30
20 74.50 5.10 3.92 0.56 -0.38 0.65 0.71 3.00
30 69.00 6.20 4.84 0.41 -0.54 0.74 0.79 3.40
50 62.00 7.60 6.58 0.06 -0.88 0.85 0.88 3.91
70 59.00 8.20 9.20 -0.26 -1.20 0.92 0.91 4.25
100 57.50 8.50 11.76 -0.60 -1.54 1.00 0.93 4.61
130 57.50 8.50 15.29 - - - - 4.87
170 56.25 8.75 19.43 - - - - 5.14
210 56.25 8.75 24.00 - - - - 5.35
240 56.25 8.75 27.43 - - - - 5.52
112

0 150.00 0.00 - 1.02 - - - -
5 138.00 2.40 2.08 0.91 -0.11 0.35 0.38 1.61
10 131.50 3.70 2.70 0.84 -0.19 0.50 0.63 2.30
20 120.50 5.90 3.39 0.67 -0.36 0.65 0.77 3.00
30 115.00 7.00 4.29 0.55 -0.47 0.74 0.85 3.40
50 107.00 8.60 5.81 0.29 -0.73 0.85 0.93 3.91
70 101.25 9.75 7.18 -0.10 -1.12 0.92 0.99 4.25
100 99.00 10.20 9.80 -0.46 -1.48 1.00 1.01 4.61
130 98.25 10.35 12.56 -0.70 -1.72 - - 4.87
170 97.25 10.55 16.11 - - - - 5.14
210 97.25 10.55 19.91 - - - - 5.35
240 97.25 10.55 22.75 - - - - 5.52

0 200.00 0.00 - 1.11 - - - -
5 182.50 3.50 1.43 0.98 -0.14 0.35 0.54 1.61
10 175.00 5.00 2.00 0.90 -0.21 0.50 0.70 2.30
20 169.25 6.15 3.25 0.84 -0.28 0.65 0.79 3.00
30 161.25 7.75 3.87 0.72 -0.39 0.74 0.89 3.40
50 150.00 10.00 5.00 0.48 -0.64 0.85 1.00 3.91
70 139.00 12.20 5.74 -0.10 -1.21 0.92 1.09 4.25
100 137.50 12.50 8.00 -0.30 -1.41 1.00 1.10 4.61
130 136.00 12.80 10.16 -0.70 -1.81 1.06 1.11 4.87
170 135.00 13.00 13.08 - - - - 5.14
210 135.00 13.00 16.15 - - - - 5.35
240 135.00 13.00 18.46 - - - - 5.52
113
Carbon with 50mg/l of Cu2+.

(mins) (mg/l) (mg/g) (qeqt) [1 (U)T]
0 50.00 0.00 - 0.80 - - - -
5 45.25 0.95 5.26 0.73 -0.07 0.35 -0.02 1.61
10 40.75 1.85 5.41 0.65 -0.15 0.50 0.27 2.30
20 36.25 2.75 7.27 0.55 -0.25 0.65 0.44 3.00
30 32.25 3.55 8.45 0.44 -0.36 0.74 0.55 3.40
50 28.50 4.30 11.63 0.30 -0.50 0.85 0.63 3.91
70 26.00 4.80 14.58 0.18 -0.62 0.92 0.68 4.25
100 23.00 5.40 18.52 -0.05 -0.85 1.00 0.73 4.61
130 20.50 5.90 22.03 -0.40 -1.20 1.06 0.77 4.87
170 18.50 6.30 26.98 - - 1.12 0.80 5.14
210 18.50 6.30 33.33 - - - - 5.35
240 18.50 6.30 38.10 - - - - 5.52

(mins) (mg/l) (mg/g) (qe qt) [1-(U)T]
0 100.00 0.00 - 0.85 - - - -

5 94.25 1.15 4.35 0.78 -0.08 0.35 0.06 1.61
10 89.00 2.20 4.55 0.69 -0.16 0.50 0.34 2.30
20 84.00 3.20 6.25 0.60 -0.26 0.65 0.51 3.00
30 79.25 4.15 7.23 0.48 -0.38 0.74 0.62 3.40
50 75.25 4.95 10.10 0.34 -0.51 0.85 0.69 3.91
70 72.25 5.55 12.61 0.20 -0.65 0.92 0.74 4.25
100 68.25 6.35 15.75 -0.10 -0.95 1.00 0.80 4.61
130 64.75 7.05 18.44 -1.00 -1.85 1.06 0.85 4.87
170 64.25 7.15 23.78 - - 1.12 0.85 5.14
210 64.25 7.15 29.37 - - - - 5.35
240 64.25 7.15 33.57 - - - - 5.52
114

0 150.00 0.00 - 0.93 - - - -

5 143.75 1.25 4.00 0.87 -0.06 0.35 0.10 1.61
10 138.00 2.40 4.17 0.79 -0.13 0.50 0.38 2.30
20 131.75 3.60 5.56 0.70 -0.22 0.65 0.56 3.00
30 127.00 4.50 6.67 0.61 -0.30 0.74 0.65 3.40
50 123.00 5.30 9.43 0.52 -0.38 0.85 0.72 3.91
70 118.50 6.00 11.67 0.41 -0.50 0.92 0.78 4.25
100 114.25 6.85 14.60 0.24 -0.65 1.00 0.84 4.61
130 110.25 7.55 17.22 0.02 -0.87 1.06 0.88 4.87
170 107.00 8.15 20.86 -0.35 -1.19 1.12 0.91 5.14
210 104.00 8.60 24.42 - - 1.16 0.93 5.35
240 104.00 8.60 27.91 - - - - 5.52
t Ct qt t/qt log log 0.5log t log qt ln t

0 200.00 - - - -
0.00 - 1.01
5 193.50 1.30 3.85 0.95 -0.06 0.35 0.11 1.61
10 187.50 2.50 4.00 0.89 -0.12 0.50 0.40 2.30
20 181.00 3.80 5.26 0.81 -0.20 0.65 0.58 3.00
30 176.00 4.80 6.25 0.74 -0.27 0.74 0.68 3.40
50 170.00 6.00 8.33 0.63 -0.38 0.85 0.78 3.91
70 166.75 6.65 10.53 0.56 -0.45 0.92 0.82 4.25
100 160.00 8.00 12.50 0.36 -0.65 1.00 0.90 4.61
130 157.50 8.50 15.29 0.26 -0.76 1.06 0.93 4.87
170 151.00 9.80 17.35 -0.30 -1.31 1.12 0.99 5.14
210 148.50 10.30 20.39 - - 1.16 1.01 5.35
240 148.50 10.30 23.30 - - - - 5.52
115
Table A.9: Effects of Contact Time using Gambeya albida Seed Shell Activated Carbon
with 50mg/l Pb2+.

(mins) (mg/l) (mg/g) (qeqt) [1 (U)T]
0 50.00 0.00 - 0.89 - - - -
5 43.75 1.25 4.00 0.82 -0.08 0.35 0.10 1.61
10 37.75 2.45 4.08 0.73 -0.16 0.50 0.39 2.30
20 31.25 3.75 5.33 0.61 -0.28 0.65 0.57 3.00
30 26.25 4.75 6.32 0.48 -0.41 0.74 0.68 3.40
50 21.25 5.75 8.70 0.31 -0.58 0.85 0.76 3.91
70 17.50 6.50 10.77 0.11 -0.78 0.92 0.81 4.25
100 14.50 7.10 14.08 -0.15 -1.05 1.00 0.85 4.61
130 12.25 7.55 17.22 -0.60 -1.49 1.06 0.88 4.87
170 11.25 7.75 21.94 -1.30 -2.19 1.12 0.89 5.14
210 11.00 7.80 26.92 - - - - 5.35
240 11.00 7.80 30.77 - - - - 5.52
with 100mg/l Pb2+.

(mins) (mg/l) (mg/g) (qeqt) [1-(U)T]
0 100.00 0.00 - 1.03 - - - -
5 92.00 1.60 3.13 0.96 -0.07 0.35 0.20 1.61
10 84.50 3.10 3.23 0.88 -0.15 0.50 0.49 2.30
20 76.75 4.65 4.30 0.79 -0.25 0.65 0.67 3.00
30 69.75 6.05 4.96 0.67 -0.36 0.74 0.78 3.40
50 62.50 7.50 6.67 0.51 -0.52 0.85 0.88 3.91
70 56.50 8.70 8.05 0.31 -0.72 0.92 0.94 4.25
100 51.00 9.80 10.20 -0.02 -1.05 1.00 0.99 4.61
130 48.00 10.40 12.50 -0.46 -1.49 1.06 1.02 4.87
170 46.75 10.65 15.96 -1.00 -2.03 1.12 1.03 5.14
210 46.25 10.75 19.23 - - - - 5.35
240 46.25 10.75 22.33 - - - - 5.52
116
with 150mg/l Pb2+.

0 150.00 0.00 - 1.17 - - - -
5 138.50 2.30 2.17 1.10 -0.07 0.35 0.36 1.61
10 128.25 4.35 2.30 1.02 -0.15 0.50 0.64 2.30
20 118.75 6.25 3.20 0.93 -0.24 0.65 0.80 3.00
30 110.50 7.90 3.80 0.84 -0.33 0.74 0.90 3.40
50 102.75 9.45 5.29 0.73 -0.44 0.85 0.98 3.91
70 96.00 10.80 6.48 0.60 -0.57 0.92 1.03 4.25
100 89.00 12.20 8.20 0.41 -0.76 1.00 1.09 4.61
130 82.50 13.50 9.63 0.11 -1.06 1.06 1.13 4.87
170 78.50 14.30 11.89 -0.30 -1.47 1.12 1.16 5.14
210 76.00 14.80 14.19 - - - - 5.35
240 76.00 14.80 16.22 - - - - 5.52
with 200mg/l Pb2+.

(mins) (mg/l) (mg/g) (qe qt) [1 -(U)T]
0 200.00 - - - - -
0.00 1.29
5 183.00 3.40 1.47 1.21 -0.08 0.35 0.53 1.61
10 168.00 6.40 1.56 1.12 -0.17 0.50 0.81 2.30
20 151.25 9.75 2.05 1.00 -0.30 0.65 0.99 3.00
30 138.25 12.35 2.43 0.87 -0.43 0.74 1.09 3.40
50 128.00 14.40 3.47 0.72 -0.57 0.85 1.16 3.91
70 120.75 15.85 4.42 0.59 -0.71 0.92 1.20 4.25
100 113.75 17.25 5.80 0.39 -0.91 1.00 1.24 4.61
130 107.00 17.60 7.39 0.04 -1.25 1.06 1.27 4.87
170 102.00 18.30 8.67 -1.00 -2.29 1.12 1.29 5.14
210 101.50 18.40 10.66 - - - - 5.35
240 101.50 18.40 12.18 - - - - 5.52
117
with 50mg/l Cu2+.

0 50.00 0.00 - 0.88 - - - -
5 44.00 1.20 4.17 0.81 -0.07 0.35 0.08 1.61
10 38.50 2.30 4.35 0.72 -0.16 0.50 0.36 2.30
20 32.75 3.45 5.80 0.62 -0.26 0.65 0.54 3.00
30 27.75 4.45 6.74 0.50 -0.38 0.74 0.65 3.40
50 21.50 5.70 8.77 0.28 -0.60 0.85 0.76 3.91
70 17.25 6.55 10.69 0.02 -0.86 0.92 0.82 4.25
100 14.25 7.15 13.99 -0.35 -1.23 1.00 0.85 4.61
130 12.00 7.60 17.11 - - 1.06 0.88 4.87
170 12.00 7.60 22.22 - - - - 5.14
210 12.00 7.60 27.45 - - - - 5.35
240 12.00 7.60 31.37 - - - - 5.52
with 100mg/l Cu2+.

(mins) (mg/l) (mg/g) (qe -qt) [1- (U)T]
0 100.00 0.00 - 1.00 - - - -
5 92.50 1.50 3.33 0.93 -0.07 0.35 0.18 1.61
10 86.25 2.75 3.64 0.86 -0.14 0.50 0.44 2.30
20 79.75 4.05 4.94 0.77 -0.23 0.65 0.61 3.00
30 73.50 5.30 5.66 0.67 -0.33 0.74 0.72 3.40
50 67.25 6.55 7.63 0.53 -0.45 0.85 0.82 3.91
70 61.50 7.70 9.09 0.35 -0.65 0.92 0.89 4.25
100 55.50 8.90 11.24 0.02 -0.98 1.00 0.95 4.61
130 52.25 9.55 13.61 -0.40 -1.40 1.06 0.98 4.87
170 50.25 9.95 17.09 - - 1.12 1.00 5.14
210 50.25 9.95 21.11 - - - - 5.35
240 50.25 9.95 24.12 - - - - 5.52
118
with 150mg/l Cu2+.

0 150.00 - - - - -
0.00 1.08
5 141.00 1.80 2.78 1.01 -0.07 0.35 0.26 1.61
10 133.75 3.25 3.08 0.94 -0.14 0.50 0.51 2.30
20 125.00 5.00 4.00 0.85 -0.23 0.65 0.70 3.00
30 119.00 6.20 4.84 0.76 -0.32 0.74 0.79 3.40
50 110.25 7.95 6.29 0.61 -0.47 0.85 0.90 3.91
70 103.75 9.25 7.57 0.44 -0.64 0.92 0.97 4.25
100 97.75 10.45 9.57 0.19 -0.89 1.00 1.02 4.61
130 92.75 11.45 11.35 -0.26 -1.34 1.06 1.06 4.87
170 90.00 12.00 14.17 - - 1.12 1.08 5.14
210 90.00 12.00 17.50 - - - - 5.35
240 90.00 12.00 20.00 - - - - 5.52
with 200mg/l Cu2+.

0 200.00 - - - - -
0.00 1.21
5 188.25 2.35 2.13 1.14 -0.07 0.35 0.37 1.61
10 177.25 4.55 2.20 1.06 -0.14 0.50 0.66 2.30
20 165.25 6.95 2.88 0.96 -0.25 0.65 0.84 3.00
30 154.25 9.15 3.28 0.84 -0.36 0.74 0.96 3.40
50 143.75 11.25 4.44 0.69 -0.52 0.85 1.05 3.91
70 134.75 13.05 5.36 0.48 -0.72 0.92 1.12 4.25
100 129.75 14.05 7.12 0.31 -0.90 1.00 1.15 4.61
130 122.50 15.50 8.39 -0.22 -1.43 1.06 1.19 4.87
170 119.50 16.10 10.56 - - 1.12 1.21 5.14
210 119.50 16.10 13.04 - - - - 5.35
240 119.50 16.10 15.53 - - - - 5.52

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PREPARATION, CHARACTERIZATION AND

ADSORPTIVE EVALUATION OF ACTIVATED

DEPARTMENT OF PURE AND INDUSTRIAL

A RESEARCH PROJECT SUBMITTED IN PARTIAL

PREPARATION, CHARACTERIZATION AND ADSORPTIVE EVALUATION OF

OKOYE, Amalachukwu I, a postgraduate student in the Department of Pure and

Industrial Chemistry with Registration Number PG/M.Sc./07/42984 has satisfactorily

Prof. O. D. Onukwuli Dr. P.O. Ukoha

This work is dedicated to Almighty God and to my loved ones.

I wish to express my profound gratitude to my supervisor, Professor O.D Onukwuli, whose

sustained me throughout my period of study. Finally, my appreciation goes to all my friends

LIST OF TABLES ...xi

CHAPTER ONE: INTRODUCTION ..1

1.1 Research Objectives ................3

CHAPTER TWO: LITERATURE REVIEW5

2.1 Historical Background of Activated Carbon5

2.3 Characteristics of Activated Carbon ..15

2.3.1 Classifications of Activated Carbon........................16

2.3.2 Properties of Activated Carbon...18

2.3.2.1 Physical properties...19

2.4.1 Adsorption Isotherm........................27

2.4.1.2 Freundlich Isotherm.........................30

2.4.1.3 Temkin Isotherm..32

2.4.2 Adsorption Kinetics.33

2.4.2.2 Lagergren Pseudo-first Order Model...34

2.4.2.3 Pseudo-second Order Model................................35

2.4.2.4 Elovich Model..........................36

2.4.2.5 Intra-particle and Film Diffusion Kinetics...36

CHAPTER THREE: EXPERIMENTAL.....43

3.1 Chemicals and Instrumentation..43

3.2 Production of Activated Carbon.....43

3.2.1 Effect of Activating Conditions..43

3.2.2 Effect of Carbonization Temperature..44

3.2.3 Effect of Carbonization Time..44

3.3 Characterization of Adsorbents..44

3.3.1 Determination of Yield and Weight Loss............44

3.3.2 Surface Area Measurement.....45

3.3.3 Determination of Ash Content....................45

3.3.4 Determination of Bulk Density...46

3.3.5 Determination of Total Pore Volume..46

3.4 Adsorption Tests46

3.4.1 Effect of Particle Size.....47

3.4.2 Effect of Solution pH.....47

3.4.3 Effect of Adsorbent Weight...48

3.4.4 Effect of Temperature.48

3.5 Kinetic Study..48

3.6 Isotherm Study...............48

CHAPTER FOUR: RESULTS AND DISCUSSION..49

4.1 Characterization of Adsorbents..............................49

4.1.1 Characterization of Adsorbents Produced Using Different Activating

4.1.3 Characterization of Adsorbents Carbonized for Different Lengths of

4.2 Effect of Process Variables on Adsorption....53

4.2.1 Effect of Activating Agent on Adsorption..53

4.2.2 Effect of Carbonization Temperature on Adsorption..55

4.2.3 Effect of Carbonization Time..57

4.3.4 Effect of Particle Size on Adsorption..59

4.2.5 Effect of Solution pH on Adsorption .61

4.2.4 Effect of Adsorbent Weight on Adsorption ..62

4.2.7 Effect of Adsorption Temperature on Amount of Metals Adsorbed.64

4.2.8 Effect of Contact Time and Initial Metal Ion Concentration on

4.3 Kinetic Studies...69

4.3.1 Kinetic analysis of Pb2+ adsorption on TOSS carbon.69

4.3.2 Kinetic analysis of Cu2+ adsorption on TOSS carbon.73