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Comparative Adsorption Capacity of Modified Activated Carbon From Pennisetum Glaucum and

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International Journal of Scientific Engineering and Research (IJSER)

www.ijser.in
ISSN (Online): 2347-3878, Impact Factor (2015): 3.791

Comparative Adsorption Capacity of Modified


Activated Carbon from Pennisetum Glaucum and
Sorghum Bicolor.
O. A. Babatunde1, S. Garba2, Z. N. Ali3
1

Chemistry Department, Nigerian Defence Academy, Kaduna


mail4abiodun[at]yahoo.com

Chemistry Department, Nigerian Defence Academy, Kaduna


abubakarsaidu63[at]gmail.com

Applied Science Department, Kaduna Polytechnic, Kaduna


Jdanasabe[at]gmail.com

Abstract: The influence of surface modification of activated carbons prepared from straws of Pennisetum glaucum (millet)
and Sorghum bicolor (sorghum) with nitric acid and sodium hydroxide showed excellent improvement in their surface
characteristics. The effects of the oxidizing treatments on the surface area pore dimension and surface chemical characteristics were analyzed by means of iodine adsorption, Fourier Transform Infrared and Scanning Electron Microscopy analyses. Results obtained showed that modification with nitric acid increased the adsorptive capacity of the activated carbon
samples to a greater extent compared to sodium hydroxide.
Keywords: Pennisetun glaucum, Sorghum bicolor, surface chemical modification, adsorptive capacity

1. Introduction

activated carbon from low-cost agricultural by-products and


wastes such as straws offers an alternative source for acti-

The modification of the surface chemistry of activated car-

vated carbon. [20] prepared activated carbons from Sorghum

bon is considered an important and relevant technique used

and Millet straws by chemical activation; the carbons were

to alter the surface polarity and create functional groups on

used for adsorption of methylene blue and iodine from

the carbons surface in order to enhance its adsorptive capac-

aqueous solutions. The results obtained from their study

ity. The presence of functional groups such as the carboxyl,

showed that the activated carbons had high adsorptive capac-

carbonyl, phenols, lactones, quinines e.t.c. are usually consi-

ities. The utilization of these straws for production of acti-

dered to be responsible for the uptake of substances from

vated carbons to be used for adsorption of substances in ga-

gaseous streams or aqueous solutions [5]. These oxygen sur-

seous steams can also be investigated to ascertain their suita-

face complexes are formed on activated carbons when they

bility for gaseous and liquid phase adsorption. Iodine is

are treated with oxidizing agents in solution [13; 15] such as

usually used as test chemical to measure the capacity of an

nitric acid, tannic acid, citric acid, ammonia [18] or by micro

activated carbon to adsorb chemical compounds in liquid

wave, ozone and plasma treatment. The treatments usually

phase [12]. Iodine number (milligram iodine adsorbed per

produce three types of oxides, acidic, basic and neutral [15].

gram of activated carbon) is usually used to measure the po-

Fixation of the acidic groups on the surface of the activated

rosity of the activated carbon [10]. Each 1.0mg of iodine

carbons makes it more hydrophilic, removes mineral ele-

adsorbed is ideally considered to represent 1.0m2 of the acti-

ments present on the carbons surface and also affects the

vated carbons internal surface area [10].

surface area and pore texture of the activated carbons [16].


Base treatment of activated carbon produces positive surface

The focus of this paper was to study the influence of surface

charge which in turn is helpful towards adsorption of nega-

chemical modification of activated carbons prepared from

tively charged species in higher amounts [5]. Production of

two different precursors for adsorption of I2 from aqueous

Paper ID: 1071602

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ISSN (Online): 2347-3878, Impact Factor (2015): 3.791
solution.

2.2.2. Modification of Activated Carbon

2. Experimental

(a) Modification with Nitric Acid

2.1. Materials

To 10 g of the activated carbon sample, 100 cm3 of 2.0 M


nitric acid was added and soaked for 24 hrs. The residual

Millet and sorghum straws were obtained from Maguzawa

nitric acid was removed by soaking it in distilled water for 2

Farm in Rigasa Kaduna and were identified at the Herbarium

hrs and then washed several times with distilled water. The

section of the Herbarium Section of Biological Sciences

sample was then dried at 120 oC, cooled in a desiccator and

Department of Ahmadu Bello University Zaria Iodine

stored in plastic sample bottles.

(99.5 %), Potassium iodide (99.9 %), Sodium thiosulphate


(99.5 %), Potassium dichromate (99.5 %), Phosphoric acid

(b) Modification with Sodium hydroxide

(85 %) Nitric acid (69 %), Acetic acid (99.7 %) Ascorbic acid
(94.5 %), Hydrochloric acid (35.4 %), Sodium hydroxide

To 10 g of the activated carbon sample, 100 cm3 of 2.0 M

(99.0 %) Formic acid (90 %) and potassium hydroxide (90 %) sodium hydroxide was added and soaked for 24 hrs. The rewere all of analytical grade.

sidual sodium hydroxide was removed by soaking it in distilled water for 2 hrs and then washed several times with distilled water. The sample was then dried at 120 oC, cooled in a

2.2. Methods

desiccator and stored in plastic sample bottles.


2.2.1. Carbonization and Activation Process
2.2.3. Characterization of Activated carbon
Prior to carbonization, the millet and sorghum straws were
washed, dried, cut into pieces of approximately 3cm and then

The surface physical morphology of the unmodified and

pulverized to obtain particle sizes of about 1180m [14].The

modified activated carbons was observed using Phenom

activated carbon was then prepared by the two-step chemical

scanning electron microscope model proX and surface func-

activation process. The first step involves carbonization with

tional groups were identified using FTIR spectroscope (FTIR

60 % phosphoric acid solution and the second step involves

8400s, shimadzu) and the spectra recorded from 4000 to

activation using muffle furnace model SXL using and 1.0 M

500cm-1.

KOH at 600 oC for 1 hr [19]. The prepared activated carbon


was first washed with water containing 0.15 % formic acid

2.2.4. Iodine Number Test

and then washed severally with distilled water. They were


filtered through a Buchner funnel dried at 120 oC and then

The iodine number was determined according to the ASTM

weighed to determine the activated carbon yield. It was then

D4607-94 method [4] is based upon a three-point isotherm. A

stored in plastic sample bottles to prevent adsorption of dust

0.1 M standard iodine solution was added to three different

and other particles from the atmosphere.

weights of activated carbon samples in three 250 cm3 conical


flasks. The experiment involved treating the activated carbon
sample with 10.0 cm3 of 5 % HCl. This mixture was boiled

The activated carbon yield was calculated using Eq. 1

for 30 seconds and then cooled soon afterwards, 100 cm3 of


Yield % =

100

(1)

0.1 M iodine solution was added to the mixture and stirred


for 30 seconds. The resulting solution was filtered and 50.0

Where Wa is the weight of activated carbon and Wp is the

cm3 of the filtrate was titrated with 0.1 M sodium thiosul-

weight of precursor.

phate using starch solution as indicator. The amount of iodine


adsorbed per gram of carbon (iodine number) and the residual iodine concentration in the filtrate were calculated using
Eq 2.
IN =

Paper ID: 1071602

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ISSN (Online): 2347-3878, Impact Factor (2015): 3.791
Where IN is the iodine number, VB is the volume of Na2S2O3
used for blank titration, VS is the volume of Na2S2O3 used for
(6)

test titration, M1 is molarity of iodine solution, V1 is volume


of iodine solution used and W is weight of activated carbon.

The Freundich Isotherm model represented by Eq. 7 de2.2.5. Batch Adsorption Experiment and Adsorption Iso-

scribes the heterogeneous surface energies by multilayer ad-

therm of I2

sorption [7].

Batch Adsorption experiments were carried out to determine


(7)

the optimum contact time and adsorption isotherms of I2 onto


the activated carbon in a series of 250 mL conical flasks. The
procedure involved filling each flask with 100 cm3 of 0.1 M

Freundich Isotherm when expressed in the logarithmic form;

iodine solution. Equal weights of activated carbon were add-

the empirical equation becomes a straight line and the con-

ed into the different flasks and the flasks were shaken using
the Griffin flask shaker to achieve equilibrium. The adsorp-

are found by linear regression.

stants KF and

tion isotherm for I2 were studied by varying the activated


carbon weights between 0.4 to 2.4 g at a concentration of 0.1
M iodine solution and for an optimal period of 1 hr, while the

Log qe = log KF +

log Ce

(8)

effect of contact time was studied at different time periods of


10, 20, 30, 60, 90 and 120 minutes.

3. Results and Discussion

2.2.6. Adsorption Isotherm Models

3.1. Characterization of Unmodified and Modified Activated Carbons

The Langmuir and Freundlich isotherms models were employed to determine the relationship between the amount of

The FTIR spectra of the unmodified activated carbons present

I2 uptake (qe) and its concentration at equilibrium (Ce)

broad and intense peak of O-H stretching vibrating of hydroxyl groups of alcohols, phenols or absorbed water at

The amount of I2 adsorbed per gram of carbon was calculated

3414.12 & 3444.98 cm-1 for the millet and sorghum straws

using Eq 3

respectively. The bands were found to be slightly shifted in the


modified samples at 3472.95 and 3390.97 cm-1 respectively.
(3)
The bands at 1644.37 & 1640.51 cm-1 due to C=C stretching

Where C1 and Ce are the initial and equilibrium concentration

vibration in alkenes observed in the unmodified samples, were

(mg/L), M is the mass of activated carbon (g) and V is the

found to occur at 1642.44 & 1643.41 cm-1 for the modified

volume of the solution (mL). Percent I2 removal was calcu-

samples. The bands in the region of 1378.18 & 1385.90 cm-1

lated using Eq. 4

that are due to the stretching vibration of the nitro group


(C-NO2) [8], were only detected in the modified samples.
Other bands detected are 1138.04 & 1146.72 cm-1 in the un(4)

modified samples due to C-O stretching vibration in alcohols

The Langmuir model which assumes monolayer adsorption

or ether but were found at 1160.22 & 1146.01 cm-1 in the

onto the activated carbon is given by Eq. 5

modified samples.
The SEM micrographs of the activated carbons are shown in
(5)

This when manipulated to the linear form gives Eq. 6

Figures 1 a-f more open structures are exhibited in the modified activated carbon samples than the unmodified activated
carbons, caused by the collapse of the micropores and creation
of macropores which may be due to the introduction of oxy-

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ISSN (Online): 2347-3878, Impact Factor (2015): 3.791
gen containing functional groups from the modifying agents.

sorption of cadmium ions from aqueous solution. The adsorption of Perchlorate (ClO4-) from aqueous solution was
examined with ammonia treated activated carbon by [6]; the
researchers noted that higher adsorption capacity for perchlorate was achieved without undermining the pore structure.
3.3. Effect of Contact Time
The effect of contact time on I2 adsorption efficiency using the
modified activated carbons showed that about 80 % of I2 was
absorbed by millet straw activated carbon while 72 % of I2 was
absorbed by sorghum straw activated carbon within 1 hr,
while about 89 % of I2 was absorbed by millet straw and 77 %
of I2 was observed by sorghum straw after 2 hrs.

Figure 1: SEM images of (a) unmodified millet straw acti-

Figure 2: The percent iodine adsorbed against contact time

vated carbon, (b) unmodified sorghum straw activated carbon,

by unmodified millet straw activated carbon and the various

(c) nitric acid modified millet straw activated carbon, (d) nitric

modified millet straw activated carbon (2.0 M HNO3 and 2.0

acid modified sorghum straw activated carbon, (e) sodium

M NaOH) using 1.0 M KOH at 600 oC

hydroxide modified millet straw activated carbon and (f)


sodium hydroxide modified sorghum straw activated carbon
3.2. Iodine number
Table 1 showed that the iodine numbers of the unmodified
activated carbons (UMS and USS) were 689.3mg/g and
565.4mg/g, and after modification with nitric acid and sodium
hydroxide higher iodine number values were obtained as
presented in Table 1. Between the two modifying agents used
nitric acid improves the pore structure and surface area of the

Figure 3: The percent iodine adsorbed against contact time

activated carbons more there by leading to enhanced adsorp-

by unmodified sorghum straw activated carbon and the vari-

tive capacity. Similar results were obtained by other re-

ous modified sorghum straw activated carbon (2.0 M HNO3

searchers; [1] observed that the adsorption of Cr (III) was

and 2.0 M NaOH) using 1.0 M KOH at 600 oC

increased on oxidation of granular activated carbons with


nitric acid, hydrogen peroxide and ammonium persulphate in

3.4. Adsorption Isotherms

aqueous solution. Another report [11] showed that the incorporation of acidic oxygen functional groups into activated

Table 2 represents the Langmuir and Freundlich isotherm

carbon by HNO3 oxidation dramatically enhanced the ad-

parameters for adsorption of iodine. It was found that the

Paper ID: 1071602

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International Journal of Scientific Engineering and Research (IJSER)


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ISSN (Online): 2347-3878, Impact Factor (2015): 3.791
equilibrium data were fitted into both isotherm models with R2

4. Conclusion

of the modified activated carbons being higher (0.964, 0.973)


than those of the unmodified activated carbons (0.759, 0.828).

The present study highlighted the importance and relevance


of chemical modification of the surface chemistry of acti-

KF and , indicated normal adsorption [9] and the maximum

vated carbon produced from Pennisetum glaucum and Sorghum bicolor. SEM images and FTIR analysis showed in-

monolayer coverage (Qo) was also found to be generally

creased pore formation and increase in the number of surface

higher in the modified activated carbons (50.0 mg/g and 47.62

functional groups as a result of the modification treatment. A

mg/g) compared to the unmodified activated carbons (2.976

significant increase in iodine number was achieved after

mg/g and 3.311 mg/g).The equilibrium parameter (RL) was

modification, but the best results was obtained for the nitric

found to be greater than zero but less than 1 indicating that all

acid modified activated carbon samples; between the two

the adsorption processes were favourable [17].

precursors studied, nitric acid modified sorghum straw activated (MSS) apparently absorbed higher amount iodine
(IN=911.2 mg/g).

Table 1: Iodine Number (IN) Values of Unmodified and Modified Activated Carbon
Unmodified Activated
carbon

Iodine Number mg/g

Modified Activated
carbon

Modifying Agents
(2.0 M)

UMS

689.3

MMS

HNO3
NaOH

USS

565.4

MSS

HNO3
NaOH

Iodine Number (mg/g)


898.0
835.5
911.2
595.2

Key:
UMS Unmodified Millet Straw Activated Carbon, USS- Unmodified Sorghum Straw Activated Carbon.
MMS Modified Millet Straw Activated Carbon, MSS- Modified Sorghum Straw Activated Carbon.
Table 2: Freundlich and Langmuir Parameters for Adsorption of Iodine unto Modified and Unmodified Activated Carbon
Activated
Carbon
MMS
MSS
UMS
USS

Freundlich parameters
n Kf
0.382 2.62 5.90
0.4 2.5 4.94
0.302 3.31 3.60
0.312 3.21 2.838

Langmuir parameters
Qo K RL
50.0 5.03 x 10-2 2.95 x10-2
47.62 4.56 x 10-2 3.34 x 10-2
2.976 0.316 4.936 x10-3
3.311 0.239 6.515x10-3

References

Correlation coefficients
Freundlich Langmuir (R2)
0.964 0.732
0.973 0.716
0.759 0.758
0.828 0.829

Determination of Iodine Number of Activated Carbon


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