Journal of Colloid and Interface Science 287 (2005) 14–24

www.elsevier.com/locate/jcis

Adsorption of phenols from wastewater

M. Ahmaruzzaman ∗ , D.K. Sharma
Centre for Energy Studies, Indian Institute of Technology Delhi, New Delhi 1110016, India
Received 20 October 2004; accepted 24 January 2005
Available online 12 April 2005

Abstract
The present work involves an investigation of the possible use of coal, residual coal, and residual coal treated with H3 PO4 as a means of
removal of phenol from wastewater. The study was realized using batch experiments, with synthetic wastewater having phenol concentration
of 1000 ppm. Other low-cost adsorbents such as petroleum coke, coke breeze, rice husk, and rice husk char have also been used. The
effect of system variables such as pH, contact time, and temperature has been investigated. The suitability of the Freundlich, Langmuir, and
Redlich–Peterson adsorption models to the equilibrium data was investigated for each phenol–adsorbent system. The results showed that the
equilibrium data for all the phenol–sorbent systems fitted the Redlich–Peterson model best. Kinetic modeling of removal of phenols was
done using the Lagergren first-order rate expression. A series of column experiments were performed to determine the breakthrough curves.
 2005 Elsevier Inc. All rights reserved.

Keywords: Adsorption; Equilibrium isotherm; Freundlich isotherm; Redlich–Peterson isotherm; Langmuir isotherm; Kinetics; Column

1. Introduction
Adsorption is one of the most effective processes of ad-
vanced wastewater treatment, which industries employ to
reduce hazardous organic and inorganic wastes in efflu-
ents. It is also used to remove toxic inorganic and organic
compounds from contaminated ground water. Phenolic com-
pounds are considered to be hazardous wastes, which are
released into the aquatic environment by industries such as
coke ovens in steel plants, petroleum refineries, petrochem-
ical, phenolic resin, and fertilizer, pharmaceutical, chemi-
cal, and dye industries and have been reported in hazardous
wastes sites.
The adsorption technique is also used to reducing phenols
in wastewater. In fact, wastewater treatment using activated
carbon is one of the most important uses of activated carbon.
The content of phenolic compounds in industrial wastewa-
ter (about 200–2000 mg/L) is usually higher than the stan-
dard limits (mostly less than 0.5 mg/L) established for their
release into aquatic environment. Therefore, extensive re-
* Corresponding author.
E-mail address: md_a2002@rediffmail.com (M. Ahmaruzzaman).
0021-9797/$ – see front matter  2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2005.01.075
search work has been carried out using activated carbons and
resins [1–3]. The use of activated carbon as an adsorbent for
industrial wastewater treatment is capital-intensive and has
several other problems, such as (1) regeneration of activated
carbon, (2) intraparticle resistance in adsorption processes in
practice, and (3) high cost of manufacture.
There is scope for developing adsorbents from low-cost
materials, such as fertilizer wastes [4], wood [5], and rice
husk [6], by several chemical treatments. The use of saw-
dust for the removal of phenol from aqueous solution has
been studied by Sivanandam and Anirudhan [7]. Dutta et
al. [8] carried out studies on adsorption of p-nitrophenol on
charred sawdust. They found that the degree of agitation has
a significant effect on the rate of removal of p-nitrophenol.
Higher initial concentration and lower temperature are more
favorable for the adsorption of p-nitrophenol. Adsorption
equilibrium data were found to fit the Langmuir adsorp-
tion isotherm most satisfactorily. Kinetics and mechanism
of removal of 2,4-dimethylphenol from aqueous solutions
with fly ash have been reported by Batabyal et al. [9]. They
showed that the rate of adsorption followed first-order kinet-
ics before attaining equilibrium. Both diffusional and kinetic
resistance affect the rate of adsorption and their relative ef-
fects vary with operating temperatures. Equilibrium adsorp-
 M. Ahmaruzzaman, D.K. Sharma / Journal of Colloid and Interface Science 287 (2005) 14–24
tion data satisfied both Langmuir and Freundlich isotherm.
The use of peat, fly ash, and bentonite for the removal of
phenol from wastewater has been studied by Viraraghavan
and Maria Alfaro [10]. They reported that the adsorption
of phenol on peat and bentonite was described well by the
Freundlich isotherm, whereas the Langmuir isotherm de-
scribed the adsorption of phenol on fly ash. Peat, fly ash,
and bentonite were found to adsorb 46.1, 41.6, and 42.5%
phenol respectively from an initial concentration of approxi-
mately 1 mg/L. Alemany et al. [11] also studied the removal
of phenol from aqueous solution by adsorption on coal fly
ash. The phenol adsorption capacity was found to depend on
the solubility or hydrophobicity of the adsorbate and on the
pH-modified fly ash. They reported that temperature has a
relatively minor influence on the adsorption process.
Jain et al. [12] recently reported on the removal of methyl
phenol from water by low-cost adsorbents such as blast fur-
nace sludge, dust, and slag. They also utilized some carbona-
ceous adsorbents prepared from fertilizer industry for the
removal of methyl phenol. The adsorption of phenols on this
carbonaceous adsorbent as a function of contact time, con-
centration, and temperature has been studied by the batch
method. The adsorption has been found to be endothermic
and the data conform to the Langmuir equation. Analysis of
the data indicated that adsorption was a first-order process
and pore-diffusion controlled. They also found that carbona-
ceous adsorbent was about 45%, as efficient as standard ac-
tivated charcoal.
Aksu and Yener [13] also used dried activated sludge and
fly ash for the removal of monochlorinated phenols from
wastewater. The suitability of the Freundlich, Langmuir, and
Redlich–Peterson adsorption models to the equilibrium data
was investigated for each monochlorinated phenol–sorbent
system. The results showed that the equilibrium data for the
monochlorinated phenol–sorbent system fitted the Redlich–
Peterson model best within the concentration range studied.
Gupta and Ali [14] developed low-cost adsorbents to car-
bon for water treatment. Removal of chlorophenols from
wastewater using red mud has also been studied by Gupta et
al. [15]. Jain et al. [16] reported the removal of phenols us-
ing industrial wastes. Gupta et al. [17] also utilized Bagasse
fly ash generated from the sugar industry for the removal
and recovery of phenol and p-nitrophenol from wastewater.
Srivastava et al. [18,19] also reported the removal of 2,4,6-
trinitrophenol and 2,4-dinitrophenol using Bagasse fly ash.
In fact, research work has been carried out on develop-
ment of some low-cost adsorbents, such as rice husk, cotton,
bark, and coal. One advantage of the adsorption technique is
that it may easily be linked up with biochemical or chemical
techniques. Use of biologically activated carbons is possible.
However, due to the high cost of the manufacture of activated
carbon and the difficulty of regeneration of carbon, there has
been significant interest in studies of coal with or without
pretreatment as an adsorbent for phenols.
Coal has been reported to be a good adsorbent for p-ni-
trophenol [20]. The adsorption of phenolic compounds onto
15
coal-reject-derived adsorbents has also been reported [21].
However, pretreated coal has been found to be better than
original coal as an adsorbent for the removal of phenol [22].
Attempts have also been made to activate the coal to in-
crease its capacity to adsorb phenol from phenol-rich waste-
water. Bituminous coal was acid-activated for adsorption of
chlorophenol [23].
Coal is known to possess good microporosity and thus
a large surface area, although the utilization of the pore in
the reaction/interaction of the surface is poor. Attempts to
improve the surface and porosity of coal by different coal
conversion processes such as oxidation, pyrolysis, and sol-
vent extraction, separately or in combination, seem to be
a rewarding field of research on adsorption. Reed et al.
[24] have reviewed recent research work on physicochem-
ical processes for wastewater treatment. It was reported that
adsorption kinetics was first-order, indicating that pore dif-
fusion is rate-limiting. Equilibrium isotherms were fit by the
Langmuir equation.
Solvent extraction of coal may result in increased poros-
ity (because of selective dissolution of specific organic com-
ponents, that is, leaching of coal by solvent) and reduction
of particle size. These, in turn, may improve the adsorption
capacity of the coal.
In fact, solvent extraction (organorefining) of coal using
N -methyl-2-pyrrolidone containing a small amount of eth-
ylenediamine results in the production of an extract from
the coal. This extract, on removal of the solvent, would af-
ford an ultra-low-ash coal as a cleaner fuel (superclean coal)
and a chemical feedstock. The residual coal obtained after
organorefining has undergone solvolytic leaching, resulting
in regeneration of new pores, reduction of particle size, and
creation of cracks, channels, defects, etc. in the surface of
coal. These would help increased surface area of the coal
and a consequent increase in adsorption capacity.
Utilization of residual coal for removal of phenol from
wastewater would integrate the process of organorefining of
coal to obtain superclean coal with the advanced process of
adsorption of phenol from wastewater.
In addition, cracking of petroleum vacuum residue also
generates petroleum coke as a by-product, which may be
used for the removal of phenol from industrial wastewater.
Therefore, the present studies were extended toward the po-
tential use of residual coal, petroleum coke, biomass char,
and other low-cost adsorbents for the removal of phenol,
p-chlorophenol, and p-nitrophenol.
2. Experimental
2.1. Preparation of adsorbents
Samla coal (5 g) was taken in a 250-ml round-bottomed
flask containing EDA (5 ml) and NMP (65 ml). A coal-to-
EDA ratio of 1:1 (wt/vol%) and a coal-to-NMP ratio of 1:17
(wt/vol%) were used. The mixture was refluxed for 2 h and
16 M. Ahmaruzzaman, D.K. Sharma / Journal of Colloid and Interface Science 287 (2005) 14–24

filtered. The residual coal (RC) obtained after filtration was
dried overnight in an oven at 105 ◦ C. The residual coal was
washed with 2% aqueous HCl to remove EDA and then with
distilled water to remove excess acid. Final washing was
done in a Soxhlet apparatus with a 1:1 methanol–water mix-
ture.
Residual coal is also treated with H3 PO4 and used for ad-
sorption study. Petroleum coke was obtained from the crack-
ing of petroleum vacuum residue. Rice husk was obtained
from a local mill and rice husk char was prepared in the labo-
ratory by pyrolyzing the rice husk char at 550 ◦ C in nitrogen.
Different adsorbents, as mentioned above, were used here
for adsorption study of phenols. The wastewater used in this
study was synthetic wastewater prepared in the laboratory.
The initial concentration of phenol used was 1000 ppm.
The experimental program consisted of three parts:
1. Batch studies to compare the performance and effective-
ness of different adsorbents in removing phenol.
2. Batch studies to see the effect of pH and contact time on
the removal of phenol.
3. Column studies for the removal of phenol.
Studies were extended to the adsorption of p-nitrophenol
and p-chlorophenol.
2.2. Batch studies
Batch experiments were conducted by contacting known
amounts of different adsorbents with 20 ml of synthetic
wastewater containing 1000 ppm aqueous phenol solution.
The solution containing the adsorbents was left for 72 h. Af-
ter the equilibrium time the treated solution was centrifuged
and the supernatant solution was analyzed for residual con-
centration of phenol at αmax = 500 nm using spectrophotom-
etry by the 4-aminoantipyrene method.
2.3. Kinetic studies
Fixed amounts of adsorbents were taken in a conical flask
containing 1000 ppm aqueous phenol solution (20 ml) and
the solution containing the adsorbent was left for different
time intervals. The concentration of phenol after different
time intervals was determined spectrophotometrically by us-
ing UV spectrophotometer.
2.4. Column studies
Fixed bed studies were conducted in a fixed bed of down-
flow 20-mm-diameter glass columns. The treated solution
was collected from the bottom of the column and analyzed
for phenols. The flow rate was kept at 30 ml/h.
3. Results and discussion
Table 1 shows the characteristics of the adsorbents used
for the adsorption. Particle size distributions of the adsor-
bents were shown in Table 2.
Modelling of the equilibrium data has been done using
Freundlich, Langmuir, and Redlich–Peterson isotherms.
Langmuir equation: The Langmuir equation is the most
widely used two-parameter equation, commonly expressed
as
Ce 1 Ce
= + , (1)
x/m ab a
where Ce = equilibrium concentration of adsorbate in so-
lution after adsorption; x/m = amount adsorbed per unit
weight of adsorbent; and a and b are the Langmuir constants.
From a plot of Ce /(x/m) versus Ce , a (mg/g) and b (L/mg)
can be determined from the slope and intercept, respectively.
Freundlich equation: At equilibrium conditions, the ad-
sorbed amount x/m can also be predicted using the Fre-
undlich equation,
x 1/n
= kCe , (2)
m
where the parameters k and n can be obtained using the lin-
ear form
x 1
log = log k + log Ce , (3)
m n

Table 1
Characteristics of adsorbents
Adsorbent Total Total Median pore Median pore Average pore Surface Bulk Apparent Porosity Stem
intrusion pore area diameter diameter diameter area density skeletal (%) volume
volume (m2 /g) (volume) (area) (4V /A) (m2 /g) (g/ml) density used (%)
(ml/g) (µm) (µm) (µm) (g/ml)
Samla coal 0.6081 6.89 18.3987 0.0128 0.353 135.30 0.7784 1.478 47.33 56
Residual Samla 1.0293 6.763 31.8526 0.0153 0.6088 165.07 0.6046 1.6007 62.23 55
coal (RC)
RC treated with 0.6894 12.157 12.7645 0.0138 0.2268 312.56 0.7483 1.5455 51.59 34
H3 PO4
Petroleum coke 0.6723 5.166 24.3912 0.0131 0.5205 96.44 0.7381 1.4653 49.63 65
Coke breeze 0.4469 0.128 13.6808 12.3074 13.9753 – 0.8454 1.3587 37.78 41
Rice husk 1.5343 10.625 34.8641 0.0126 0.5776 – 0.4425 1.3779 67.89 41
Rice husk char 1.0807 11.269 8.8909 0.0162 0.3836 230.09 0.6067 1.7623 65.57 79
 M. Ahmaruzzaman, D.K. Sharma / Journal of Colloid and Interface Science 287 (2005) 14–24 17

Table 2
Particle size distribution of adsorbents
Under (%) Size (µm) Over (%)
Samla coal Residual coal RCP Activated carbon Petroleum coke Coke breeze Rice husk Rice husk char
5 16.96 13.39 10.20 3.20 20.68 16.24 25.71 20.36 95
10 27.71 22.22 22.14 4.13 27.09 26.98 36.40 31.49 90
15 35.29 28.72 28.60 4.87 31.55 32.99 40.82 39.15 85
20 41.74 33.86 34.21 5.66 35.52 37.95 44.66 45.25 80
25 47.01 37.97 38.42 6.80 38.97 41.78 48.46 50.24 75
30 53.63 42.57 41.85 8.84 42.36 46.27 54.97 55.67 70
35 58.35 46.09 45.60 11.21 47.31 50.70 60.32 61.07 65
40 64.54 49.77 47.95 13.76 51.70 55.71 68.85 69.35 60
45 70.43 53.10 51.65 16.40 59.45 61.10 75.37 75.68 55
50 78.96 57.11 54.24 19.00 67.30 65.98 83.99 80.82 50
55 86.06 63.50 56.57 21.95 75.46 70.37 93.07 86.31 45
60 91.00 69.19 58.48 24.97 83.58 76.11 101.8 92.88 40
65 96.69 74.28 60.91 29.77 93.68 82.44 109.1 100.5 35
70 101.8 79.88 64.27 33.12 101.1 90.74 116.5 107.5 30
75 104.8 85.65 68.92 38.34 111.2 99.30 122.3 113.8 25
80 112.3 97.74 74.16 43.83 121.8 107.2 126.0 118.3 20
85 119.2 107.3 78.87 48.29 127.9 113.4 130.4 126.3 15
90 127.2 114.4 89.37 58.60 134.1 120.3 136.1 131 10
95 136.3 128.1 96.17 67.92 141.1 135.3 139.5 138.9 5
97 138.7 136.5 103.6 72.96 144.6 136.4 141.8 143.3 3
99 145.2 139.7 108.5 83.77 146.5 138.9 145.9 146.2 1
100 147.5 141.5 121.0 101.5 147.5 141.0 147.0 148 0

where k is an indication of the adsorbent capacity and 1/n

is a measure of the surface heterogeneity, ranging between 0
and 1, becoming more heterogeneous as its value gets closer
to zero. Using Eq. (3) from the plot of log x/m versus log Ce ,
the parameters n and k were obtained from the slope and
intercept, respectively.
Redlich–Peterson equation: The Redlich–Peterson equa-
tion has three parameters, A, B and β. Parameter β ranges
between 0 and 1:
Fig. 1. Freundlich adsorption isotherm for phenol (petroleum coke).
Ce B 1 β
= + Ce . (4)
x/m A A
the models were estimated by nonlinear regression and by
This isotherm describes adsorption on heterogeneous sur- fitting transformed data to the linearized forms of the mod-
faces, as it contains the heterogeneity factor β. It can be els.
reduced to the Langmuir equation [25] as β approaches 1.
Using Eq. (4), the parameters A, B, and β were determined 3.1. Adsorption isotherm of phenol
by curve fitting.
Analysis of the isotherm is important in order to de- 3.1.1. Petroleum coke
velop an equation that accurately represents the results and Petroleum coke obtained from the thermal cracking of
which could be used for design purposes. Out of the several petroleum vacuum residue was used for the removal of phe-
isotherm equations, three have been applied in this study, the nol. Using Eq. (2), from the plot of log(x/m) versus log Ce
Langmuir (1), Freundlich (2), and Redlich–Peterson models. (Fig. 1), the parameters n and k were obtained from the
To compare the validity of isotherm equations more defi- slope and intercept, respectively. Fig. 2 shows the plot of
nitely, a normalized deviation q is calculated, Ce /(x/m) versus Ce for phenol using petroleum coke as ad-

N  qeq,i,exp −qeq,i,calc  sorbent, and Langmuir constants were determined from the
i=1 qeq,i,exp slope and intercept. Fig. 3 shows the plot of Ce /(x/m) ver-
qeq (%) = × 100, (5)
N sus Ceb for petroleum coke and Redlich–Peterson constants
where the subscripts “exp” and “calc” show the experimental were determined.
and calculated values and N is the number of measurements. Comparing the values of q and R 2 , the Langmuir
Adsorption model constants, the values of which express isotherm fits the phenol adsorption data better than the
the surface properties and affinity of the adsorbent, can be Freundlich isotherm. However, the Redlich–Peterson model
used for different adsorbents (sorbates). The parameters in showed an improved fit for phenol. The adsorption constants
18 M. Ahmaruzzaman, D.K. Sharma / Journal of Colloid and Interface Science 287 (2005) 14–24
Fig. 2. Langmuir adsorption isotherm for phenol (petroleum coke).
Fig. 3. Redlich–Peterson isotherm for phenol (petroleum coke).
were found to be as follows:
a = 0.0026, b = 6.009, k = 0.259,
1/n = 0.4149.
The adsorption capacity thus determined from the Langmuir
isotherm was 6 mg/g for petroleum coke. The essential char-
acteristics of the Langmuir isotherm have been described by
the term separation factor or equilibrium constant RL , which
is defined as RL = 1/1+bC0 (where C0 is the initial concen-
tration of adsorbate, phenol, and b is its Langmuir constant).
This indicates the nature of adsorption [26] as
RL > 1 (unfavorable),
0 < RL < 1 (favorable),
RL = 0 (irreversible),
RL = 1 (linear).
The values of RL in the present investigation have been
found to be below 1.0 for phenol, showing that the adsorp-
tion of phenol is very favorable. The values of 1/n are also
found to be less than 1, which suggests favorable adsorption
behavior of phenol onto petroleum coke.
3.1.2. Coke breeze
Coke breeze has also been used for the phenol adsorption.
Adsorption data were analyzed by the three models as men-
tioned above. The adsorption data showed a better linear fit
for Langmuir isotherm rather than Freundlich isotherm. The
isotherm constants are shown in Table 3. The adsorption ca-
pacity thus determined from Langmuir isotherm was found
to be very low (0.18 mg/g). The value of 1/n was not found
to be less than 1, which suggests the unfavorable adsorption
behavior of phenol onto coke breeze.
3.1.3. Rice husk and rice husk char
Other low-cost adsorbents such as rice husk and its char
were used for the adsorption of phenol. In the case of rice
husk, the Langmuir model fits the adsorption data slightly
better than the Freundlich isotherm. The Langmuir constant,
a, was found to be 4.50 mg/g for phenol. For rice husk char
the Langmuir model indicates a better fit for phenol. The
constants are shown in Table 3. The adsorption capacity was
found to be 7.9 mg/g for phenol. The values of 1/n and RL
for phenol are found to be less than 1 for both rice husk and
rice husk char, thus showing favorable adsorption of phenol
onto rice husk and its char.
3.1.4. Samla coal
Using Eq. (2), from the plot of log(x/m) versus log Ce ,
the parameters n and k were obtained from the slope and
intercept, respectively, for Samla coal. The results obtained
are given in Table 3. Comparison of the q values and the
correlation coefficient, R 2 , demonstrates that the Langmuir
isotherm fits phenol adsorption data better than the Fre-
undlich isotherm. The values of 1/n were found to be less
than 1 for Samla coal, which suggested favorable adsorption
behavior of phenols on Samla coal.
The parameters of the Langmuir equation, the monolayer
capacities obtained from the isotherm data, the normalized
deviations, q, and the correlation coefficient (R 2 ) for phe-
nol are determined and given in Table 3. The value of the
Langmuir constant, a, which denotes the adsorption capac-
ity, was found to be 13.28 mg/g for phenol.
The essential characteristics of Langmuir isotherm have
been described by the separation factor or equilibrium con-
stant, RL , which is defined as RL = 1/1 + bC0 (where C0
is the initial concentration and b is its Langmuir constant).
This indicates the nature of adsorption as
RL > 1 (unfavorable),
0 < RL < 1 (favorable),
RL = 0 (irreversible),
RL = 1 (linear).
The values of RL in the present investigation have been
found to be below 1.0 for phenol showing that the adsorp-
tion of phenol is very favorable.
3.1.5. Residual Samla coal
Earlier work [27] from the laboratory had shown that sol-
vent extraction of coal helps in enhancing the adsorption
of coal. Therefore, residual coal obtained after solvent ex-
traction of coal using NMP containing a small amount of
EDA was used for the adsorption of phenol. For this residual
coal, the three models as applied for coal was studied. Sim-
ilarly, Langmuir isotherm was studied for residual coal and
different parameters obtained are shown in Table 3. Com-
paring the value of q and R 2 , it indicates a slightly better
linear fit than Freundlich isotherm. However, the Redlich–
Peterson model showed an improved fit for phenol (Table 3).
 M. Ahmaruzzaman, D.K. Sharma / Journal of Colloid and Interface Science 287 (2005) 14–24 19

Table 3
Adsorption parameters obtained from Langmuir, Freundlich, and Redlich–Peterson isotherm
Adsorbent Adsorbate Langmuir model Freundlich model Redlich–Peterson model
b a R2 qeq k 1/n R2 qeq A B β R2 qeq
(%) (%) (%)
Samla coal Phenol 0.00813 13.28 0.9675 9.85 1.442 0.3176 0.9442 6.41 0.377 0.495 0.9898 5.14
p-Nitrophenol 0.00372 51.54 0.9862 5.71 1.453 0.4955 0.9959 2.66 3.35 5.91 0.619 0.9983 1.31
p-Chlorophenol 0.00376 50 0.984 5.52 1.469 0.4894 0.994 3.36 2.87 4.21 0.603 0.9966 2.47
Residual Phenol 0.0133 45.45 0.9347 26.3 6.357 0.2728 0.9333 12.6 1.8 0.510 0.9997 2.01
Samla p-Nitrophenol 0.0171 86.95 0.9953 12.6 6.359 0.4164 0.9754 9.02 24.27 9.66 0.805 0.9987 6.91
coal p-Chlorophenol 0.0133 82.64 0.9886 16.3 5.478 0.417 0.9868 6.35 16.28 7.58 0.755 0.9983 8.64
Residual Phenol 0.00283 142.8 0.9917 1.75 7.278 0.3912 0.9888 1.20 2.66 0.486 0.9932 1.30
Samla coal p-Nitrophenol 0.00308 256.4 0.9916 2.69 8.765 0.4571 0.9945 1.62 38.3 26.8 0.739 0.9954 1.48
treated with p-Chlorophenol 0.00378 243.9 0.9862 3.74 11.738 0.4147 0.9903 1.86 27.93 9.20 0.705 0.9995 2.38
H3 PO4
Activated Phenol 0.0154 322.5 0.9856 13.7 53.272 0.266 0.9448 6.79 53.47 0.740 0.9968 4.28
carbon p-Nitrophenol 0.0339 526.31 0.9896 7.93 165.84 0.1625 0.9628 5.56 129.8 0.376 0.793 0.999 3.18
p-Chlorophenol 0.0257 500 0.9904 13.0 133.07 0.1921 0.9565 111.1 0.775 0.9995 3.98
Phenol 0.00174 4.508 0.9588 1.87 0.1172 0.4652 0.9535 1.58 0.0103 0.267 0.9621 0.795
Rice husk p-Nitrophenol 0.0021 15.31 0.9612 1.95 0.8049 0.3917 0.932 15.5 0.0867 0.368 0.9640 1.92
p-Chlorophenol 0.00153 14.36 0.9904 0.875 0.372 0.4554 0.9891 1.26 0.0602 0.340 0.9922 0.89
Rice husk Phenol 0.00318 7.91 0.9867 0.807 0.909 0.2739 0.9316 0.774 0.0306 0.336 0.9884 0.79
char p-Nitrophenol 0.00102 39.21 0.9776 2.23 0.2532 0.6345 0.9929 1.91 2.71 46.3 649 0.9789 1.92
p-Chlorophenol 0.00110 36.23 0.9775 1.54 0.2812 0.6133 0.991 2.23 35.3 0.636 0.9796 0.89
Petroleum Phenol 0.00267 6.009 0.9655 3.29 0.2591 0.4149 0.9477 2.80 0.022 0.298 0.974 2.58
coke p-Nitrophenol 0.00133 11.061 0.9757 1.62 0.1051 0.6007 0.9907 1.40 0.0711 0.355 0.9799 1.44
p-Chlorophenol 0.00183 9.337 0.9145 3.64 0.1859 0.51 0.9422 3.15 0.0578 0.350 0.9431 2.86
Coke Phenol 0.00150 0.1723 0.9721 0.9171 2.855 0.9569 0.0096 0.165 0.9732
breeze p-Nitrophenol 0.00120 4.64 0.9684 1.06 0.0696 0.5217 0.9733 1.05 0.0318 0.391 0.9694 1.07
p-Chlorophenol 0.00294 2.946 0.9817 1.53 0.2423 0.3056 0.9256 9.93 0.0060 0.268 0.983 1.52

The adsorption capacity of residual coal was found to be
45.45 mg/g for phenol. The values of RL indicate the fa-
vorable adsorption for phenol removal onto residual coal.
3.1.6. Residual coal treated with H3 PO4 (RCP)
Thus, it was found that adsorption capacity of residual
coal increased for the removal of phenol. To increase the ad-
sorption capacity of residual coal further, it was treated with
H3 PO4 and used for the adsorption study and adsorption
data were analyzed by the models described. As described
earlier, by comparing the values of q and R 2 , Langmuir
isotherm fits the phenol adsorption data better than Fre-
undlich isotherm. The adsorption capacity thus determined
from the Langmuir model was found to be 142.8 mg/g for
phenol. Thus, it was observed that the adsorption capacity
of residual coal was enhanced significantly after treatment
with H3 PO4 and gave the best results for phenol adsorption
among the adsorbents studied. Comparison were made with
phenol adsorption on activated carbon in order to see how
efficient residual coal was (RCP) as compared to activated
carbon.
3.1.7. Activated carbon
Following the same procedure as mentioned previously,
Langmuir and Freundlich parameters are determined for
phenol using activated carbon as adsorbent. By comparing
the values of q and R 2 , it is found that the Langmuir
isotherm fits the phenol adsorption data much better than
Freundlich equation, although the Redlich–Peterson model
showed an even more improved fit for the phenol.
The adsorption capacity of activated carbon was found to
be 322.5 mg/g for phenol. The adsorption of phenolic com-
pounds on activated carbon implies the formation of electron
donor–accepter complexes in which the basic surface oxy-
gen groups act as acceptors [28,29]. Furthermore, as recently
demonstrated [30], there are basic sites on the surface of the
carbons, probably located at π -electron-rich regions with the
basal planes of carbon crystallite edges. These regions pre-
dominate in carbons with low oxygen content [30] and may
give rise to the formation of the above electron donor com-
plexes with the aromatic ring of the phenolic compounds.
Thus, Coughlin and Ezra [31] suggested that phenol ad-
sorption on carbons involves dispersive forces between the
π -electrons in carbons. Direct experimental support for this
view was given by Mahajan et al. [32] studying phenol ad-
sorption on graphite and boron-doped graphite samples. The
results obtained showed that the substitution of boron into
the lattice of polycrystalline graphite, with accompanying
removal of π -electrons from graphite, resulted in a lower-
ing of phenol uptake from water. Therefore, the increase in
surface basicity of the activated carbons favors the formation
of the above complexes, which results in an increase in the
value of ab.
20 M. Ahmaruzzaman, D.K. Sharma / Journal of Colloid and Interface Science 287 (2005) 14–24
3.2. Adsorption isotherm of p-nitrophenol
Adsorption isotherms of para-nitrophenol were also ana-
lyzed by three models as mentioned above for all the adsor-
bents.
Petroleum coke was used for the adsorption of p-nitro-
phenol. By comparing the value of q and R 2 , the Fre-
undlich isotherm was found to fit the p-nitrophenol adsorp-
tion data much better than the Langmuir isotherm. The con-
stants were determined and shown in Table 3. The adsorption
capacity thus determined from the Langmuir isotherm was
found to be 11.06 mg/g.
Low-cost adsorbents such as coke breeze, rice husk, and
rice husk char have also been used for the adsorption of
p-nitrophenol from wastewater. Adsorption data were ana-
lyzed by the three models as mentioned above. In the case
of coke breeze, the Freundlich isotherm showed a better
linear fit than the Langmuir isotherm. The adsorption con-
stants are shown in Table 3. For rice husk, the Langmuir
isotherm indicates a much better linear fit than the Fre-
undlich isotherm, whereas in the case of rice husk char,
the Freundlich isotherm shows a much better linear fit than
the Langmuir isotherm. The adsorption capacity determined
from the Langmuir isotherm was found to be 15.31 mg/g
for rice husk and 39.21 mg/g for rice husk char. The val-
ues of 1/n and RL were found to be less than 1, indicating
favorable adsorption for p-nitrophenol.
Samla coal was also used for the adsorption of p-nitro-
phenol. By comparing the value of q and R 2 , it was found
that the Freundlich isotherm fits p-nitrophenol adsorption
data better than the Langmuir isotherm. The adsorption ca-
pacity was found to be 51.54 mg/g.
Similarly, adsorption of p-nitrophenol was analyzed for
residual coal and RCP. For residual coal, the Langmuir
isotherm showed a much better linear fit than the Fre-
undlich isotherm, whereas in the case of RCP, the Fre-
undlich isotherm showed a slightly better fit than the Lang-
muir isotherm. The adsorption capacity was found to be
86.95 mg/g for residual coal and 256.4 mg/g for RCP.
In the case of activated carbon, the Langmuir isotherm
showed a better linear fit than the Freundlich isotherm. The
Redlich–Peterson model showed an even better fit for p-ni-
trophenol. The constants are shown in Table 3.
In all cases, the values of 1/n and RL were found to be 1,
suggesting favorable adsorption for p-nitrophenol.
3.3. Adsorption isotherm of p-chlorophenol
Adsorption isotherms of p-chlorophenol were also ana-
lyzed by three models as mentioned above for all the adsor-
bents.
For petroleum coke, comparison of the value of q and
R 2 demonstrates that the Freundlich isotherm indicates a
better linear fit than the Langmuir isotherm. The adsorption
capacity was found to be 9.33 mg/g for p-chlorophenol. For
coke breeze, Langmuir isotherm showed a much better lin-
ear fit than Freundlich isotherm. The adsorption constants
are shown in Table 3.
Similarly, rice husk and rice husk char was used for the
adsorption of p-chlorophenol.
For rice husk char, the Langmuir isotherm showed a
slightly better fit than Freundlich isotherm, whereas for rice
husk char, the Freundlich isotherm showed a much better lin-
ear fit than Langmuir isotherm. The values of the Langmuir
and Freundlich constants were determined and are shown in
Table 3.
The Freundlich isotherm showed a better linear fit than
the Langmuir isotherm for Samla coal. The adsorption ca-
pacity was found to be 50 mg/g. Residual coal and RCP
were also used for p-chlorophenol adsorption. The Lang-
muir isotherm showed a slightly better linear fit than the Fre-
undlich isotherm for residual coal. However, the Redlich–
Peterson model showed an improved fit for residual coal (Ta-
ble 3). For RCP, the Freundlich isotherm showed a slightly
better linear fit than Langmuir isotherm. The adsorption ca-
pacity was determined and shown in Table 3.
In the case of activated carbon, the Langmuir isotherm
showed a much better linear fit than the Freundlich isotherm.
However, the Redlich–Peterson model showed an improved
fit for p-chlorophenol adsorption. The adsorption constants
for p-chlorophenol are shown in Table 3.
In all cases, the values of 1/n and RL were found to be 1,
indicating favorable adsorption for p-chlorophenol.
3.4. Comparison of adsorption capacity of phenol,
p-nitrophenol, and p-chlorophenol
The adsorption capacity and relative affinity (ab) of
the phenols toward the surface of the adsorbent (Samla
coal) increases in the order phenol < p-chlorophenol <
p-nitrophenol. This order seems to be related to the electron-
withdrawing properties of the substituents of the phenolic
compound. Therefore, electron withdrawal or deactivation
of the benzene ring favors the formation of electron-donor–
acceptor complexes between these rings and basic groups
on the surface of the Samla coal, increasing in that way the
ab value. The adsorption capacity of phenol, p-nitrophenol,
and p-chlorophenol for other adsorbents followed the same
trend as mentioned for Samla coal. This order may also be
related to the electron withdrawing of the substituents of the
phenol compound as explained for the adsorption of phenols
on Samla coal.
Thus, it was found that residual coal treated with H3 PO4
is about 48% as efficient as standard activated carbon and
can therefore be employed for the removal of phenols from
wastewater.
Comparison of all theoretical approaches used in this
work shows that the Redlich–Peterson equation fits the ex-
perimental data best. This is expected, as the Redlich–
Peterson equation has three fitting parameters, with β being
a more direct parameter for adsorbate–adsorbent interaction
strength.
 M. Ahmaruzzaman, D.K. Sharma / Journal of Colloid and Interface Science 287 (2005) 14–24
Fig. 4. Effect of contact time on the removal of phenol (Samla coal).
Fig. 5. Kinetics of removal of phenol (Samla coal).
3.5. Kinetics of the adsorption process
The kinetics of adsorption is important from the point
of view that it controls the process efficiency. Various ki-
netic models have been used by various workers, where the
adsorption has been treated as a first-order [33,34], a pseudo-
first-order [35,36], and a pseudo-second-order process [37].
Different systems conform to different models. Lagergren’s
rate equation is the one most widely used [34,35,38] for the
sorption of a solute from a liquid solution. Thus the first-
order equation,
kads
log(qe − q) = log qe − t, (6)
2.303
where qe and q are the amounts of phenol adsorbed at equi-
librium and at time t in milligrams per gram, respectively,
and kads is the first-order rate constant, was applied to the
present studies of phenol adsorption. As such, the values of
log(qe − q) for phenol using Samla coal as adsorbent were
calculated from the kinetic data of Fig. 4 and plotted against
time in Fig. 5. The plots were found to be linear with good
correlation coefficient, indicating that Lagergren’s equation
is applicable to phenol adsorption on coal, residual coal,
RCP, and activated carbon. Thus, the adsorption process is
a first-order process.
The first-order rate constants were calculated from the
slope of the plots, as shown in Fig. 5. In the case of RCP, the
first-order rate constants were found to be 0.221, 0.3454, and
0.3592 h−1 for phenol, p-chlorophenol, and p-nitrophenol,
respectively. A higher rate constant for p-nitrophenol in-
dicates that the adsorbent (RCP) has a higher affinity for
phenol. This is consistent with higher adsorption (qm val-
ues) observed for this phenol as compared to others. As a
matter of fact, the rate constants for phenol are in an order
parallel to their qm values. A similar trend was followed for
other adsorbents, such as coal, residual coal, and activated
carbon, as shown in Table 4.
21
Fig. 6. Intraparticle diffusion plot for phenol removal (Samla coal).
Fig. 7. Kinetics of mass transfer of phenol (Samla coal).
The plot of q, the amount of adsorbate adsorbed per unit
weight of adsorbent, versus square root of time has been
commonly used to describe whether the adsorption process
is controlled by diffusion in the adsorbent particles and con-
secutive diffusion in the bulk of the solution [39]. The plot
of q versus t 0.5 for adsorption of phenol is given in Fig. 6
for Samla coal. This plot showed that the adsorption of phe-
nol on Samla coal was controlled by external mass transfer
followed by intra particle diffusion mass transfer.
The pore diffusion coefficient, D, for the removal of phe-
nols by different adsorbents have been calculated using the
following equation, assuming spherical shape geometry for
the adsorbent particles [40,41],
t1/2 = 0.03r02 /D, (7)
where t1/2 is time for half adsorption, r0 is diameter of
the particle, and D is the pore diffusion constant, cm2 /s.
The values of the pore-diffusion coefficient of phenol were
found to be 1.36 × 10−10 , 1.17 × 10−10 , 1.01 × 10−10 , and
3.72 × 10−11 cm2 /s, respectively, for Samla coal, residual
coal, RCP, and activated carbon. Thus, the values of pore
diffusion rate constants were found to be on the order of
10−10 –10−11 cm2 /s for all the adsorbent samples, indicat-
ing that the pore diffusion is not significant [42,43].
The transport number to know the mode of diffusion was
computed from the equation [44,45]
Qt
log = log k + n log t, (8)
Qα
where Qα = weight of adsorbent with adsorbent at equilib-
rium time, k = adsorbate–adsorbent interaction coefficient,
n = transport number, and t = time.
In order to calculate n and k, log(Qt /Qα ) was plotted
against log t. Fig. 7 shows the plot for Samla coal. This were
22 M. Ahmaruzzaman, D.K. Sharma / Journal of Colloid and Interface Science 287 (2005) 14–24

Table 4
Adsorption rate constant, intraparticle diffusion rate constant, pore diffusion coefficient, and transport number
Adsorbents Adsorbate Adsorption rate constant Intraparticle diffusion Pore diffusion coefficient D Transport number
(h−1 ) rate constant (cm2 /s) (n)
Samla coal Phenol 0.1519 0.0353 1.36×10−10 0.0009
p-Nitrophenol 0.1934 0.0541 1.73×10−10 0.0066
p-Chlorophenol 0.1923 0.1076 1.72×10−10 0.0067
Residual Samla Phenol 0.1796 0.0307 1.17×10−10 0.0009
coal p-Nitrophenol 0.2763 0.0979 1.81×10−10 0.0131
p-Chlorophenol 0.2375 0.1514 1.55×10−10 0.0133
RCP Phenol 0.221 0.1634 1.01×10−10 0.0404
p-Nitrophenol 0.3592 0.128 1.64×10−10 0.0653
p-Chlorophenol 0.3454 0.1855 1.57×10−10 0.0655
Activated Phenol 0.2901 0.0268 3.72×10−11 0.0923
carbon p-Nitrophenol 0.4559 0.1664 5.85×10−11 0.1137
p-Chlorophenol 0.4421 0.1222 5.67×10−11 0.1155

found to be a straight line. The slope of which was used to

find n and k was calculated using the intercept. The values
of transport number, n, were found to be 0.0009, 0.0404, and
0.0923, respectively, for phenols using Samla coal, RCP, and
activated carbon respectively. The values of n indicate the
type of transport mechanism. A value of n = 0.5 represents
the Fickian mechanism and n = 1 indicates the non-Fickian
mechanism. The constants k depends on the characteristics
of the adsorbents in addition to its interaction with the phe-
nol. Thus, the values of n was found to be less than 0.5 Fig. 8. Effect of pH on adsorption of p-nitrophenol on Samla coal.
(Table 4), indicating the Fickian diffusion of phenols with
surface of interaction of the phenols in the adsorbents.

3.6. Thermodynamic studies

Temperature affects the adsorption rate by altering the

molecular interactions and the solubility. The uptake of phe-
nols decreases with increase in temperature. The enthalpy of
adsorption H is related to the Langmuir constant b accord-
ing to the van’t Hoff equation [46],
Fig. 9. Effect of pH on adsorption of p-nitrophenol on activated carbon.
H
log b = log b0 − . (9)
2.303RT
The plot of log b versus 1/T yielded a straight line. The val-
ues of H for phenol, p-nitrophenol, and p-chlorophenol
calculated from the slope of the plots were found to be
−1.44, −1.99, and −1.13 kJ/mol, respectively, using Samla
coal as adsorbent. Since the adsorption is exothermic,
b should decrease with increased temperature [46]. The val-
ues of b for the removal of phenol at different temperatures
and the negative value of H show the exothermic nature
of adsorption. Halhouli et al. [47] observed the same trend Fig. 10. Effect of pH on adsorption of p-nitrophenol on residual coal.
with phenol adsorption on activated charcoal.
of dissociation of the electrolyte and the other is the dom-
3.7. Effect of pH inant charge on the surface of the solid. Both factors are
dependent on the pH of the aqueous solution. The first factor
The adsorption of weak electrolyte such as phenol com- can be qualitatively predicted by the pKa (activity constant)
pounds, on the surface of a porous amphoteric solid, such of the weak electrolyte, because at a solution pH lower than
as coal or activated carbon, from aqueous solutions depend, the pKa it will remain undissociated [48]. However, the sec-
mainly on two important factors. One of them is the degree ond factor is more difficult to ascertain.
 M. Ahmaruzzaman, D.K. Sharma / Journal of Colloid and Interface Science 287 (2005) 14–24 23

The effect of the solution pH on the adsorption capacity

of coal, activated carbon, and residual coal for the substituted
phenols studied is shown in Figs. 8–10, respectively. At acid
pH, the amount of phenols adsorbed, q, remains constant or
increases slightly with the pH, and at a certain value of pH,
there is a decrease in the value of q, which continues while
pH increases.
The results indicate that the phenolic compounds are pref-
erentially adsorbed on the surfaces of coal and activated
carbons in their molecular form, because at acidic pH val-
Fig. 11. Column studies of phenol: (F) activated carbon, (2) RCP,
ues they are not dissociated. (Q) residual coal, (×) Samla coal.
The phenol compounds start to dissociate at a pH close
to their pKa values, which vary between 9.96 (phenol) and
7.13 (p-nitrophenol). However, the amount of phenol com-
pound adsorbed depends also on the surface charge of the
coal and activated carbon. At pH values higher than 10, both
the external and internal surfaces are negatively charged and
the phenol compounds are also dissociated.

3.8. Column studies

Column-type continuous flow operations appear to have

a distinct advantage over batch type operations because the Fig. 12. Column studies of p-nitrophenol: (F) activated carbon, (2) RCP,
rate of adsorption depends on the concentration of solute in (Q) residual coal, (×) Samla coal.
the solution being treated. For column operation the adsor-
bents are continuously in contact with a fresh solution. Con- Table 5
sequently the concentration in the solution in contact with a Adsorption capacity of phenols in batch and column operations
given layer of adsorbent in a column is relatively constant. Adsorbents Phenol p-Nitrophenol
For batch treatment, the concentration of solute in contact
Batch Column Batch Column
with a specific quantity of adsorbent steadily decreases as capacity capacity capacity capacity
adsorption proceeds, thereby decreasing the effectiveness of (mg/g) (mg/g) (mg/g) (mg/g)
the adsorbent for removing the solute. The breakthrough ca- Samla coal 13.3 21 51.5 65
pacity, which is the amount adsorbed before the appearance Residual Samla coal 45.5 52 87 96
of adsorbates in the effluent, and the total capacity, which RCP 143 166 256.5 273
is the amount adsorbed until the effluent concentration of Activated carbon 322.5 345 526.3 549
the adsorbate is equal to the influent solution concentration,
are computed from the breakthrough curves. The results of
the column studies plotted in Fig. 11 reveal that up to 2 h, capacity was found to be higher than the batch capacity in all
there is no trace of phenol in the effluent when Samla coal is the phenols for different adsorbents as shown in Table 5. The
used as adsorbent. The adsorption capacity of the adsorbent higher column capacity may be due to the fact that the con-
(Samla coal) was exhausted after 20 h of column operation. tinuously large concentration gradient at the interface zones
Thus, the breakthrough time for phenol by using Samla coal occurred as it passes through the column, while the concen-
was found to be 2 h. The breakthrough time for RCP and ac- tration gradient decreases with time in batch experiments.
tivated carbon was found to be 4 and 8 h, respectively, for
phenol. Thus, it was found that the breakthrough time in-
creases using RCP as adsorbent. For p-nitrophenol, there is 4. Conclusions
no trace of phenol up to 4 h using Samla coal as adsorbent
(Fig. 12). Again, the adsorption capacity was exhausted af- 1. The order of adsorption capacities of adsorbents studied
ter 30 h of column operation. Thus, the breakthrough time for different phenols was found to be in the following
increased for p-nitrophenol compared to that of phenol. order: phenol < p-chlorophenol < p-nitrophenol.
2. The adsorption capacity of residual coal increased after
3.9. Comparisons of adsorption capacity of phenols in treatment with phosphoric acid.
batch and column operations 3. The adsorption of phenol, p-chlorophenol, and p-nitro-
phenol follows first-order kinetics.
Table 5 compares the adsorption capacity of phenol and 4. pH significantly affects the adsorption capacity of the
p-nitrophenol in batch and column operations. The column different adsorbents.
24 M. Ahmaruzzaman, D.K. Sharma / Journal of Colloid and Interface Science 287 (2005) 14–24
5. Residual coal treated with phosphoric acid was found to
give better results among the adsorbents studied.
6. Adsorption capacity of residual coal treated with phos-
phoric acid was found to be 142.8, 256.4, and 243.9
mg/g for phenol, p-nitrophenol, and p-chlorophenol,
respectively.
7. Transport number was found to be less than 0.5 indi-
cating the Fickian diffusion of phenol with surface of
interaction of the phenol in the adsorbent studied.
8. The adsorption process is controlled by external mass
transfer followed by intraparticle diffusion mass trans-
fer.
9. The column capacity was found to be higher than the
batch capacity in all the phenols for different adsorbents.
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