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International Journal of Chemical

& Petrochemical Technology (IJCPT)
ISSN(P): 2277-4807; ISSN(E): 2319-4464
Vol. 5, Issue 3, Oct 2015, 23-28
© TJPRC Pvt. Ltd.

ADSORPTION OF HUMIC ACID FROM AQUEOUS SOLUTION
ONTO FE3O4 COATED CARBON: KINETICS STUDY
HENRY SETIYANTO & MUHAMMAD ALI ZULFIKAR
Analytical Chemistry Research Group, Bandung Institute of Technology, Bandung, Indonesia

ABSTRACT
The main objective of this study is to investigate the kinetics sorption of humic acid (HA) from aqueous solution
onto Fe3O4 coated carbon. Batch adsorption experiments were carried out using HA solution as an adsorbate under variety
of concentration in the range of 50-200 mg/L. The experimental results indicate that, the percentage of HA adsorption
decreases with an increase in the HA concentrations. The kinetic experimental data proportionally correlated with the
pseudo-second-order kinetic model with a rate constant in the range of 0.042-0.085g mg-1 min-1.

KEYWORDS: Adsorption, Carbon Coated, Humic Acid, Kinetics
INTRODUCTION
One of problems that are faced by people who live inlowland and marshy area is the scarcity of available clean
water. This is due to the fact that the abundant source of water in that area is peat water.Humic substance is one of the main
components of peat water that is consisted of large molecules with molecular weights ranging from thousands to hundreds
of thousands (Gezici et al., 2005) and have a backbone of aromatic and aliphatic residues with numerous substituents such
as OH groups, ketones, carboxylic acid groups, amino acids/peptides, saccharides and amino saccahrides (Albers et al.,
2008). Humic acid compounds tend to react with a variety of oxidants and disinfectants to form carcinogenic disinfection
byproducts (DBPs) such as trihalomethanes and haloacetic acids during drinking water production(Rojas et al., 2011;
Uygunera et al., 2007; Sonea et al., 2010; Sun et al., 2011). At the same time, humic acid may cause water to have color,
taste and odor, and bind heavy metals, making water treatment necessary.
At present, there are several methods used to remove humic acid from aqueous solution, such ascoagulation and
flocculation (Rojas et al., 2011; Uygunera et al., 2007; Sun et al., 2011), oxidation (Uygunera et al., 2007), photocatalysis
(Sonea et al., 2010), biofiltration (Hu et al., 2003) and membrane filtration (Rojas et al., 2011), techniques have been
developed to remove these substances. All of these alternative processes, however, have disadvantageous, e.g high
operational cost and requires some chemicals.
Adsorption is known to be a promising technique, which has great importance due to the ease of operation and
comparable low cost of application in the adsorption process. Commercially activated carbon is the most widely studied
and used as adsorbents for water and wastewater treatments. However, activated carbon is an expensive adsorbent due to
its high cost of manufacturing and regeneration (Aksu and Aisoglu, 2005). For the purpose of removing unwanted
hazardous compounds from contaminated water at a low cost, much attention has been focused on various naturally
occurring adsorbents. Among these adsorbents, Fe3O4 coated carbon have been shown to be the most promising
alternatives.These magnetic nano-particles can adsorb pollutants from aqueous solutions and then be separated from the
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24

Henry Setiyanto & Muhammad Ali Zulfikar

water with a simple magnetic process. Many researchers have been focused on modification of the Fe3O4 nano-particles to
provide a better surface specificity to removal of different pollutans from aqueous solutions
The main objective of this study is to investigate the kinetics sorption of humic acid (HA) from aqueous solution
onto Fe3O4 coated carbon.

MATERIALS AND METHODS
Materials
Fe3O4 coated carbon was obtained from Analytical Chemistry Laboratory, Institut Teknologi Bandung, Indonesia.
HA was obtained from Merck. Sodium hydroxide and hydrochloric acid used to adjust pH was purchased from Merck.
Water used was generated from aqua demineralization system. All materials were used without further purification.
Methods
Adsorption experiments were carried out in 100 mL flasks containing 50 mL of HA solution with various initial
concentrations (50-200 mg/L) and 0.5 g Fe3O4 coated carbon as an adsorbent. These mixtures immersed in a thermostatic
shaker bath at 25 oC in thermostatic shaker bath for 2, 5, 10, 15, 20, 30, 40, 60, 80, 100, 120 and 180 minutes. At the end of
the predetermined time interval, the suspension was taken out and the supernatant was sentrifugated at 300 rpm for 10
minutes. The HA concentration was determined by spectrophotometer (Shimadzu UV-Vis 1601 model) at the λ300 nm.
The percent of HA adsorption was calculated using the following equation:
Adsorption (%) = [(Ci-Ce)/Ci] x 100%

(1)

where Ci and Ce are initial and final concentration of HA in solution, respectively. The adsorption capacity of an
adsorbent at equilibrium with solution volume V, was calculated using the following equation:
qe (mg/g) = [(Ci-Ce)/m] x V

(2)

where Ci and Ce are the initial and final concentration of HA in solution, respectively. V is the volume of solution
(L) and m is mass of adsorbent (g) used.

RESULTS AND DISCUSSIONS
The effect of contact time on HA adsorption onto Fe3O4 coated carbon at various initial concentrations is shown
in Fig.1. The percentage of adsorption increased with increase in agitation time and reached a constant value with the
increase in contact time. A rapid increased is observed for the first 20 minutes and it then proceeds slowly until reached
equilibrium.The sorption equilibrium was achieved during the same period of 50 minutes.

Impact Factor (JCC): 3.5367

Index Copernicus Value (ICV): 3.0

Adsorption of Humic Acid from Aqueous Solution on to
Fe3o4 Coated Carbon: Kinetics Study

25

Figure 1:: Effects of Contact Time and Initial Concentration
on HA Adsorption on to Fe3O4 Coated Carbon
From Figure 1, it also shows that the amount of HA adsorbed onto Fe3O4 coated carbon is decreased with
increasing initial concentration. It is thought that this may be due to its molecules tending to aggregate at higher
concentration, so HA diffusion ontoFe3O4 coated carbon being restricted (Amran and Zulfikar, 2010).
2010)
In order to investigate the adsorption mechanism of humic acid onto Fe3O4 coated carbon,
carbon the kinetic data
obtained were analysis using the pseudo
eudo-first-order adsorption and the pseudo-second-order
order. The linearized form of the
pseudo-first-order
order rate equation is given as:
log (qe-qt) = log qe – (k1/2.303) t

(3)

where qeand qt are the amounts of HA adsorbed (mg/g) at equilibrium and at time (t),
( respectively, and k1 (min-1)
is the rate constant of this equation. The value of qe and k1 was obtained from intercepts and slope of the linear plots of log
(qe-qt) against t.
Figure 2 shows the kinetics of HA adsorption by using pseudo-first-order
pseudo
order model, and its kinetics parameters are
shown in Table 1. It was observed that the pseudo-first-order
pseudo
order kinetic model did not adequately fit the experimental values.
Also from Table 1, it is indicated
ndicated that the values of the correlation coefficients are not high for the various HA
concentrations. Furthermore,, a large differenceof equilibrium adsorption capacity (q
( e) between the experimentand
calculation was observed, indicating a poor pseudofirst-order
pseudofirs
fit to the experimental data.

logq
(e-qt)

1
0.5
0
0
-0.5
-1

50 mg/L 20
100 mg/L
150 mg/L
200 mg/L

40

60

t (min)

Figure 2: Pseudo-First-Order
Pseudo
Plots for Adsorption of HA on to Pyrophyllite
The pseudo-second-order
order rate equation assumes that the adsorption capacity is proportional to the number of
active sites on the surface. The pseudo-second
second- order equation is expressed as:

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Henry Setiyanto & Muhammad Ali Zulfikar

t/qt=1/k2.qe2+t/qe

(4)

where qeand qtare the amounts of HA adsorbed (mg/g) on adsorbents at equilibrium, and at time t, respectively
and k2 is the rate constant (g/mg.min−1).
The linear plots of t/qtvs t show a good agreement of experimental data with the pseudo-second-order kinetic
model for different initial HA concentrations (Fig. 3). The correlation coefficients for the pseudo-second-order kinetic
model are greater than 0.995 (Table I). Also, the calculated qe values agree very close to the experiment data (qexp). These
indicate that the adsorption system belongs to the pseudo-second-order kinetic model.
Tabel 1: Pseudo-Fist And Pseudo Second Order Kinetics Parameters For HA Adsorption
Initial
Conc.
(mg/L)
50
100
150
200

qexp
(mg/g)

k1
(min-1)

qcal
(mg/g)

2.885

0.098

2.458
1.715
1.482

0.086
0.075
0.064

3.208
0.978 0.085
Table 1: contd.,
3.004
0.972 0.074
2.799
0.983 0.058
2.623
0.983 0.042

k2
(g.mg-1.min-1)

R2

qcal
(mg/g)

R2

3.315

0.999

3.172
2.746
2.625

0.999
0.999
0.999

t/qt (min.g/mg)

80
50 mg/L
100 mg/L
150 mg/L
200 mg/L

60
40
20
0
0

50

100

150

200

t (min)

Figure 3: Pseudo-Second-Order Plots for Adsorption of HA on to Pyrophyllite
Table 1, it also show that the values of the rate constant k2 decrease with increasing initial concentrations. The
reason for this behavior can be attributed to the decrease in the mobility of its molecule with increasing initial
concentration which may be due to these molecules to aggregate at higher concentration and consequently lower diffusion
rates are obtained.

CONCLUSIONS
Fe3O4 coated carboncan be effectively used as an adsorbent for the HA adsorption from aqueous solution. The
result from this work showed that the HA initial concentration has an important role in the adsorption of HA onto Fe3O4
coated carbon. Kinetic parameters data indicated that the HA sorption process follow pseudo-second-order model, with a
rate constant in the range of 0.042-0.085 g mg-1 min-1.

ACKNOWLEDGMENT
The author is very grateful to Bandung Institute of Technology for the financial support this research study.

Impact Factor (JCC): 3.5367

Index Copernicus Value (ICV): 3.0

Adsorption of Humic Acid from Aqueous Solution on to
Fe3o4 Coated Carbon: Kinetics Study

27

REFERENCES
1.

Albers, C.N., Banta, G.T., Hansen, P.E. andJacobsen, O.S. 2008.Effect of different of humic substances on the
fate of diuron and its main metabolite 3,4-dichloroaniline in soil, Environmental Science and Technology, 42,
8687-8691.

2.

Aksu, Z. and Aisoglu, I. 2005. Removal of Cu (II) ions from aqueous solution by bio sorption onto agricultural
waste sugar beet pulp, Processes Biochemistry, 40, 3031-3044.

3.

Amran, M.B. and Zulfikar, M.A. 2010. Color removal of congo red dyestuff by adsorption onto phyrrophyllite,
International Journal of Environmental Science, 67(6), 911-920.

4.

Dogan, M., Ozdemir, Y. and Alkan, M. 2007. Adsorption kinetics and mechanism of cationic methyl violet and
methyl blue dyes onto sepiolite, Dyes and Pigments, 75, 701-713.

5.

Erdemoglu, M., Erdemoglu, S., Sayilkan, F., Akarsu, M., Sener, S. And Sayilkan, H. 2004. Organo-functional
modified pyrophyllite: preparation, characterisation and Pb(II) ion adsorption property, Applied Clay Science, 27,
41-52.

6.

Gezici, O., Kara, H., Ersoz, M.and Abali, Y. 2005. The sorption behaviour of nickel-insolubilized humic acid
system in a column arrangement, Journal of Colloid Interface Science, 292, 381-391.

7.

Gucek, A., Sener, S., Bilgen, S. and Mazmanci, M.A. 2005. Adsorption and kinetic studies of cationic and anionic
dyes on pyrophyllite from aqueous solutions, Journal of Colloid Interface Science, 286, 53-60.

8.

Hu, C. Yu, J.C., Hao, Z. and Wong, P.K. 2003. Effects of acidity and inorganic ions on the photocatalytic
degradation of different azo dyes, Applied Catalyst B,46, 35-47.

9.

Rojas, J. C., Pérez, J. Garralón, G., Plaza, F., Moreno, B. and Gómez, M.A. 2011. Humic acids removal by
aerated spiral-wound ultrafiltration membrane combined with coagulation–hydraulic flocculation, Desalination,
266, 128-133.

10. Sonea, D., Pode, R., Manea, F., Ratiu, C., Lazau, C., Grozescu, I.and Burtica, G. 2010.The comparative
assessment of photolysis, sorption and photocatalysisprocesses to humic acids removal from water, Chemical
Bulletin of "POLITEHNICA" Univ. (Timisoara), 55(69), 148-151.
11. Sun, C., Yue, Q., Gao, B., Mu, R., Liu, J., Zhao, Y., Yang, Z.and Xu, W. 2011. Effect of pH and shear force on
flocs characteristics for humic acid removal usingpolyferric aluminum chloride organic polymer dual-coagulants,
Desalination, 281, 243-247.
12. Uygunera, C.S., Suphandaga, S.A., Kercb, A.and Bekbolet, M. 2007. Evaluation of adsorption and coagulation
characteristics of humic acids preceded by alternative advanced oxidation techniques, Desalination, 210, 183-193.

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