Chemosphere 61 (2005) 492501

www.elsevier.com/locate/chemosphere

Removal of congo red from aqueous solution by bagasse

y ash and activated carbon: Kinetic study and
equilibrium isotherm analyses
Indra Deo Mall *, Vimal Chandra Srivastava,
Nitin Kumar Agarwal, Indra Mani Mishra
Department of Chemical Engineering, Indian Institute of Technology, Roorkee, Roorkee 247667, India

Received 24 August 2004; received in revised form 25 February 2005; accepted 7 March 2005
Available online 24 May 2005

Abstract

Present investigation deals with the utilisation of bagasse y ash (BFA) (generated as a waste material from bagasse
red boilers) and the use of activated carbonscommercial grade (ACC) and laboratory grade (ACL), as adsorbents
for the removal of congo red (CR) from aqueous solutions. Batch studies were conducted to evaluate the adsorption
capacity of BFA, ACC and ACL and the eects of initial pH (pH0), contact time and initial dye concentration on
adsorption. The pH0 of the dye solution strongly aected the chemistry of both the dye molecules and BFA in an aque-
ous solution. The eective pH0 was 7.0 for adsorption on BFA. Kinetic studies showed that the adsorption of CR on all
the adsorbents was a gradual process. Equilibrium reached in about 4 h contact time. Optimum BFA, ACC and ACL
dosages were found to be 1, 20 and 2 g l
1, respectively. CR uptake by the adsorbents followed pseudo-second-order
kinetics. Equilibrium isotherms for the adsorption of CR on BFA, ACC and ACL were analysed by the Freundlich,
Langmuir, RedlichPeterson, and Temkin isotherm equations. Error analysis showed that the RP isotherm best-ts
the CR adsorption isotherm data on all adsorbents. The Freundlich isotherm also shows comparable t. Thermody-
namics showed that the adsorption of CR on BFA was most favourable in comparison to activated carbons.
2005 Published by Elsevier Ltd.

Keywords: Dye removal; Bagasse y ash; BFA; Congo red; CR; Adsorption kinetics; Isotherms; Error analyses

1. Introduction acid, 3,3 0 -(4,4 0 -biphenylenebis (azo)) bis (4-amino-) diso-

Many dyes and pigments are toxic in nature with sus-
pected carcinogenic and mutagenic eects (McKay et al.,
1985) that aect aquatic biota and humans (Gregory
et al., 1991). Congo red (CR) (1-naphthalenesulfonic
*
Corresponding author. Tel.: +91 1332 285319/285106; fax:
+91 1332 276535/273560.
E-mail address: id_mall2000@yahoo.co.in (I.D. Mall).
dium salt) is a benzidine-based anionic disazo dye. This
dye is known to metabolize to benzidine, a known hu-
man carcinogen.
Dyes and pigments represent one of the problematic
groups; they are emitted into wastewaters from various
industrial branches, mainly from the dye manufacturing
and textile nishing (Janos et al., 2003) and also from
food colouring, cosmetics, paper and carpet industries.
Synthetic dyes have complex aromatic structures which
provide them physico-chemical, thermal and optical

0045-6535/$ - see front matter 2005 Published by Elsevier Ltd.

doi:10.1016/j.chemosphere.2005.03.065
 I.D. Mall et al. / Chemosphere 61 (2005) 492501
stability (Mckay et al., 1981; Seshadri et al., 1994). CR
containing euents are generated from textiles, printing
and dyeing, paper, rubber, plastics industries, etc. Due
to its structural stability, CR is dicult to biodegrade.
Physico-chemical or chemical treatment of such waste-
waters is, however, possible (Mckay et al., 1981; Banat
et al., 1996). Adsorption is considered an attractive op-
tion in treating such wastewaters (Chern and Wu,
2001; Namasivayam and Kavitha, 2002). Granular acti-
vated carbon is the most popular adsorbent that has
been used with great success (McKay, 1982). However,
adsorbent-grade activated carbon is cost-prohibitive
and both regeneration and disposal of the used carbon
are often very dicult. Consequently, many investiga-
tors have studied the feasibility of using low cost sub-
stances. Critical reviews of low cost adsorbents for
wastewater treatment have been presented by Mall
et al. (1996) and Bailey et al. (1999).
In the present investigation bagasse y ash (BFA), a
waste collected from the particulate collection equip-
ment attached upstream to the stacks of bagasse red
boilers, and activated carbons of commercial grade
(ACC) and laboratory grade (ACL) have been used as
adsorbents for the removal of CR. The aim of the pres-
ent work is to explore the possibility of utilizing BFA for
the adsorptive removal of CR from wastewater. The ef-
fect of such factors as pH0, adsorbent dose, contact time
and initial concentration was investigated. The kinetics
of CR adsorption on the adsorbents was analysed by t-
ting various kinetic models. Experimental equilibrium
data were tted to the Freundlich, Langmuir, Redlich
Peterson (RP), and Temkin isotherm equations to
determine the best-t isotherm equation. Error analysis
was carried out to test the adequacy and the accuracy
of the model equations.
2. Material and methods
2.1. Adsorbents and their characterisation
BFA was obtained from a local sugar mill, washed
with hot water (70 C) and dried. ACC manufactured
by Rajasthan Breweries Ltd. was procured from the
NH2
N N
SO3Na
Fig. 1. Molecular structure of congo red.
493
open market in New Delhi. ACL manufactured by
GSE Chemical Testing Laboratory and Allied Industry,
New Delhi was procured locally. The carbons were used
as procured. ACL was used as the standard adsorbent
for comparison of adsorptive characteristics of ACC
and BFA. The origin of the activated carbons is not
known, but being from dierent manufacturers, they
possess dierent characteristics. The physico-chemical
characteristics of these adsorbents were determined
using standard procedures. Proximate analysis of the
adsorbents was carried out using the standard procedure
(IS:1350 (part I), 1984). Bulk density was determined by
using a MAC bulk density meter. X-ray diraction ana-
lysis was carried out with a Phillips (Holland) diraction
unit (Model PW 1140/90), using copper target with
nickel as a lter medium, and K radiation maintained
at 1.542 A . Goniometer and chart speeds were main-
tained at 1 min
1 and 1 cm min
1, respectively. Scan-
ning electron micrographs (SEM) were obtained by
using LEO 435 VP Scanning electron microscope. The
specic surface area and the pore diameter of the sample
were measured by N2 adsorption isotherm using an
ASAP 2010 Micromeritics instrument and by the
BrunauerEmmettTeller (BET) method, using the soft-
ware of Micromeritics. Nitrogen was used as cold bath
(77.15 K). The BarrettJoynerHanlenda (BJH) method
(Barret et al., 1951) was used to calculate the mesopore
distribution.
2.2. Adsorbate
The adsorbate CR dye [C.I. = 22 120, chemical for-
mula = C32H22N6Na2O6S2, FW = 696.7, kmax = 500 nm]
was supplied by the Sigma Chemical Company, USA.
The structure of CR is illustrated in Fig. 1 (Fu and Vir-
araghavan, 2002). An accurately weighed quantity of the
dye was dissolved in double-distilled water to prepare
stock solution (500 mg l
1).
2.3. Analytical measurements
Concentrations of dyes were determined by nding
out the absorbance at the characteristic wavelength
using a double beam UV/vis spectrophotometer (model
NH2
N N
SO3Na
494 I.D. Mall et al. / Chemosphere 61 (2005) 492501
UV 210 A; Shimadzu, Japan). The kmax for CR was
found to be 500 nm. Calibration curves were plotted bet-
ween absorbance and concentration of the dye solution.
2.4. Batch experimental programme
To study the eect of important parameters like the
pH0, adsorbent dosage (m), contact time (t), initial dye
concentration (C0), etc., on the adsorptive removal of
CR, batch experiments were conducted at 30 1 C.
For each experimental run, 50 ml of CR solution of
known concentration, pH and a known amount of the
adsorbent were taken in a 100 ml stoppered conical
ask. This mixture was agitated in a temperature con-
trolled shaking water bath at a constant speed of
145 rpm at 30 1 C. Samples were withdrawn at
appropriate time intervals and centrifuged using Re-
search Centriguge (Remi scientic works, Mumbai), at
10 000 rpm for 30 min and the absorbance of the super-
natant was measured. Experiments were carried out at
pH0 7. Eect of pH0 on dye removal was studied over
a pH0 range of 313. pH0 was adjusted by the addition
of dilute aqueous solutions of HCI or NaOH (0.10 M).
For the optimum amount of adsorbent per unit mass
of adsorbate, a 50 ml dye solution was contacted with
dierent amounts of adsorbents till equilibrium was at-
tained. Kinetics of adsorption was determined by ana-
lyzing adsorptive uptake of the dye from aqueous
solution at dierent time intervals. For adsorption iso-
therms, dye solutions of dierent concentrations were
agitated with known amount of adsorbents till the equi-
librium was achieved. The residual dye concentration
(C) was then determined. Batch tests were carried out
to compare the adsorptive capacity and intensity of dif-
ferent adsorbents. Blank runs, with only the adsorbents
in 50 ml of double-distilled water, were conducted simul-
taneously at similar conditions to account for any colour
leached by the adsorbents and adsorbed by glass
containers.
3. Results and discussion
3.1. Characterisation of adsorbents
Physico-chemical characteristics of BFA, ACC and
ACL are given in Table 1. It was observed that BFA
has the lowest bulk density among the adsorbents, and
Table 1
Characteristic of adsorbents
Adsorbent Bulk density (kg m
3) BET surface area (m2 g
1)
BFA 133.33 168.83
ACC 740.74 390.00
ACL 588.23 492.00
the amount of ash was very high in BFA in comparison
to that in ACC and ACL (Table 1). ACL has lower den-
sity than ACC and also has highest xed carbon in com-
parison to that in BFA and ACC. ACL also has larger
BET surface area and lower ash content than for
ACC. SEM of BFA (Fig. 2) shows brous structure with
large pore size with strands in each bre. ACL also
shows similar structure like BFA, which may be due to
inherent bre structure in the original raw material.
The size of the bre and inter bre space is similar to
BFA. ACC has structure similar to ACL and partially
similar to BFA. Number of pores in BFA is lesser than
that in ACL. However, the brous nature of the struc-
ture is not so predominant in the micrograph, which
may be due to its large size. d-Spacing values provided
by the X-ray spectra of BFA reected the presence of
alumina (Al2O3), CaSiO3, Ca8Si5O18, and amorphous
silica, where as silicate carbon and tridymite were the
major components identied in ACC and ACL. Dirac-
tion peaks corresponding to crystalline carbon were not
observed in the adsorbents. Other peaks indicate the
presence of Fe2O3, MgO and CaO. Amorphous form
of silica was identied in all the adsorbents. The sum-
mary of the porous structure of BFA is also shown in
Table 1. BFA has a wide pore size distribution (Fig. 3)
giving wide distribution of surface area. The BET sur-
face area is 168.8 m2 g
1 whereas BJH adsorption/
desorption surface area of pores is 54.2/49.9 m2 g
1.
The single point total pore volume of micropores
(<1042.3 A ) is 0.101 cm3 g
1 whereas cumulative pore
volume of pores (17 < d < 3000 A ) is 0.053 cm3 g
1.
The average pore diameter by BET is 23.97 A whereas
the BJH adsorption/desorption average pore diameter
is 39.36 A /33.90 A.
3.2. Eect of pH
The adsorptive treatment of dye containing wastewa-
ter is pH dependent. However, pH is also known to af-
fect the structural stability of CR and, therefore, its
colour intensity. Hence the eect of pH0 was studied
with blank CR solutions of concentration 10 mg l
1 hav-
ing the natural pH0 = 6.8. The solution was kept for 1 h
after the pH adjustment and, thereafter, the absorbance
of the solution was found out. It is found that the colour
is stable at pH0 around 7. Fig. 4 shows the colour re-
moval without BFA over a pH0 range of 313. pH re-
duces the colour below pH0 6 and above pH0 10,
Moisture (%) Volatile matter (%) Ash (%) Fixed carbon (%)
07.64 17.37 26.43 48.56
09.07 17.32 05.49 68.12
08.61 16.62 02.67 72.10
 I.D. Mall et al. / Chemosphere 61 (2005) 492501 495

our removal due to pH change alone may be due to the

structural changes being eected in the dye molecules.
Eect of pH0 on the removal of CR with BFA is also
shown in Fig. 4 for C0 = 10 mg l
1, t = 5 h, and m =
1 g l
1. More than 80% colour removal is observed in
the pH0 range 410. When pH0 is increased from 4 to
7, the colour removal increases slightly from 80% to
85% and then decreases slightly up to pH0 10. There is
signicant decrease of 19% in colour removal, in the
pH0 range of 1012.
In the aqueous solution, the acid dye is rst dissolved
and the sulfonate groups of the acid dye (D-SO3Na) are
dissociated and converted to anionic dye ions.
H2 O
D-SO3 Na ! D-SO

3 Na

Dye ions tend to aggregate (or self-associate) in aqueous

solutions (Coates, 1969). Aggregation can be likened to
Fig. 2. Scanning electron micrograph of bagasse y ash,
polymerization where dye molecules are complexed. Due
activated carbon (commercial grade) and activated carbon
(laboratory grade).
to aggregation, the adsorption of dyes takes place in the
mesopores. CR is a relatively large molecule and nega-
tively charged for much of the pH range (>5). Rapid
0.055 60
adsorption kinetics is facilitated by the presence of mes-
opores in the adsorbent structure and the mesopores are
Pore volume 50 generally more important than the negative surface
Pore area (cm2 g-1)

0.044
Pore volume (cm3 g-1)

Pore area
40
charge of the adsorbent.
0.033 The oxides of alumina, calcium and silica present in
30 the BFA develop charge in contact with water. Except
0.022
20
silica, all other oxides possess positive charge in the
pH0 range of interest because zero point charge of
0.011
10 SiO2, Al2O3 and CaO are 2.2, 8.3 and 11.0, respectively.
The negatively charged silica sites of adsorbent are neu-
0.000 0
10 100 1000 10000 tralized by H+ ions thereby reducing hindrance to diu-
Pore diameter (A) sion of dye ions. For pH0 below 7, a signicantly high
electrostatic attraction exists between the positively
Fig. 3. Pore size distribution of BFA.
charged surface of the adsorbent and the anionic dye.
As the pH of the system increased, the number of nega-
tively charged sites increased and the number of posi-
tively charged sites decreased. A negatively charged
100
With BFA surface site on the adsorbent did not favour the adsorp-
80 Without BFA tion of dye anions due to electrostatic repulsion. Also,
there was competition between OH
(at high pH0) and
%Removal

60
coloured ions of CR for positively charged adsorption
40
sites. However, in the alkaline pH0 range 710, signi-
cant adsorption still occurred. This suggests that chemi-
20 sorption might have been operative in this pH0 range. In
the pH0 range 1012, Al2O3 and CaO become negatively
0
2 4 6 8 10 12 14 charged. Thus, electrostatic repulsion between nega-
pH0 tively charged surface of adsorbent and anionic dye
causes signicant reduction in the removal of dye from
Fig. 4. Eect of pH0 on the removal of CR with and without the solution.
BFA (temperature = 30 C, t = 4 h, C0 = 10 mg l
1, BFA
dosage = 1 g l
1).
3.3. Eect of adsorbent dosage (m)

however, colour change is negligible over a pH0 range of The eect of m on the removal of CR showed that the
610. Maximum colour removal is at pH0 3 and 13. Col- colour removal increases up to a certain limit and then it
496 I.D. Mall et al. / Chemosphere 61 (2005) 492501
remains almost constant. Optimum BFA, ACC and
ACL dosages were found to be 1, 20 and 2 g of adsor-
bents per litre of dye solution, respectively. Increase in
the adsorption with adsorbent dosage can be attributed
to increased adsorbent surface area of mesopores and
the availability of more adsorption sites. But unit
adsorption decreased with an increase in the adsorbent
dosage.
3.4. Eect of initial dye concentration (C0)
The eect of C0 on the removal of CR by the adsor-
bents at optimum dosage of each adsorbent is shown in
Fig. 5. It may be seen that BFA performs the best.
Experiments were also done for a constant dosage of
the adsorbents (m = 1 g l
1) which showed that the CR
removal by BFA at high C0 (>50 mg l
1) is 35% higher
than that by ACL. From the gure, it is evident that
the CR removal decreased with the increase in C0,
although the actual amount of dye adsorbed per unit
mass of adsorbent increased with the increase in C0.
The CR removal increased with the increase in the
adsorbate concentration as the resistance to the uptake
of CR from the solution decreases with the increase in
CR concentration. The rate of adsorption also increases
with the increase in C0 due to increase in the driving
force.
3.5. Eect of contact time
Eect of contact time for the removal of CR by the
adsorbents at m = 1 g l
1 showed rapid adsorption of
dye in the rst 15 min and, thereafter, the adsorption
rate decreased gradually and the adsorption reached
equilibrium in about 4 h. 99.4% of CR removal was ob-
tained with BFA in 4 h. ACL and ACC eected 79.8%
and 30.1% CR removal only. Increase in contact time
up to 7 days showed that the CR removal by BFA
and ACL increases only by about 0.5% over those ob-
tained for 4 h contact time. Aggregation of dye mole-
100
95
%Removal
90
BFA
85 ACC
ACC
80
75
0 5 10 15 20 25 30
Initial concentration (mg l-1)
Fig. 5. Eect of initial adsorbate concentration on the adsorp-
tion of CR by various adsorbents at optimum dosages
(pH0 = 7, temperature = 30 C, t = 4 h, BFA dosage = 1 g l
1,
ACC dosage = 20 g l
1, ACL dosage = 2 g l
1).
cules with the increase in contact time makes it almost
impossible to diuse deeper into the adsorbent structure
at highest energy sites. This aggregation negates the
inuence of contact time as the mesopores get lled up
and start oering resistance to diusion of aggregated
dye molecules in the adsorbents. This is the reason
why an insignicant enhancement in adsorption is ef-
fected in 7 days as compared to that in 4 h. Since the dif-
ference in the adsorption values at 4 h and at 7 days is
very small, further experiments were conducted for 4 h
contact time only. The adsorption curves (not shown
here) were single, smooth and continuous leading to sat-
uration and indicated the possible mono-layer coverage
on the surface of adsorbents by the dye molecules
(Wong and Yu, 1999; Malik, 2003).
3.6. Adsorption kinetic study
In order to investigate the adsorption processes of
CR on the adsorbents, pseudo-rst-order, pseudo-sec-
ond-order, Bangham and intra-particle diusion kinetic
models kinetic were used.
3.6.1. Pseudo-rst-order model
The pseudo-rst-order equation is
dqt
k f qe
qt 1
dt
where qt is the amount of adsorbate adsorbed at time t
(mg g
1), qe is the adsorption capacity in equilibrium
(mg g
1), kf is the pseudo-rst-order rate constant
(min
1), and t is the contact time (min). The integration
of Eq. (1) with the initial condition, qt = 0 at t = 0 leads
to:
kf
logqe
qt log qe
t 2
2.303
Values of adsorption rate constant (kf) for CR adsorp-
tion on BFA, ACC and ACL were determined from
the plot of log(qe
qt) against t (not shown). These val-
ues (kf = 0.022 min
1 for ACL, 0.016 min
1 for BFA
and 0.013 min
1 for ACC) (Table 2) indicate that the
rate of removal was fastest by ACL followed by BFA
and ACC.
The reported kf values for the adsorption of CR on
coir pith and Azadirachta indica (neem) leaf powder
are 0.210 and 0.012 min
1, respectively (Namasivayam
and Kavitha, 2002; Bhattacharyya and Sharma, 2004).
These values are close to the values obtained in the pres-
ent work.
35
3.6.2. Pseudo-second-order model
The pseudo-second-order model is represented as
(Ho and McKay, 1999):
dqt
k s qe
qt 2 3
dt
 I.D. Mall et al. / Chemosphere 61 (2005) 492501 497

Table 2
Kinetic parameters for the removal of congo red by various adsorbents
Adsorbent kf (min
1) qe (mg g
1) R2 (linear) R2
Pseudo-rst-order constants
BFA 0.016 2.073 0.9763 0.9881
ACC 0.013 0.203 0.9702 0.9923
ACL 0.022 1.471 0.9702 0.9850
h (mg g
1 min
1) ks (g mg
1 min
1) qe (mg g
1) R2
Pseudo-second-order constants
BFA 5.663 0.061 9.638 0.9946
ACC 0.094 0.413 0.477 0.9935
ACL 1.594 0.069 4.789 0.9971

kid,1 (mg g
1 min
1) I (mg g
1) R2 kid,2 (mg g
1 min
1) I (mg g
1) R2
Intra-particle diusion constants
BFA 0.291 6.976 0.9797 0.041 9.177 0.9248
ACC 0.024 0.233 0.9662 0.008 0.365 0.7739
ACL 0.243 2.742 0.9473 0.024 4.435 0.9058

where ks is the pseudo-second-order rate constant
(g mg
1 min
1). Integrating Eq. (3) and noting that
qt = 0 at t = 0, the following equation is obtained:
tk s q2e
qt
1 tk s qe
The initial sorption rate, h (mg g
1 min
1), at t ! 0 is
dened as
h k s q2e
h, qe and ks can be determined from the non-linear tting
of the data using a statistical software STATISTICA
version 5.0 for Windows. The best-t values of h, qe
and ks along with correlation coecients for the pseu-
do-rst-order and pseudo-second-order models are
shown in Table 2. Since correlation coecients are clo-
ser to unity for the pseudo-second-order kinetics than
that for the pseudo-rst-order kinetics, the sorption
kinetics can be represented better by the pseudo-sec-
ond-order kinetics for all the three adsorbents. The ks
and h values as calculated are listed in Table 2. It can
be seen that the BFA has highest h and qe values. Bhat-
tacharyya and Sharma (2004) have reported a ks value of
0.0104 g mmol
1 min
1 for the adsorption of CR on A.
to Eq. (6), did not yield satisfactory linear curves for the
CR removal by the adsorbents. This shows that the diu-
sion of adsorbate into the pores of the sorbent was not
the only rate-controlling step (Tutem et al., 1998). It
4 may be that both the lm and pore diusion were impor-
tant to dierent extents in the removal process.
3.6.4. Intra-particle diusion study
The possibility of intra-particle diusion resistance
5
aecting adsorption was explored by using the intra-par-
ticle diusion model as
qt k id t1=2 I 7
where kid is the intra-particle diusion rate constant. In
Fig. 6, a plot of mass of CR adsorbed per unit mass of
adsorbent, qt versus t1/2 is presented for all the three
adsorbents. Values of I (Table 2) give an idea about
the thickness of the boundary layer, i.e., the larger inter-
cept the greater is the boundary layer eect (Kannan and
10
8 BFA
ACC
qt (mg g )
-1

ACL
6
indica (neem) leaf powder. Due to dierence in the nat-
ure of the adsorbents used in the present work, a direct 4
comparison of the values of ks is not possible.
2

3.6.3. Banghams equation 0

Banghams equation (Aharoni et al., 1979) is given as 0 5 10 15 20


 (Time)1/2 (min)1/2
C0 k0 m
log log log a logt 6 Fig. 6. Weber and Morris intra-particle diusion plots for the
C 0
qt m 2.303V
removal of CR by various adsorbents (pH0 = 7, tempera-
where V is the volume of the solution (ml), and a (<1) and ture = 30 C, t = 4 h, C0 = 10 mg l
1, BFA dosage = 1 g l
1,
k0 are constants. The double logarithmic plot, according ACC dosage = 20 g l
1, ACL dosage = 2 g l
1).
498 I.D. Mall et al. / Chemosphere 61 (2005) 492501
Sundaram, 2001). The deviation of straight lines from
the origin (Fig. 6) may be because of the dierence bet-
ween the rate of mass transfer in the initial and nal
stages of adsorption. Further, such deviation of straight
line from the origin indicates that the pore diusion is
not the sole rate-controlling step (Poots et al., 1978).
From Fig. 6, it may be seen that there are two separate
regionsthe initial portion is attributed to the bulk dif-
fusion and the linear portion to intra-particle diusion
(Allen et al., 1989). The values of kid,1 and kid,2 as ob-
tained from the slopes of the two straight lines are listed
in Table 2.
3.7. Adsorption equilibrium study
To optimize the design of an adsorption system for
the adsorption of adsorbates, it is important to establish
the most appropriate correlation for the equilibrium
curves. Various isotherm equations like those of Freund-
lich, Langmuir, RP, and Temkin have been used to de-
scribe the equilibrium characteristics of adsorption.
The Freundlich isotherm is derived by assuming a
heterogeneous surface with a non-uniform distribution
of heat of adsorption over the surface. Whereas in the
Langmuir theory, the basic assumption is that the sorp-
tion takes place at specic homogeneous sites within the
adsorbent.
The RP isotherm (1959) can be described as follows:
K R Ce
qe 8 librium binding constant (l mol
1) corresponding to the
1 aR C be
where KR is RP isotherm constant (l g
1), aR is RP
isotherm constant (l mg
1) and b is the exponent which
lies between 0 and 1, Ce is the equilibrium liquid phase
concentration (mg l
1).
For high concentrations, Eq. (8) reduces to Freund-
lich isotherm
qe K F C 1=n
e 9

1
where, KF = KR/aR is the Freundlich constant (l mg ),
and (1/n) = (1
b) is the heterogeneity factor.
For b = 1, Eq. (8) reduces to Langmuir equation, i.e.
qm K L C e
qe 10
1 K L Ce
where KL (=aR) is the Langmuir adsorption constant
(l mg
1) related to the energy of adsorption and qm
(=KR/aR) signies adsorption capacity (mg g
1).
For b = 0, Eq. (8) reduces to Henrys equation, i.e.
K R Ce
qe 11
1 aR
The RP isotherm incorporates three parameters and
can be applied either in homogenous or heterogeneous
systems. Eq. (8) can be converted to a linear form by
taking logarithms of both the sides as


Ce
ln K R
1 ln aR b ln C e 12
qe
A minimization procedure has been adopted to solve Eq.
(12) by maximizing the correlation coecient between
the predicted values of qe from Eq. (12) and the experi-
mental data using the solver add-in function of the MS
excel.
The Temkin isotherm is given as
RT
qe lnK T C e 13
b
which can be linearized as:
qe B1 ln K T B1 ln C e 14
RT
where B1 15
b
Temkin isotherm contains a factor that explicitly
takes into the account adsorbing speciesadsorbent
interactions. This isotherm assumes that (i) the heat of
adsorption of all the molecules in the layer decreases lin-
early with coverage due to adsorbentadsorbate interac-
tions, and that (ii) the adsorption is characterized by a
uniform distribution of binding energies, up to some
maximum binding energy (Temkin and Pyzhev, 1940;
Kim et al., 2004). A plot of qe versus ln Ce enables the
determination of the isotherm constants B1 and KT from
the slope and the intercept, respectively. KT is the equi-
maximum binding energy and constant B1 is related to
the heat of adsorption.
The experimental data for the equilibrium adsorption
of CR on the three adsorbents have been tted to the
Freundlich, Langmuir, RP and Temkin isotherms.
The isotherms constants have been obtained by using
the regression analysis using a statistical software
STATISTICA version 5.0 for Windows. Error analysis
showed the adequacy of a particular isotherm equation
to represent the experimental equilibrium adsorption
data. It was found that the RP isotherm best represents
the equilibrium adsorption of CR on all the three adsor-
bents. The Freundlich isotherm also shows comparable
t with the experimental data.
The RP isotherm constants aR, KR and b and the
correlation coecient, R2, of the RP isotherm with
the experimental data are listed in Table 3. The correla-
tion coecients for RP isotherm are highest in compar-
ison to the values obtained for the Freundlich,
Langmuir and the Temkin isotherms. Therefore, RP
is the best-t isotherm equation for the adsorption of
CR on BFA, ACC and ACL.
Fig. 7 shows the linearized form of the RP isotherm
plots for the sorption of CR on the three adsorbents.
Fig. 8 shows the comparative t of dierent isotherms
with the equilibrium data plotted as qe versus Ce. It is
 I.D. Mall et al. / Chemosphere 61 (2005) 492501 499

Table 3
Isotherm parameters and error analyses values for the removal of congo red by various adsorbents
Adsorbent KF ((mg g
1) (mg l
1)
1/n) 1/n R2 HYBRID MPSD
Freundlich constants
BFA 8.162 0.288 0.9983 0.123 3.483
ACC 0.402 0.234 0.9936 0.049 2.048
ACL 0.939 0.341 0.9914 0.168 4.004
KL (l mg
1) qm (mg g
1) R2 HYBRID MPSD
Langmuir constants
BFA 3.334 11.885 0.924 2.216 14.888
ACC 1.867 0.635 0.968 0.199 4.469
ACL 1.378 1.875 0.956 0.652 8.074

KR (l g
1) aR (l mg
1) b R2 HYBRID MPSD

RedlichPeterson constants
BFA 15 864.8 1935.376 0.712 0.9973 0.121 3.483
ACC 5.56 12.749 0.804 0.9937 0.035 1.883
ACL 205.12 217.516 0.662 0.9912 0.221 4.027

KT (l mg
1) B1 R2 HYBRID MPSD

Temkin constants
BFA 52.951 2.161 0.9747 0.733 8.560
ACC 39.614 0.110 0.9921 0.043 2.066

7 clear from this gure that the RP and Freundlich iso-

BFA therms show very good t with the data.
6
ln (KR Ce/qe - 1)

ACC
ACL
5 3.8. Error analysis

4
Due to the inherent bias resulting from linearisation,
3
dierent error functions of non-linear regression basin
were employed in this study to nd out the best-t iso-
2
-3 -2 -1 0 1 2
therm model to the experimental equilibrium data.
ln Ce Based on the error functions and their limitations, the
hybrid fractional error function (HYBRID) was chosen
Fig. 7. RedlichPeterson isotherm plots for the removal of along-with Marquardts percent standard deviation
CR by various adsorbents (pH0 = 7, temperature = 30 C, (MPSD).
t = 4 h). HYBRID is given as
" #
100 X n
qe;exp
qe;calc
HYBRID 16
16 n
p i1 qe;exp
i
14
2 1, 3
4
This error function was developed (Porter et al., 1999) to
12
improve the t of the error analysis at low concentration
qe (mg g-1)

10 values. Instead of n as used in the average relative error

8
Experimental (ARE) analysis proposed by Kapoor and Yang (1989),
Freundlich, 1
Langmuir, 2
the sum of the fractional errors is divided by (n
p)
6
R-P, 3 where p is the number of parameters in the isotherm
4
Temkin, 4 equation.
2 MPSD (Marquardt, 1963) has been used by a num-
0 1 2 3 4 5 6
-1 ber of researchers in the eld (Ng et al., 2003; Wong
Ce (mg l )
et al., 2004) to test the adequacy and accuracy of the
Fig. 8. Equilibrium isotherms for the removal of CR by BFA. model t with the experimental data. It has somewhat
500 I.D. Mall et al. / Chemosphere 61 (2005) 492501
similarity to the geometric mean error distribution, but
modied by incorporating the number of degrees of free-
dom. This error function is given as
v (BFA) is an eective adsorbent for the removal of CR
u !2
u 1 X n
q
q from aqueous solutions. Higher CR removal by BFA,
MPSD 100t
e;exp
n
p i1 qe;exp
Since each of the error functions produce a dierent set
of isotherm parameters, an overall optimum parameter
set is dicult to identify directly. Thus, a normalisation
of each parameter is employed in order to have a better
comparison between the parameter sets for the single iso-
therm model (Wong et al., 2004). In the normalisation
processes each error function was selected in turn and
the results for each parameter set were determined. Sec-
ondly, the errors determined for a given error function
were divided by the maximum to obtain the normalised
errors for each parameter set. Lastly, the normalised
errors for each parameter set were summed up.
The values of the two error functions are presented
in Table 3. By comparing the results of the values of
the error functions, it is found that RP model best-ts
the CR adsorption isotherm data for the BFA and
ACC. Freundlich isotherm best-tted the isotherm data
for CR adsorption on ACL. It may, however, be noted
that the non-linear correlation coecients, R2 and the
error analysis values are similar for the Freundlich
and RP isotherms and hence any one of the isotherms
could be used for CR adsorption on BFA, ACC and
ACL.
3.9. Thermodynamic study
Thermodynamic data such as adsorption energy can
be obtained from Langmuir, RP and Temkin equations
(Kim et al., 2004).

DG0ads RT lnK
where DG0 is the free energy change (kJ mol
1), T is the
absolute temperature (K), R is the universal gas constant
(8.314 J mol K
1), and K is the Langmuir, RP or
Temkin constant. For the Langmuir isotherm, the Gibbs
free energy of adsorption for CR on BFA, ACC and
ACL were found to be
32.253,
16.722 and

8.587 kJ mol
1, respectively. For the Temkin iso-
therm, the values of KT as given in Table 3 were used.
The corresponding Gibbs free energy values were

106.316,
98.543 and
64.101 kJ mol
1, respectively.
From RP constant aR (Table 3), corresponding Gibbs
free energy values were computed as
202.704,

68.178 and
144.160 kJ mol
1, respectively. All the
three adsorption isotherms show highest negative value
of Gibbs free energy for BFA in comparison to those
for ACC and ACL. Therefore, adsorption will be most
favoured on BFA.
4. Conclusion
The present study shows that the bagasse y ash
e;calc
17 ACC and ACL is possible provided that the initial adsor-
i bate concentration is low in the solution. Equilibrium
adsorption was practically achieved in 4 h. Adsorption
kinetics followed pseudo-second-order rate expression
with initial sorption rate being highest for adsorption
on BFA. Freundlich and RP isotherms show very good
t with the experimental adsorption equilibrium data for
CR on all the adsorbents studied. Thermodynamic study
showed that CR adsorption will be most favoured on
BFA.
Acknowledgement
The authors thank the reviewers of the manuscript
for their useful comments and suggestions.
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