CHAPTER V

RESULTS AND DISCUSSION

Adsorption process has been identified as an efficient and economical technique to

remove heavy metal ions from aqueous solutions. Sorption process has gained a big attention in
removing heavy metals in wastewater since it offers advantages such as high efficiency and low
operating cost. Moreover, it is ecofriendly when compared to conventional treatment methods.
Almost all sorbents used for the removal of heavy metals from wastewater are derived from
waste materials that are abundant and low cost. This include seaweed, spent tea, fly ash, orange
peels, coral waste, coconut husk and animal bones.
The mechanism of the removal of metal ions can be any or combination of the following
mechanisms: ion-exchange, adsorption, chelation, complexation, coordination, electrostatic
interaction or microprecipitation.
Waste eggshells contain high contents of calcium carbonate, usually, 85-95%. Moreover,
the use of lime based waste materials such as eggshells and oyster shells can be used as an
alternative calcium carbonate for the immobilization of heavy metal ions in wastewater.
The objective of this study is to produce an adsorbent based from eggshell with higher
adsorption capacity. Moreover, this study aims to characterize the produced adsorbent from
calcined waste eggshell, determine the adsorption capacity and percentage removal with different
dosages and contact time and to determine the optimum dosage and contact time for the removal
of Pb(II) and Hg(II).

5.1 SCANNING ELECTRON MICROSCOPY

5.1.1 MORPHOLOGY
To observe the morphological structure of the prepared adsorbent from eggshell,
Scanning Electron Microscopy (SEM) was utilized. SEM helps in providing a deeper
insight on the structural features and distribution of particles and pores
Scanning electron microscopy (SEM) was used to observe the morphology of the
activated waste eggshell. SEM also provide a deeper insight on the structural features and
distribution of particles and pores.

Figure
5.1 image
and Figure
5.2 showed
pores
of the
activated
waste
eggshell
Figure
5.2: SEM
image
for activated
eggshell
Figure
5.1: SEM
for unactivated
eggshellthat the
increased its pore size compared to the unactivated waste eggshell. The shapes of the
pores for both activated and unactivated waste eggshell can be described as spherical
bubbles. It can be said that the activated waste eggshell exhibited macroporous structure
due to the void spaces shown in the figure above. Furthermore, the surface area of the
activated waste eggshell increases as the pore size of the activated waste eggshell
increases. As a result, the number of vacant sites for adsorption process also increases.

5.1.2 ELEMENTAL ANALYSIS

Electron Dispersive Spectroscopy (EDS) was used to determine the elemental
analysis of the activated waste eggshell. This is shown in Figure 5.3 and Table 5.1. Figure
5.3 shows that the activated eggshell is composed of C, Ca and O. Moreover, Table 5.1
shows that 41.94% of the activated eggshell is composed of Ca. It is followed by O and C
with 41.90% and 16.16% composition respectively.
Counts
2500

Ca

2000
1500
1000
O
500 C
0

Ca

Ca
0

10

15

20
Energy (keV)

Figure 5.3: Elemental analysis of activated eggshell

Table 5.1: Elemental Composition of activated Eggshell

Element
C
O
Ca

Percentage Composition
16.16
41.90
41.94

5.2 EFFECT OF CONTACT TIME ON ADSORPTION

The adsorption equilibrium time between the adsorbate and the adsorbent is essential for
designing batch adsorption experiments. As a result, the adsorption of Pb(II) and Hg(II) ions onto
the surface of the activated eggshell was studied as a function of time.
In Figure 5.4 and Figure 5.5, it is shown that, for the first trial, the activated waste
eggshell obtained the highest adsorption of 9.21 mg/g and 8.55 mg/g for Pb(II) and Hg(II) for 80
min and 100 min respectively. This pertains to 92.14% Pb(II) removal and 85.52% Hg(II)
removal. This is shown in Figure 5.6 and Figure 5.7 respectively.

Figure 5.4: Effect of Contact Time on the adsorption capacity of Pb(II) onto activated waste eggshell fo

Adsorption Capacity vs Contact Time of Hg(II)

qt (mg/g)

20

40

60

80

Contact Time (min)

100

120

140

Percentage Removal of vs Contact Time

100
80
60

Removal (%)

40
20
0

20

40

60

80

100

120

140

Contact Time (min)

Figure 5.6: Effect of Contact Time on the percentage removal of Pb(II) onto
activated waste eggshell for trial 1

Figure 5.5: Effect of Contact Time on the percentage removal of Hg(II) onto
activated waste eggshell for trial 1

Percentage of vs Contact Time

90
80
70
60
50

Removal (%) 40
30
20
10
0

20

40

60

80

100

120

140

Contact Time (min)

Figure 5.7: Effect of Contact Time on the percentage removal of Hg(II) onto activated
waste eggshell for trial 1

In addition to that, the adsorption rate of Pb(II) onto the surface of the activated
eggshell was very fast within 60 min and thereafter, it became slower within the range of
60 min to 80 min. Finally, the adsorption capacity did not vary significantly after 80 min
(9.21 mg/g). This is shown in Figure 5.4.

In the case of the adsorption of Hg(II) onto the activated eggshell, the rate of
adsorption is very fast not until it reached 100 min. The adsorption capacity (8.55 mg/g)
remains constant after 100 min.

Adsorption Capacity vs Contact Time

10
8
6
4
2
0

20

40

60

80

100

120

140

Contact Time (min)

Figure 5.8: Effect of Contact Time on the adsorption capacity of Pb(II) onto
activated waste eggshell for trial 2

Adsorption Capacity vs Contact Time

qt (mg/g)

9
8
7
6
5
4
3
2
1
0

20

40

60

80

100

120

140

Contact Time (min)

Figure 5.9: Effect of Contact Time on the adsorption capacity of Hg(II) onto
activated waste eggshell for trial 2

In Figure 5.8 and Figure 5.9, it is shown that, for the second trial, the waste
eggshell obtained the highest adsorption of 9.18 mg/g and 8.45 mg/g for Pb(II) and
Hg(II) for 80 min and 100 min respectively which is the same with the result of the first
trial. Figure 5.10 and Figure 5.11 pertained to 91.81% and 84.53% removal for Pb(III)

Percentage Removal vs Contact Time

90
80
70
60
50

Removal (%) 40
30
20
10
0

20

40

60

80

Contavt Time (min)

and

Hg(II)

100

120

140

Percentage Removal vs Contact Time

100
80
60

Removal (%)

40
20
0

20

40

60

80

100

120

140

Contavt Time (min)

Figure 5.10: Effect of Contact Time on the percentage removal of Pb(II) onto activated
waste eggshell for trial 2

Figure 5.11: Effect of Contact Time on the percentage removal of Hg(II) onto
activated waste eggshell for trial 2

Adsorption Capacity vs Contact Time

10
8
6

qt (mg/g(

4
2
0

20

40

60

80

100

120

140

Contact Time (min)

While
in figure 5.12 and figure 5.13, it is shown that, for the third trial, the activated waste
eggshell obtained the highest adsorption of 9.08 mg/g and 8.50 mg/g for Pb(III) and
Hg(II) respectively which is the same result for trial 1 and trial 2. In figure 5.14 and
figure 5.15 pertained to the percent removal of 90.81% and 85.03% for Pb(III) and Hg(II)
respectively.

Figure 5.12: Effect of Contact Time on the adsorption capacity of Pb(II) onto
activated waste eggshell for trial 3

AdsorptionCapacity vs Contact Time

9
8
7
6
5

qt (mg/g) 4
3
2
1
0

20

40

60

80

100

120

140

Contact Time (min)

Figure 5.13: Effect of Contact Time on the adsorption capacity of Hg(II)

onto activated waste eggshell for trial 3

Percentage Removal vs Contact Time

100
80
60

Removal (%)

40
20
0

20

40

60

80

100

120

140

Contact Time (min)

Figure 5.14: Effect of Contact Time on the percentage removal of Pb(II) onto
activated waste eggshell for trial 3

Percentage Removal vs Contact Time

90
80
70
60
50

Removal (%) 40
30
20
10
0

20

40

60

80

100

120

140

Contact Time (min)

Figure 5.15: Effect of Contact Time on the percentage removal of Hg(II) onto
activated waste eggshell for trial 3

5.2 EFFECT OF ADSORBENT DOSAGE

The values of the percentage removal of metal ions, namely Pb(II) and Hg(II) ions, at
different dosages of activated eggshell are presented in Figure 5.16 and 5.17 for trials 1, 2 and 3
respectively. It is observed that as the dosage of the activated waste eggshell increases from 0.5 g
to 1 g, the percentage removal of Pb(II) and Hg(II) ions increases. In trial 1, the percentage
removal increased from 85.79% to 92.14% for Pb(II) and 49.82% to 85.52% for Hg(II).
Moreover, percentage removal increased from 85.10% to 91.70% and 47.39% to 85.53% for
Pb(II) and Hg(II) for 2 trial. For the case of the 3 rd trial, percentage removal of Pb(II) increased
from 85.62% to 91.93% and 49.24% to 85.04% for Hg(II).The increase of percentage removal is
due to the greater availability of active sites on the adsorbent at higher dosage. As a result, there
is an easier penetration of metal ions to the vacant sites.

Effect of Dosage
94
92
90
88

Trial 1

Removal (%) 86

Trial 2
Trial 3

84
82
80

0.5

1.5

Dosage (g)

In addition to
that, it is also observe that the percentage removal of Pb(II) and Hg(II) above 1 g did not
increased remarkably. This is also shown in Figure 5.16 and Figure 5.17. We can therefore
conclude that the appropriate dosage for all other batch adsorption experiments is 1 g.

Figure 5.16: Effect of Dosage on Percentage Removal of Pb(II) for Trial 1, 2

and 3

Effect of Dosage
90
80
70
60

Trial 1

50

Trial 2

Removal (%) 40

Trial 3

30
20
10
0

0.5

Dosage (g)

1.5

Figure 5.17: Effect of Dosage on Percentage Removal of Pb(II) for Trial 1, 2

and 3

5.3 DETERMINATION OF OPTIMUM DOSAGE AND CONTACT TIME

The effect of adsorbent dosage on the removal of Pb(II) and Hg(II) ions at varying
dosages has been examined. It is observed that the removal efficiency of Pb(II) and Hg(II) ions
tends to increased when the adsorbent dosage is increased from 0.5 g to 1 g. This is mainly
because there is more vacant sites available at higher amount of dosage. However, when the
adsorbent dosage is increased from 1 g to 1.5 g, there is no significant increase on the removal of
Pb(II) and Hg(II), therefore, 1 g should be employed for batch adsorption experiment.
To determine the optimum contact time, batch adsorption experiment is done at 1 g while
varying the contact time. For the removal of Pb(II), optimum contact time is 80 min while
optimum contact time of 100 min is observed for Hg(II).