Bioresource Technology 98 (2007) 1421

Experimental and kinetic studies on methylene blue adsorption

by coir pith carbon
a,* b
D. Kavitha , C. Namasivayam
a
Department of Environmental System Engineering, Hallym University, 1 Okchon-dong, Chuncheon, Gangwon-do 200-702, Republic of Korea
b
Environmental Chemistry Division, Department of Environmental Sciences, Bharathiar University, Coimbatore 641 046, India

Received 22 August 2005; received in revised form 29 November 2005; accepted 2 December 2005
Available online 19 January 2006

Abstract

Varying the parameters such as agitation time, dye concentration, adsorbent dose, pH and temperature carried out the potential fea-
sibility of thermally activated coir pith carbon prepared from coconut husk for removal of methylene blue. Greater percentage of dye was
removed with decrease in the initial concentration of dye and increase in amount of adsorbent used. Kinetic study showed that the
adsorption of dye on coir pith carbon was a gradual process. Lagergren rst-order, second-order, intra particle diusion model and
Bangham were used to t the experimental data. Equilibrium isotherms were analysed by Langmuir, Freundlich, DubninRadushkevich,
and Tempkin isotherm. The adsorption capacity was found to be 5.87 mg/g by Langmuir isotherm for the particle size 250500 lm. The
equilibrium time was found to be 30 and 60 min for 10 and 20 mg/L and 100 min for 30, 40 mg/L dye concentrations, respectively. A
maximum removal of 97% was obtained at natural pH 6.9 for an adsorbent dose of 100 mg/50 mL and 100% removal was obtained
for an adsorbent dose of 600 mg/50 mL of 10 mg/L dye concentration. The pH eect and desorption studies suggest that chemisorption
might be the major mode of the adsorption process. The change in entropy (DS0) and heat of adsorption (DH0) of coir pith carbon was
estimated as 117.20 J/mol/K and 30.88 kJ/mol, respectively. The high negative value of change in Gibbs free energy indicates the feasible
and spontaneous adsorption of methylene blue on coir pith carbon.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Adsorption; Coir pith carbon; Methylene blue; Kinetic study

1. Introduction can further exploit activated carbon. Recently, various

Dye removal from wastewater has received considerable
attention with several adsorbents and several classes of dye
being investigated (Meyer et al., 1992; Allen et al., 1998).
The successful prediction of adsorption isotherms of dyes
on activated carbon has been reported (McKay et al.,
1998). The conventional methods for removal of dyes using
alum, ferric chloride, coconut shell based activated carbon
etc., are not economical in the Indian context. Pollard et al.
(1992) and Namasivayam (1995) have reviewed non-con-
ventional adsorbents used for the removal of dyes and
heavy metals. Research is therefore needed to develop
new alternative environmental friendly applications that
*
Corresponding author. Tel.: +82 33 248 2165; fax: +82 33 241 1536.
E-mail address: srikavi1@gmail.com (D. Kavitha).
kinds of activated carbon have been used as low-cost
adsorbents for removal of heavy metals, organics and dyes
from waters.
Activated carbon has many applications, one of which is
used as an ecient and versatile adsorbent for purication
of water, air and many chemical and natural products
(Hassler, 1963). This is possible due to the highly porous
nature of the solid and its extremely large surface area to
volume ratio. Much of this surface area is contained in
micropores and mesopores. Currently, activated carbon
has been an eective adsorbent for dye removal (Walker
and Weatherley, 2000; Kannan and Sundaram, 2001).
The adsorption capacity of a certain carbon is known to
be a function of porous structure, chemical nature of the
surface, and pH of the aqueous solution. In addition, the
adsorption process is inuenced by the nature of the adsor-

0960-8524/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2005.12.008
 D. Kavitha, C. Namasivayam / Bioresource Technology 98 (2007) 1421 15

bate and its substituent groups. The presence and concen- Table 1
tration of surface functional groups plays an important Characteristics of coir pith carbon
role in the adsorption capacity and the removal mechanism Physical parameters
of the adsorbates (Yenisoy et al., 2004). Specic surface area (m2/g) 167 pHZPC 8.0
Bulk density (g/mL) 0.12 pH (1% solution) 10.1
The recent studies on methylene blue adsorption onto Conductivity 2.3 Ash content (%) 79.87
activated carbon (Shaobin et al., 2005), rice husk (Vadive- (1% solution) (mS/cm)
lan and Vasanth Kumar, 2005), peanut hull (Renmin et al., Mechanical moisture 5.88 Porosity (%) 93.11
2005) KOH-activated and steam-activated carbons (Wu content (%)
et al., 2005), pumice powder (Feryal, 2005), glass bers Specic gravity 1.742 Volatile matter (%) 58.38
Decolourising power (mg/g) 21.0 Fixed carbon (%) 41.62
(Sampa and Binay, 2005) basic and acid dyes onto oxihum- Iodine number (mg/g) 101.52 Ion exchange capacity Nil
olite (oxidised young brown coal) (Pavel et al., 2005), cat-
Chemical parameters (%)
ionic and anionic dyes on pyrophyllite (Aslhan et al.,
Sodium 0.14 Potassium 0.18
2005), have been reported. Calcium 0.22 Phosphorous 0.01
Coir pith is a byproduct of coconut coir industries in Iron 0.18
southern India. It is a soft biomass separated from the
coconut husk during the preparation of coir ber. Eorts
have been made to carbonize the coir pith and to use it absorbance was measured. Eect of adsorbent dosage was
for wastewater treatment. Since the coir pith is abundantly studied with dierent adsorbent doses (25600 mg) and
available in Tamil Nadu and Kerala, coir pith carbon may 50 mL of dye solutions and agitated for equilibrium time.
prove to be not only as cost-eective and non-conventional Langmuir, Freundlich, Tempkin and DubininRadush-
adsorbent but also help reduce the solid waste disposal kevich isotherms were employed to study the equilibrium
problems. The colour removal by coir pith carbon (94%) adsorption. Eect of pH was studied by adjusting the pH
was comparable with commercial carbon (90%) at natural of dye solutions using dilute HCl and NaOH solutions
pH 8.6. coir pith carbon was also found to be eective for and the solutions were agitated with 300 mg/50 mL adsor-
the removal of metals (Kadirvelu and Namasivayam, bent dose at 40 and 60 min for 10 and 20 mg/L dye concen-
2001), and chlorophenols (Namasivayam and Kavitha, trations, respectively. Desorption studies of the adsorbent
2004). The purpose of this work was to investigate the that was used for the adsorption of 10 or 20 mg/L of dye
removal of methylene blue by coir pith carbon. solution was separated from the solution by centrifugation.
The dye-loaded adsorbent was ltered using Whatman lter
2. Methods paper and washed gently with water to remove any unad-
sorbed dye. Several such samples were prepared. Then the
2.1. Physico-chemical analysis of adsorbent spent adsorbent was agitated for 40 or 60 min with 50 mL
of distilled water and adjusted to dierent pH values. The
Coir pith was collected from nearby coconut coir indus- desorbed dye was estimated as before. For temperature
tries, dried in sunlight for 5 h and ground. The dried coir studies, adsorption of 10 mg/L of methylene blue by
pith powder was sieved to 250500 lm size. It was sub- 200 mg of adsorbent was carried out at 35, 40, 50 and
jected to carbonization at 700 C for 1 h using a mue fur- 60 C in the thermostated rotary shaker, respectively.
nace under closed condition. The carbonized material was
taken out, sieved to 250500 lm size again and used for 3. Results and discussion
adsorption studies. The characteristics of coir pith carbon
(APHA, 1980, 1998; ISI, 1977) reported in Table 1. The 3.1. Scanning electron micrograph analyses
porous texture was further examined by scanning electron
microscope (SEM) observation. The SEM analysis was car- The textural structure examination of coir pith particles
ried out on the Hitachi 2300 scanning electron microscope. can be observed from the SEM photographs (Fig. 1). This
photomicrograph shows brous structure of coir pith car-
2.2. Experimental procedures bon reveals surface texture and porosity. SEM is widely
used to study the morphological features and surface char-
Adsorption experiments were carried out by agitating acteristics of the adsorbent materials (Nelly and Isaco,
300 mg of carbon with 50 mL of dye solution of desired 1982; Rook, 1983).
concentration and pH at 200 rpm, 35 C in a thermostated
rotary shaker (ORBITEK, Chennai, India). Methylene blue 3.2. Adsorption experiment studies
concentration was estimated spectrophotometrically by
monitoring the absorbance at 660 nm using UVVIS spec- 3.2.1. Eects of agitation time and concentration of
trophotometer (Hitachi, model U-3210, Tokyo). pH was dye on adsorption
measured using pH meter (Elico, model LI-107, Hydera- The amount of dye adsorbed (mg/g) increased with
bad, India). The dye solution was separated from the adsor- increase in agitation time and reached equilibrium. The
bent by centrifugation at 20,000 rpm for 20 min and its equilibrium time was 40 and 60 min for 10 and 20 mg/L
16 D. Kavitha, C. Namasivayam / Bioresource Technology 98 (2007) 1421
Fig. 1. Scanning electron micrograph coir pith carbon.
dye concentration, respectively and 120 min for both 30
and 40 mg/L dye concentration. The amount of dye
removed at equilibrium increased from 1.6 to 5.4 mg/g with
the increase in dye concentration from 10 to 40 mg/L. It is
clear that the removal of dyes depends on the concen-
tration of the dye. It also observed that for an initial dye
concentration of 10 mg/L, the maximum amount (approx-
imately 97.3% of total amount of dye removed) of dye was
adsorbed within the rst 30 min at an average adsorption
rate of 0.054 mg/g min and thereafter the adsorption rate
tends to decrease and proceeds at an average adsorption
rate of 0.016 mg/g min. A similar trend was observed for
the remaining range of initial dye concentrations (20
40 mg/L) studied. The initial rapid phase may be due to
increased the number of vacant sites available at the initial
stage, as a result there exist increased concentration gradi-
ent between adsorbate in solution and adsorbate in the
adsorbent.
3.2.2. Studies on pH eect
Eect of pH on the removal of methylene blue is shown
in Fig. 2. The percent removal was more than 90% in the
pH range 211. At pH 2, though positively charged surface
sites on the adsorbent do not favor the adsorption of dye
cations due to the electrostatic repulsion, dye removal
102
100
98
96 A 14
% Removal
94
92
90 Dye conc.
10 mg/L
88
20 mg/L
86
B 4
84
82
2 3 4 5 6 7 8 9 10
Initial pH
Fig. 2. (A) Eect of pH on removal of methylene blue, adsorbent dose,
300 mg/50 mL; 10 mg/L, agitation time 40 min; 20 mg/L, agitation time
60 min. (B) Eect of pH on desorption of dye from dye-loaded adsorbent.
Adsorbent dose, 300 mg/50 mL; 10 mg/L, agitation time 40 min; 20 mg/L,
agitation time 60 min.
was still high (more than 90%). As the pH increased, the
removal increased slightly. Several investigations have
reported that methylene blue adsorption usually increases
as the pH is increased (Gupta et al., 2004; Singh et al.,
2003; Janos, 2003). Basically, methylene blue and other cat-
ionic dyes produce an intense molecular cation (C+) and
reduced ions (CH+). At high pH, OH on the surface of
adsorbent will favor the adsorption of cationic dye
molecules.
3.2.3. Eect of temperature
Increase of temperature increased the percent removal.
The change in standard free energy, enthalpy and entropy
of adsorption were calculated using the following
equations:
DG0 RT ln K c 1
where R is gas constant and Kc is the equilibrium constant
and T is the temperature in K.
According to vant Ho equation,
log10 K c DS 0 =2:303R  DH 0 =2:303RT 2
0
Positive values of DH (30.88 J/mol/K) show the endother-
mic nature of adsorption. The negative values of (5.27,
5.72, 6.50 and 7.64) DG0 indicate the spontaneous
nature of adsorption for methylene blue at 35, 40, 50 and
20
60 C. The positive values of DS0 (117.2 kJ/mol) suggest
18 the increased randomness at the solid/solution interface
16 during the adsorption of dye on coir pith carbon. Kinetic
models also applied for temperature studies and it shows
% Desorption
perfect linear curves for methylene blue at dierent temper-
12
10 ature studies and the equilibrium data obtained for all the
8 kinetics are presented in Table 2.
6
3.2.4. Desorption studies
2 Regeneration of exhausted carbon and recovery of dye
0 contribute to the economy of wastewater treatment. Also
11
desorption studies help elucidate the mechanism of adsorp-
tion. Desorption was less than 10% in the entire pH range
210 though there was slight increase from 0.5 to 9.0
(Fig. 2). Insignicant desorption at dierent pH values con-
rms that chemisorption is the major mode of adsorption
process.
 D. Kavitha, C. Namasivayam / Bioresource Technology 98 (2007) 1421 17

Table 2
Kinetic parameters for the removal of methylene blue by coir pith carbon
Concentration k1 (min1) qe (mg/g) R2 Temperature (C) k1 (min1) qe (mg/g) R2
Pseudo-rst-order constants
10 0.1089 0.3663 0.9929 35 0.117 2.314 0.967
20 0.0525 0.6108 0.9864 40 0.124 1.992 0.989
30 0.0173 0.7803 0.9655 50 0.103 1.314 0.971
40 0.0233 1.3259 0.9780 60 0.081 0.586 0.927
h (mg/g min) k2 (g/mg min) R2 Temperature (C) h (mg/g min) k2 (g/mg min) R2
Pseudo-second-order constants
10 1.6913 0.6049 0.9998 35 1.9331 0.09 0.999
20 2.3924 0.2545 0.9998 40 2.4825 0.11 0.999
30 1.9534 0.1112 0.9999 50 3.6178 0.16 0.999
40 1.845 0.0646 0.9992 60 7.813 0.34 1.000
k0 (mL/g/L) a R2 Temperature (C) k0 (mL/g/L) a R2
Bangham constants
10 6.5109 0.0737 0.9733 35 5.2837 0.1246 0.9826
20 5.7179 0.0799 0.9852 40 6.3173 0.0763 0.9887
30 5.5788 0.0464 0.9517 50 6.885 0.0559 0.9882
40 4.495 0.086 0.9926 60 7.1258 0.0447 0.9957

kid (mg/g min) R2 Temperature (C) kid (mg/g min) R2

Intra-particle diusion constants
10 0.060 0.9464 35 0.0936 0.9414
20 0.1058 0.9379 40 0.0616 0.9593
30 0.074 0.9859 50 0.0466 0.9566
40 0.1447 0.9558 60 0.0383 0.9922

3.3. Adsorption kinetic studies 70

Dye conc. R2
60
3.3.1. Adsorption dynamics 10 mg/L 0.9998
20 mg/L 0.9998
The rate constant of adsorption is determined from the 50
t/q (min.g/mg)

30 mg/L 0.999
rst-order rate expression given by Lagergren and Svenska 40 40 mg/L 0.9992
(1898).
30
logqe  q log qe  k 1 t=2:303 3 20

where qe and q are the amounts of dye adsorbed (mg/g) at 10

equilibrium and at time t (min), respectively, and k1 is the
0
rate constant of adsorption (L/min). The values of k1 and 0 20 40 60 80 100 120

qe at dierent concentrations are presented in Table 2. Time (min)

Fig. 3. Second-order kinetics plots for the removal of methylene blue, at

3.3.2. The second-order kinetic model
The second-order kinetic model (McKay and Ho, 1999)
is expressed as
t=q 1=k 2 q2e t=qe
the initial adsorption rate, h (mg/g min), as t ! 0 can be
dened s
h k 2 q2e
where the initial adsorption rate (h), the equilibrium
adsorption capacity (qe), and the second-order constants
k2 (g/mg min) can be determined experimentally from the
slope and intercept of plot t/q versus t (Fig. 3). Calculated
correlations are closer to unity for second-order kinetics
model; therefore the adsorption kinetics could well be
approximated more favorably by second-order kinetic
model for methylene blue. The k2 (g/mg min) and h values
are calculated from Fig. 3 are listed in Table 2.
dierent initial dye concentrations: adsorbent dose, 300 mg/50 mL; initial
pH, 6.9, temperature 35 C.
4
3.3.3. Intra-particle diusion study
An empirically found functional relationship, common
to the most adsorption processes, is that the uptake varies
almost proportionally with t1/2, the WeberMorris plot,
5
rather than with the contact time t (Weber and Morris,
1963).
qt k id t1=2 C 6
where kid is the intra-particle diusion rate constant.
According to Eq. (6), a plot of qt versus t1/2 should be a
straight line with a slope kid and intercept C when adsorp-
tion mechanism follows the intra-particle diusion process.
Values of intercept give an idea about the thickness of
boundary layer, i.e., larger the intercept with greater is
18 D. Kavitha, C. Namasivayam / Bioresource Technology 98 (2007) 1421

6 3.3.5. Adsorption equilibrium study

Dye conc. R
2 To optimize the design of an adsorption system for the
5
10 mg/L 0.9464 adsorption of methylene blue, it is important to establish
4
20 mg/L 0.9379
the most appropriate correlation for the equilibrium
30 mg/L 0.9859
curves. Various isotherm equations have been used to
q (mg/g)

40 mg/L 0.9558
3 describe the equilibrium nature of adsorption. Some of
1

these equations are Langmuir, Freundlich, Tempkin and

2
1
0
0 2 4 6 8 10
Time1/2(min)1/2
Fig. 4. Weber and Morris intra-particle diusion plots for removal of
methylene blue, at dierent initial dye concentrations: adsorbent dose,
300 mg/50 mL; initial pH, 6.9, temperature 35 C.
the boundary layer eect (Kannan and Sundaram, 2001).
In Fig. 4, plot of mass of dye adsorbed per unit mass of
adsorbent, qt versus t1/2 is presented for methylene blue.
The linear plots are attributed to the macro pore diusion
that is the accessible sites of adsorption. This is attributed
to the instantaneous utilization of the most readily avail-
able adsorbing sites on the adsorbent surface. The values
of kid as obtained from the slope of straight lines are listed
in Table 2.
3.3.4. Banghams equation
Kinetic data can further be used to check whether pore
diusion is the only rate-controlling step or not in the
adsorption system using Banghams equation (Aharoni
et al., 1979).
log logC 0 =C0  qt m logk 0 m=2:303V logt
where C0 is the initial concentration of adsorbate in solu-
tion (mg/L), V is the volume of solution (mL), m is the
weight of adsorbent per liter of solution (g/L), qt (mg/g)
is the amount of adsorbate retained at time t, and a (less
than 1) and k0 are constants. The double logarithmic plot
(Fig. 5) according to above equation yielded perfect linear
curves for methylene blue removal by carbon, showing that
the diusion of adsorbate into pores of the adsorbent is not
the only rate controlling step (Tutem et al., 1998).
-1.6
0 0.2 0.4 0.6 0.8 1 1.2 1.4
DubininRadushkevich (DR).
3.3.6. Adsorption isotherms
12
Langmuir isotherm (1918) is represented by the follow-
ing equation:
C e =qe l=Q0 b C e =Q0 8
where Ce is the concentration of dye solution (mg/L) at
equilibrium. The constant Q0 signies the adsorption
capacity (mg/g) and b is related to the energy of adsorption
(L/mg). Linear plot of Ce/qe versus Ce shows that adsorp-
tion follows Langmuir isotherm (gure not shown). Values
of Q0 and b were calculated from the slope and intercept of
the linear plot and are presented in Table 3. The adsorption
capacity can be correlated with the variation of surface
area and porosity of the adsorbent. Higher surface area
and pore volume will result in higher adsorption capacity.
Several investigators have been conducted using various
low-cost adsorbent. Table 4 compares the adsorption
capacity of dierent types of adsorbents using for methy-
lene blue adsorption. It is seen low cost material from bark,
rice husk, cotton waste and coal (McKay et al., 1999) re-
ported the highest adsorption capacity such as 914, 312,
277, and 250 mg/g and activated carbon prepared from rice
husk-H3PO4 impregnated (Singh and Srivastava, 2001)
7 observed 333 mg/g revealing that low cost material can
be employed as a promising adsorbent for dye adsorption.
The essential characteristics of Langmuir isotherm can
be expressed by a dimensionless constant called equilib-
rium parameter RL, dened by Weber and Chakkravorti
(1974):
RL 1=1 bC 0 9
where b is the Langmuir constant and C0 is the initial dye
concentration (mg/L), RL values indicate the type of iso-
therm. Table 3 shows RL values between zero and one,
which indicate favorable adsorption.
1.6 1.8 2

-1.65 3.3.7. Freundlich isotherm

Dye conc. R 2
Freundlich (1985) was also applied to plots of equilib-
loglog(C0/C0-qtm)

-1.7 10 mg/L 0.9733

20 mg/L 0.9852 rium adsorption data:
-1.75 30 mg/L 0.9517
40 mg/L 0.9926 log10 x=m log10 k f 1=nlog10 C e 10
-1.8
where x is the amount of dye adsorbed (mg), m is the
-1.85 weight of the adsorbent used (g), Ce is the equilibrium con-
centration of dye in solution (mg/L), kf (mg11/n L1/n g1)
-1.9
log t and 1/n are Freundlich constants. The correlation coe-
cients were found to be less than 0.9 (Fig. 6) and values
Fig. 5. Banghams plot for removal of methylene blue, at dierent initial
dye concentrations: adsorbent dose, 300 mg/50 mL; initial pH, 6.9, of kf and n were calculated from intercept and slope of
temperature 35 C. plots and are presented in Table 3.
 D. Kavitha, C. Namasivayam / Bioresource Technology 98 (2007) 1421 19

Table 3
Isotherm parameters for removal of methylene blue by coir pith carbon
Concentration Q0 (mg/g) b (L/mg) RL
Langmuir constants
10 0.766
20 5.87 0.93 0.621
30 0.522
40 0.451
kf (mg11/n L1/n g1) n R2
Freundlich constants
10 1.192 0.705 0.8972
20 0.845 0.731 0.8675
30 0.726 0.785 0.8968
40 0.778 0.860 0.8840
qs (mg/g) E (kJ/mol) R2
DubninRadushkevich constants
10
20 4.266 3.54 0.8421
30
40
KT (L/mg) B1 R2
Tempkin constants
10
20 23.25 0.9618 0.952
30
40

Table 4
Langmuir and Freundlich constants for methylene blue adsorption by various adsorbents reported in literature
Adsorbent Q0 (mg/g) b (L/mg) kf (mg11/n L1/n g1) n References
Bark 914.59 0.017 D D McKay et al. (1999)
Activated carbon 333.3 0.043 57.54 2.86 Singh and Srivastava (2001)
(rice husk-H3PO4 impregnated)
Coal 323.68 0.004 D D McKay et al. (1999)
Rice husk 312.26 0.017 D D McKay et al. (1999)
Cotton waste 277.78 0.009 D D McKay et al. (1999)
NaOH-treated raw clay 204.00 16.34 17.04 0.047 Ghosh and Bhattacharyya (2001)
Activated carbon 194.3 0.066 6.083 5.579 Rozada et al. (2003)
(sewage sludge-H2SO4 impregnated)
Hair 158.23 0.019 D D McKay et al. (1999)
Tree leaves 133.33 0.290 52.48 4.0 Singh and Srivastava (1999)
NaOH-treated pure clay 122.01 20.49 23.05 0.098 Ghosh and Bhattacharyya (2001)
Carbon slurry waste 96.2 6.67 104 D D Jain et al. (2003)
Pure clay 91.87 15.55 16.39 0.070 Ghosh and Bhattacharyya (2001)
Calcined pure clay 56.31 8.88 9.01 0.061 Ghosh and Bhattacharyya (2001)
Activated carbon from waste rubber P-700 49.0 0.05 D D Miguel et al. (2002)
Saw dust 32.26 0.38 14.58 0.26 De and Basu (1998)
Raw clay 27.49 13.99 14.85 0.151 Ghosh and Bhattacharyya (2001)
Calcined raw clay 13.44 7.59 6.57 0.075 Ghosh and Bhattacharyya (2001)
Boiler bottom ash * * 2.22 0.90 Vasanth Kumar and Bhagavanulu (2002)
Biogas residual slurry * * 21.38 1.46 Namasivayam and Yamuna (1994)
* Does not follow Langmuir isotherm/not reported.

D Does not follow Freundlich isotherm/not reported.

3.3.8. Tempkin isotherm age due to adsorbateadsorbate interactions, and (ii)

Tempkin isotherm contains a factor that explicitly takes adsorption is characterized by a uniform distribution of
into account adsorbing speciesadsorbate interactions. binding energies, up to some maximum binding energy
This isotherm assumes that: (i) the heat of adsorption of (Tempkin and Pyzhev, 1940). Tempkin isotherm is repre-
all the molecules in the layer decreases linearly with cover- sented by the following equation:
20 D. Kavitha, C. Namasivayam / Bioresource Technology 98 (2007) 1421

1.6 removal of dye follows pore diusion process since the coef-
1.4 cient values are in the range of 10111013 cm2/s. values
1.2
of Dp for methylene blue are 0.884 and 0.589 1012 cm2/s
1
Dye conc. R2
0.8972
for 10 and 20 mg/L and 0.295 1012 cm2/s for 30 and
10 mg/L
log (x/m)

20 mg/L 0.8675
40 mg/L have been observed.
0.8
30 mg/L 0.8968
0.6
40 mg/L 0.884 4. Conclusions
0.4

0.2
0
1 1.5
--1 -0.5 0 0.5
log ce
Fig. 6. Freundlich plots for the adsorption of methylene blue by coir pith
carbon.
qe RT =b lnK t C e
Eq. (11) can be expressed in its linear form as
qe B1 ln K t B1 ln C e
where
B1 RT =b
The adsorption data can be analysed according to Eq. (12).
A plot of qe versus ln Ce enables the determination of the
isotherm constants Kt and B1. Kt is the equilibrium binding
constant (L/mol) corresponding to the maximum binding
energy and constant B1 is related to the heat of adsorption.
The values of the parameters are given in Table 3.
3.3.9. Dubinin and Radushkevich isotherm
Another equation used in the analysis of isotherms was
proposed by Dubinin and Radushkevich (1947):
2 by colloid ion-coated alumina. J. Chem. Technol. Biotechnol. 29, 404
qe qs expBe
where qs is DR constant and e can be correlated:
e RT ln1 1=C e
1=2
E 1=2B
Calculated DubininRadushkevich constants for the
adsorption of methylene blue on coir pith carbon are
shown in Table 3; the values of correlation coecients
are much lower than other three isotherms values. In this
case, DR equation represents the poorer t of experimen-
tal data than the other isotherm equation.
3.4. Pore diusion coecient
Assuming spherical geometry for the adsorbent, the time
for half adsorption can be correlated to the pore diusion
coecient (Michelson et al., 1975).
t1=2 0:03r20 =Dp
where t1/2 is the time for half adsorption (s), r0 is the radius
of the adsorbent particle (cm) and Dp is the diusion coef-
cient (cm2/s). Values of Dp have been calculated for dier-
ent temperatures and dierent concentrations of dye. The
The present study shows that the coir pith carbon is an
eective adsorbent for the removal of methylene blue from
2
aqueous solution. Higher methylene blue by coir pith car-
bon is possible provided that the initial adsorbate concen-
tration was low in the solution. Equilibrium adsorption
was achieved in about 40 min. Batch kinetic studies per-
formed on the carbondye system indicated the adsorption
capacity of coir pith carbon. Kinetics data tended to t well
11
in second-order kinetics, conrming the chemisorption of
methylene blue onto coir pith carbon particles. By sec-
12 ond-order model to study the mechanism of adsorption,
calculated qe values, agreed well with the qe experimental
values, supporting the chemisorption. The Langmuir and
13 Tempkin isotherms best represent the equilibrium adsorp-
tion data. The eective diusion coecient of methylene
blue is of the order of 1012 cm2/s. As the raw material,
coir pith is discarded as waste in coir industries; the treat-
ment method using coir pith carbon is expected to be eco-
nomical. The cost and adsorption characteristics favor coir
pith carbon to be used as an eective adsorbent for the
removal of methylene blue from wastewater.
References
Aharoni, C., Sideman, S., Hoer, E., 1979. Adsorption of phosphate ions
14
412.
Allen, S.J., Mckay, G., Khader, K.Y.H., 1998. The adsorption of acid dye
onto peat from aqueous solutionsolid diusion model. J. Colloid
15 Interface Sci. 126, 517524.
APHA, 1980. Standard Methods for the Examination of Water and
16 Wastewater, 15th ed. American Public Health Association, Washing-
ton, DC.
APHA, 1998. Standard Methods for the Examination of Water and
Wastewater, 20th ed. American Public Health Association, Washing-
ton, DC.
Aslhan, G., Savas, S., Sedat, B., Ali, M.M., 2005. Adsorption and kinetic
studies of cationic and anionic dyes on pyrophyllite from aqueous
solutions. J. Colloid Interface Sci. 286, 5360.
De, D.S., Basu, J.K., 1998. Adsorption of methylene blue on to a low cost
adsorbent developed from saw dust. Indian J. Environ. Prot. 19, 416
421.
Dubinin, M.M., Radushkevich, L.V., 1947. Equation of the characteristic
curve of activated charcoal. Chem. Zentr. 1, 875.
Feryal, A., 2005. Adsorption of basic dyes from aqueous solution onto
pumice powder. J. Colloid Interface Sci. 286, 455458.
Freundlich, H., 1985. Uber die adsorption in lunsungen. J. Phys. Chem.
57, 387470.
17 Ghosh, D., Bhattacharyya, K.G., 2001. Removing colour from aqueous
medium by sorption on natural clay: a study with methylene blue.
Indian J. Environ. Prot. 21, 903910.
Gupta, V.K., Suhas, A.I., Saini, V.K., 2004. Removal of rhodamine B,
fast green, and methylene blue from wastewater using red mud, an
aluminum industry waste. Ind. Eng. Chem. Res. 43, 17401747.
 D. Kavitha, C. Namasivayam / Bioresource Technology 98 (2007) 1421
Hassler, J.W., 1963. Activated Carbon. Chem. Publ., New York.
ISI, 1977. Methods of sampling and tests for activated carbon used for
decolourising vegetable oils and sugar solutions. Indian Standards
Institution (ISI), 877.
Jain, A.K., Gupta, V.K., Bhatngar, A., Jain, S., Suhas, A.I., 2003. A
comparative assessment of adsorbents prepared from industrial wastes
for the removal of cationic dye. J. Indian Chem. Soc. 80, 267270.
Janos, P., 2003. Sorption of basic dyes onto iron humate. Environ. Sci.
Technol. 37, 57925798.
Kadirvelu, K., Namasivayam, C., 2001. Adsorption of nickel (II) from
aqueous solution onto activated carbon prepared from coir pith. Sep.
Purif. Technol. 24, 497505.
Kannan, K., Sundaram, M.M., 2001. Kinetics and mechanism of removal
of methylene blue by adsorption on various carbonsa comparative
study. Dyes Pig. 51, 2540.
Lagergren, S., Svenska, B.K., 1898. Zur theorie der sogenannten adsorp-
tion geloester stoe. Vetenskapsakad. Handl. 24, 139.
Langmuir, I., 1918. The adsorption of gases on plane surfaces of glass,
mica and platinum. J. Am. Chem. Soc. 40, 1361.
McKay, G., Al-Duri, B., Allen, S.J., Thomson, A., 1998. Adsorption for
liquid process euents. IchE Symp. Pap 17 (3), 117.
McKay, G., Ho, Y.S., 1999. Pseudo-second order model for sorption
processes. Process. Biochem. 34, 451465.
McKay, G., Porter, J.F., Prasad, G.R., 1999. The removal of dye colours
from aqueous solutions by adsorption on low cost materials. Wat. Air.
Soil. Pollut. 114, 423438.
Meyer, V., Carlsson, F.H.H., Oellermann, R.A., 1992. Decolourization of
textile euent using a low cost natural adsorbent material. Wat. Sci.
Technol. 26, 12051211.
Michelson, L.D., Gideon, P.G., Pace, E.G., Kutal, L.H., 1975. Removal
of soluble mercury from wastewater by complexing technique, US
Department Industry, Oce of Water Research and Technology, Bull.
No. 74.
Miguel, G.S., Fowler, G.D., Sollars, C.J., 2002. Adsorption of organic
compounds from solution by activated carbons produced from waste
tyre rubber. Sep. Sci. Technol. 37, 663676.
Namasivayam, C., 1995. Adsorbents for the treatment of wastewaters. In:
Trivedy, R.K. (Ed.), Encyclopedia of Environmental Pollution and
Control, Vol. 1. Enviro-media, Karad, Maharastra, India, pp. 3049.
Namasivayam, C., Kavitha, D., 2004. Adsorptive removal of 2,4-
dichlorophenol from wastewater by low-cost carbon from an agricul-
tural solid waste: coconut coir pith. Sep. Sci. Technol. 39, 14071425.
Namasivayam, C., Yamuna, R.T., 1994. Utilizing biogas residual slurry
for dye adsorption. Am. Dyestu Rep. 83, 2228.
Nelly, J.W., Isaco, E.G., 1982. Carbonaceous Adsorbents for the
Treatment of Ground and Surface Water. Marcel Dekker, New York.
Pavel, J., Pavel, S., Milena, R., Sylvie, G., 2005. Sorption of basic and acid
dyes from aqueous solutions onto oxihumolite. Chemosphere 59, 881
886.
21
Pollard, S.J.T., Fowler, G.D., Sollars, C.J., Perry, R., 1992. Low cost
adsorbents for water and wastewater treatment; a review. Sci. Tot.
Environ. 116, 3152.
Renmin, G., Yingzhi, S., Jian, C., Huijun, L., Chao, Y., 2005. Eect of
chemical modication on dye adsorption capacity of peanut hull. Dyes
Pig. 67, 175181.
Rook, J.J., 1983. In: McGuire, M.J., Suet, I.H. (Eds.), Treatment of
Water by Granular Activated Carbon. American Chemical Society,
Washington, DC.
Rozada, F., Calvo, L.F., Garcia, A.I., Villacorta, M., Otero, M., 2003.
Dye adsorption by sewage sludge-based activated carbons in batch and
xed-bed systems. Biores. Technol. 87, 221230.
Sampa, C., Binay, K.D., 2005. On the adsorption and diusion of
methylene blue in glass bers. J. Colloid Interface Sci. 286, 807811.
Shaobin, W., Zhua, Z.H., Anthony, C., Haghseresht, F., Luc, G.Q., 2005.
The physical and surface chemical characteristics of activated carbons
and the adsorption of methylene blue from wastewater. J. Colloid
Interface Sci. 284, 440446.
Singh, K.P., Mohan, D., Sinha, S., Tondon, G.S., Gosh, D., 2003. Color
removal from wastewater using low-cost activated carbon derived
from agricultural waste material. Ind. Eng. Chem. Res. 42, 19651976.
Singh, D.K., Srivastava, B., 1999. Removal of basic dyes from aqueous
solutions by chemically treated Psidium guava leaves. Indian J.
Environ. Hlth. 41, 333345.
Singh, D.K., Srivastava, B., 2001. Basic dyes removal from wastewater
by adsorption on rice husk carbon. Indian J. Chem. Technol. 8, 133
139.
Tempkin, M.J., Pyzhev, V., 1940. Acta Physiochim. URSS 12, 217222.
Tutem, E., Apak, R., Unal, C.F., 1998. Adsorptive removal of chlor-
ophenols from water by bituminous shale. Wat. Res. 32, 23152324.
Vadivelan, V., Vasanth Kumar, K., 2005. Equilibrium, kinetics, mecha-
nism, and process design for the sorption of methylene blue onto rice
husk. J. Colloid Interface Sci. 286, 90100.
Vasanth Kumar, K., Bhagavanulu, D.V.S., 2002. Boiler bottom ash, for
removal of methylene blue from synthetic dye euents. Dyes Chem.,
Textile Mag., 6566.
Walker, G.M., Weatherley, L.R., 2000. Textile wastewater treatment
using granular activated carbon adsorption in xed beds. Sep. Sci.
Technol. 35, 13291341.
Weber, T.W., Chakkravorti, P., 1974. Pore and solid diusion models for
xed-bed adsorbers. AIChEJ 20, 228.
Weber Jr., W.J., Morris, J.C., 1963. Kinetics of adsorption on carbon
from solution. J. Sanit. Eng. Div. ASCE 89 (SA2), 3159.
Wu, F.C., Tseng, R.-L., Hu, C.-C., 2005. Comparisons of pore properties
and adsorption performance of KOH-activated and steam-activated
carbons. Micropor. Mesopor. Mater. 80, 95106.
Yenisoy, K.S., Aygun, A., Gunes, M., Tahtasakal, E., 2004. Physical and
chemical characteristics of polymer-based spherical activated carbon
and its ability to adsorb organics. Carbon 42, 477484.