ARTICLE IN PRESS

Journal of Environmental Management 85 (2007) 956–964

www.elsevier.com/locate/jenvman

Removal of the hazardous dye rhodamine B through

photocatalytic and adsorption treatments
Rajeev Jaina, Megha Mathura, Shalini Sikarwara, Alok Mittalb,
a
Department of Environmental Chemistry, Jiwaji University, Gwalior 474 011, India
b
Department of Applied Chemistry, Maulana Azad National Institute of Technology, Bhopal 462 007, India
Received 14 December 2005; received in revised form 21 October 2006; accepted 3 November 2006
Available online 18 January 2007

Abstract

This paper reports on photocatalytic and adsorptive treatment of a hazardous xanthene dye, Rohdamine B, in wastewater. The
photocatalytic degradation was carried out in the presence of the catalyst TiO2 and the effects of pH, concentration of the dye, amount of
TiO2, temperature and electron acceptor H2O2 on the degradation process were observed. It was found that photocatalytic degradation
by TiO2 is an effective, economical and faster mode of removing Rohdamine B from aqueous solutions. Attempts were also made to
utilize activated carbon and rice husk as potential adsorbents to remove Rhodamine B from wastewater. The adsorption studies were
carried out at 40, 50 and 60 1C, and the effects of pH, temperature, amount of adsorbents, concentration of adsorbate, etc., on the
adsorption were measured. On the basis of adsorption data the Langmuir and Freundlich adsorption isotherm models were also
confirmed. The adsorption isotherm constants thus obtained were employed to calculate thermodynamic parameters like Gibb’s free
energy, change in enthalpy and entropy. In order to observe the quality of wastewater COD measurements were also carried out before
and after the treatments. A significant decrease in the COD values was observed, which clearly indicates that both photocatalytic and
adsorption methods offer good potential to remove Rhodamine B from industrial effluents.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Photocatalytic degradation; Adsorption; Rice husk; Activated carbon; Rhodamine B; TiO2

1. Introduction
The treatment of highly colored wastewater containing
hazardous industrial chemical effluents is one of the
growing needs of the present time (Ruthven, 1984; Suzuki,
1993). Various physical and chemical techniques like
coagulation, adsorption, chemical oxidation and froth
flotation processes have been used by a number of research
workers for the removal of organics as well as inorganics
from wastewaters, as discussed in the review article of
Bailey et al. (1999). Recently, sophisticated instrumenta-
tion involving electrochemical, photochemical, chromato-
graphic techniques, etc., has also been employed for this
purpose (Gupta and Ali, 2002). Our laboratories are also
contributing in this direction with adsorption and electro-
chemical methods for the removal of some toxic textile and
Corresponding author. Tel.: +91 9425 025427; fax: +91 7552 670904.
E-mail address: aljymittal@yahoo.co.in (A. Mittal).
food dyes (Gupta et al., 2004a; Mittal et al., 2005a, b; Jain
et al., 2004).
COOH
+
Cl−(CH2-CH3)2 N = N(CH2CH3)2
O
Rhodamine B
The dye under consideration is Rhodamine B
(C28H31N2O3Cl; mol. wt. 479; IUPAC Name N-[9-
(ortho-carboxyphenyl)-6-(diethylamino)-3H-xanthen-3-yli-
dene] diethyl ammonium chloride), with the chemical
structure indicated above, which is a highly water soluble,
basic red dye of the xanthene class. It is found as a reddish
violet powder and comes under the trade name of D & C

0301-4797/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2006.11.002
 ARTICLE IN PRESS
R. Jain et al. / Journal of Environmental Management 85 (2007) 956–964
Red No. 19. It is widely used as a colorant in textiles and
food stuffs, and is also a well-known water tracer
fluorescent (Richardson et al., 2004). It is harmful if
swallowed by human beings and animals, and causes
irritation to the skin, eyes and respiratory tract (Rochat
et al., 1978). The carcinogenicity, reproductive and
developmental toxicity, neurotoxicity and chronic toxicity
towards humans and animals have been experimentally
proven (Kornbrust and Barfknecht, 1985; IARC, 1987;
Mirsalis et al., 1989; McGregor et al., 1991; Shimada et al.,
1994; The EFSA Journal, 2005). Thus, keeping the
hazardous nature and harmful effects in view, it was
considered worthwhile to make systematic efforts to
remove Rhodamine B from wastewaters using photoche-
mical techniques and adsorption over two adsorbents—
activated carbon and rice husk.
Photocatalytic oxidation using a semiconductor such as
TiO2 as photocatalyst is one of the various advanced
oxidation processes used nowadays. As TiO2 is illuminated
by light with a wavelength below 380 nm, the photons
excite valence band electrons across the band gap into the
conduction band, leaving holes behind in the valence band.
Parra et al. (2000) suggested that hydrogen peroxide
absorbs only UV light with a wavelengtho300 nm. The
holes in TiO2 react with water molecules or hydroxide ions
(OH) producing hydroxyl radicals OHd. The generation
of OHd depends on the solution pH. Organic pollutants
which are adsorbed on the surface of the catalyst will then
be oxidized by OHd (Goncalves et al., 1999). According to
Dominguez et al. (1998) photocatalytic oxidation processes
can oxidize a wide variety of toxic and persistent organic
compounds to harmless inorganics such as mineral acids,
carbon dioxide and water. Also, this process forms some
byproducts such as halides, metals, inorganic acids and
organic aldehydes, depending on the initial materials and
the extent of decolorization (Robinson et al., 2001). The
color of dyes results from conjugated chains or rings
which absorb light at visible wavelengths. UV degradation
by the cleavage of conjugated chains was achieved by
Ma and Chu (2001). Combined photochemical and
biological processes were investigated for the destruction
of biorecalcitrant herbicides by Parra et al. (2000) and for
p-nitrotolueneortho-sulfonic acid by Pulgarin et al. (1999).
The treatability of raw and pretreated wastewater by
photocatalytic oxidation was investigated by Balciolu and
Arslan (1998). The results obtained show that the photo-
catalytic oxidation process is more efficient in the removal
of pollutants from pretreated wastewater.
Adsorption techniques have potential for removing
organics from water due to their high efficiency and ability
to separate a wide range of chemical compounds (Suffet
and McGurie, 1985; Slejko, 1985). Activated carbon has
been widely used as an adsorbent in wastewater treatment
to remove organic and inorganic pollutants (Chen and Lin,
2001; Ho and Chiang, 2001; Meshko et al., 2001; Wu et al.,
2001; Yang and Al-Duri, 2001; Gupta and Ali, 2002; Wu
et al., 2002; Tseng et al., 2003). Possessing high specific
957
surface area, activated carbon frequently exhibits high
removal efficiency for most dissolved compounds. It has a
good capacity for the adsorption of many organic
molecules. In spite of this it suffers from few disadvantages.
Activated carbon is quite expensive, and its regeneration
produces additional effluent and results in considerable loss
(10–15%) of the adsorbent. Over the years, waste materials
from agricultural products, such as rice straw, coconut
husk, peat moss, etc., have been exploited as possible
alternatives to activated carbon to remove hazardous
chemicals (Chiang et al., 2000). Gupta et al. (1997, 2000,
2003, 2004b, 2005a, b) and Jain et al. (2003a–c) have also
utilized various adsorbents for the removal of dyes from
wastewater. In this study, photocatalysis and adsorption
with both rice husk and activated carbon were used to
remove the toxic dye Rhodamine B from wastewater.
2. Experimental
2.1. Materials and methods
The photo-catalyst anatase titanium dioxide (44 mm) was
obtained from M/s Merck. All other laboratory reagents
used in the present studies were of analytical grade. The
stock solution and all other solutions of Rhodamine-B
were prepared in double distilled water, and the same was
used for the necessary dilution. Aqueous solutions of
Rhodamine B with different concentrations were prepared
from 0.01 mol/L stock solution. The adsorbent rice husk
was a free gift from a local rice mill, while activated carbon
was purchased from M/s Merck.
Measurements of pH of the solutions were carried out on
a digital pH meter DB 1011 fitted with a glass electrode.
A COD digestion apparatus (Spectra Lab 2015-S) was used
for determining COD. A Spectronic (make 20D+ Ther-
mospectronic) spectrophotometer was used to measure the
absorbance of the liquid samples at appropriate wave-
lengths. All experiments of photo-catalytic degradation
were conducted in a photo-catalytic reactor. Irradiation
was carried out using a 6 W UV lamp (l ¼ 254 nm) placed
inside the well of a quartz glass reactor of 150 mL capacity.
The reactor set-up was covered with a black colored
wooden box to prevent UV radiation leakage.
2.2. Photo-catalytic studies
In a 250 mL flask, 100 mL of the dye solution of an
appropriate concentration was placed and the pH was
taken. A known amount (varying from 0.005 to 0.02 g) of
TiO2 powder was added to the dye solution and the mixture
was irradiated with the UV lamp. To ensure efficient mixing
of TiO2 catalyst in the reactor, the solution was agitated by
bubbling oxygen from the side of the reactor continuously
throughout the reaction. At specific time intervals suitable
aliquots of the samples were withdrawn and analyzed
spectrophotometrically at lmax 554 nm after proper cen-
trifugation. The reaction was thought to be completed when
 ARTICLE IN PRESS
958 R. Jain et al. / Journal of Environmental Management 85 (2007) 956–964

the dye solution became completely colorless and at this
stage measurements were stopped. All the experiments were
carried out at room temperature (30 1C).
2.3. Adsorption studies
The adsorbent material, activated carbon, was used as
received. The other material, rice husk, was cleaned and
thoroughly washed with distilled water, and then dried.
The material was ground and sieved to desired particle
sizes. These were then treated with acetic acid and again
washed with distilled water. Thereafter, the rice husk was
treated with hydrogen peroxide (100 volumes) to remove
all adhering organic particulates and other impurities, and
further dried in a vacuum oven for 1 h at 60 1C. The final
product obtained was stored in a vacuum desiccator until
used.
All adsorption experiments were carried out at different
temperatures (40, 50 and 60 1C) using a batch technique.
Adsorption isotherms were recorded at a fixed pH (pH range
2–12) over the concentration range 1  10–5–9  10–5 mol/L
of Rhodamine-B solutions, prepared by diluting 0.01 mol/L
The influence of photo-catalyst amount on the rate of
degradation of the dye at pH 6.7 indicates that the
degradation rate increased slowly by adding TiO2 from
0.005 to 0.010 g and thereafter a rapid increase in the rate
was observed (Fig. 2). This indicates strong adsorption of
the dye over the surface of the TiO2 up to 0.010 g, which
inhibits the photo-catalytic behavior of TiO2. Therefore, all
studies were carried out by adding more than 0.010 g of
TiO2. From Fig. 2 it is apparent that at 0.015 g there is a
rapid increase in the rate of degradation. This may be due
to the fact that with the increase in the amount of TiO2, the
number of active site increased. Thus all further studies
were carried out by adding 0.015 g of TiO2 in the dye
solution and the change in the volume of the reaction
mixture was assumed to be negligible.
0.2
0
0 10 20 30 40 50 60
log (Absorbance)

of stock solution in a series of 100 mL graduated conical -0.2

flasks containing 25 mL of solution of each concentration.
Adsorption was achieved by adding a known amount of each
-0.4
adsorbent of a specific sieve size into the dye solution of
known concentration and pH, and the conical flasks were
-0.6
agitated intermittently. Once the equilibrium was thought to
be established, supernatant liquid was filtered off using
Whatman filter paper Number-42, and uptake of the dye was -0.8 Catalyst Absent + UV Light Present
Catalyst Present + UV Light Absent
determined spectrophotometrically by measuring the absor- Both Catalyst & UV Light Present
bance at 554 nm. -1
Time (minutes)

3. Results and discussion Fig. 1. Photo-catalytic degradation of Rhodamine B in different

conditions at concentration 5.0  105 mol/L (pH 6.7 and temperature
3.1. Photo-catalytic degradation 30 1C).

The photo-catalytic degradation of solutions with 100

different concentrations of the dye Rhodamine-B was
carried out for about an hour in the presence of TiO2 under
90
the absence of light, in the absence of TiO2 under UV light
and in the presence of both TiO2 and UV light at 30 1C. It
was observed that at all the concentrations in the absence 80
k × 10-3 (min-1)

of light TiO2 did not catalyze the degradation process.

However, a slight decrease in absorbance was observed, 70
which may be due to the initial adsorption of the dye on to
the TiO2 surface. Similarly in the absence of TiO2, when 60
solutions were irradiated by UV light no change in the
absorbance was recorded. However, when a small amount 50
of TiO2 was added to the solution in the presence of oxygen
and UV light an exponential decrease in the absorbance
40
was obtained. This clearly indicates that the rate of photo-
4 8 12 16
degradation of Rhodamine B in the presence of TiO2 is
Amount of TiO2 × 10-3 (g)
very sensitive to the presence of light. A typical log
(absorbance) versus contact time plot under the above- Fig. 2. Variation of the rate constant for the photo-catalytic degradation
mentioned three conditions is presented in Fig. 1 at pH 6.7 of 5.0  105 mol/L Rhodamine B at different amounts of TiO2 (pH 6.7
and a concentration of 5.0  10–5 mol/L of Rhodamine-B. and temperature 30 1C).
 ARTICLE IN PRESS
R. Jain et al. / Journal of Environmental Management 85 (2007) 956–964 959

45 50

40
45
35
40
k × 10-3 (min-1)

k × 10-3 (min-1)
30

25 35

20
30
15

25
10

5 20
2 4 6 8 10 12 0 1 2 3 4 5 6
pH -5
Initial Dye Concentration × 10 (M)

Fig. 3. Variation of rate constant for the photo-catalytic degradation of Fig. 4. Variation of rate constant for the photo-catalytic degradation of
5.0  105 mol/L Rhodamine B at different pH values (amount of TiO2 different Concentrations of Rhodamine B (amount of TiO2 0.015 g, pH
0.015 g, pH 6.7, temperature 30 1C). 6.7, temperature 30 1C).

130
At all three temperatures, the kinetics of the photo-
catalytic degradation of Rhodamine-B were studied at
different pH values and concentrations of the dye solution, 120
and it was observed that in each case the reaction followed
first-order rate kinetics.
k × 10-3 (min-1)

The effect of pH was recorded by studying the kinetics of 110

photo-catalytic degradation of Rhodamine B in the
presence of TiO2 (0.015 g) in the pH range of 4.0–11.0,
and it was found that the degradation rate remained fairly
constant from pH 2.0 to 6.7 and then increased (Fig. 3).
This shows that the pH of the dye solution has a positive
affect on the heterogeneous photo-catalytic degradation
process in neutral and alkaline media.
The photo-catalytic degradation was also investigated at
different concentrations of Rhodamine-B as a function of
irradiation time and the rate of degradation of Rhodamine-B
was plotted against its concentration. Fig. 4 clearly indicates
that the photo-catalytic degradation of Rhodamine-B
decreased with an increase in its initial concentration.
The electron–hole recombination process is a problem
that is usually associated with using TiO2 as a photo-
catalyst. To assess this parameter, the rate constants of
reactions were determined by adding H2O2 to the reaction
mixture. As shown in Fig. 5, when increasing the amount
of H2O2 the degradation rate remained constant up to
1.5 m mol, and there after it increased. This phenomenon is
due to the effect of electron acceptors on photo-catalytic
degradation of Rhodamine-B. Gerixhac (1993) suggested
that the added quantity of H2O2 not only retards the
electron–hole recombination process but also generates
hydroxyl radicals on absorption of an electron from a
conduction band. This can be explained by the following
equation:
H2 O2 þ e ! OH þ OH .
100
90
80
0 0.5 1 1.5 2 2.5
Amount of H2O2 (Millimoles)
Fig. 5. Variation of rate constant for the photo-catalytic degradation of
5.0  105 mol/L Rhodamine B at different amounts of H2O2 (amount of
TiO2 0.015 g, pH 6.7, temperature 30 1C).
3.2. Adsorption studies
The variation in adsorption of Rhodamine-B was
studied in the pH range from 2.1 to 12.1 using rice husk
and activated carbon adsorbents at the temperatures of 40,
50 and 60 1C. The removal of Rhodamine B followed the
same pattern at 40, 50 and 60 1C for both the adsorbents.
However, in each case with an increase in temperature the
dye removal increased. Fig. 6 presents the amount of dye
adsorbed by each adsorbent with varying pH at 40 1C and
indicates that in both cases the amount adsorbed decreased
with increasing pH. The graph clearly indicates that a
significant drop in the amount adsorbed took place beyond
pH 6 and 9 in the cases of rice husk and activated carbon,
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960 R. Jain et al. / Journal of Environmental Management 85 (2007) 956–964

100 8
Activated Carbon
95 Rice Husk 7
90
6
Percentage Adsorption

Dye Uptake × 10-4 (g)

85
5
80

75 4

70
3
65
2
60
1 Activated Carbon
55
Rice Husk
50 0
2 4 6 8 10 12 0 2 4 6 8 10
pH -5
Concentration × 10 (M)
Fig. 6. Effect of pH on adsorption of Rhodamine B over different
Fig. 7. Effect of Concentration on adsorption of Rhodamine B over
adsorbents at 40 1C.
different adsorbents at 40 1C.

respectively. The maximum adsorption of the dye was 5.5

obtained at pH 2.1, viz. 90% in the case of rice husk and
93.2% for activated carbon. The decrease in the adsorption
5
Amount Adsorbed × 10-4 (g)

of Rhodamine-B with increasing pH can be elucidated by

considering the surface charge of the adsorbent materials.
At low pH, neutralization of the negative charge at the 4.5
surface of the adsorbents increases the protonation and
results in higher adsorption of the dye on each adsorbent.
This facilitates diffusion and results in a larger number of 4

active sites on the surfaces of the adsorbents thereby

enhancing adsorption at the surface. However, with
increasing pH deprotonation of the dye takes place, which
hinders diffusion and a constant decrease in the amount of
dye adsorbed is observed.
The doses of the adsorbents were varied from 1 to
10 mg of activated carbon and 0.1 to 1.0 g of rice husk, and
the amount of removed dye was monitored while carrying
out the experiments at a fixed pH and adsorbate
concentration and different temperatures. It was observed
that at all the temperatures the maximum uptake of
the dye took place at 7.5 mg of activated carbon and 0.4 g
of rice husk.
For observing the effect of concentration of adsorbate
on removal of Rhodamine-B, the concentration range
of 1.0  10–5–9.0  10–5 mol/L was used and adsorption
of the dye was found to increase linearly with increasing
concentration of adsorbate for both the adsorbents
(Fig. 7).
The adsorption studies were also carried out at different
particle sizes (o47, 47–58, 58–69, 69–84, 84–120, 120–142,
4142 mm) of both the adsorbents and at a fixed adsorbent
dose contact time. It was found that the size of rice husk
particles did not alter the adsorption amount much, while
in the case of activated carbon the adsorption decreased
with increasing particle size. Both the adsorbents exhibited
maximum adsorption (about 95%) at particle sizes
3.5
3
0 5 10 15 20 25 30 35
Contact Time (minutes)
Fig. 8. Effect of contact time on adsorption of 7.0  105 mol/L
Rhodamine B over activated carbon at 60 1C.
4142 mm. Thus, adsorbent particle sizes 4142 mm were
selected for the present studies.
The increase in contact time had a significant effect on
adsorption of the dye Rhodamine-B. At all the tempera-
tures, the rate of adsorption increased with an increase in
time. It is clear from the Figs. 8 and 9 that at 60 1C the
optimum time of 30 min was sufficient for the removal of
Rhodamine-B with activated carbon, while in the case of
rice husk the adsorption increased from 1 to 2 h and
thereafter the adsorption almost became constant. The
optimum time for removal of Rhodamine-B was 3 h for rice
husk. Both the experiments were carried out at a fixed
amount of adsorbent, pH 2.1 and different temperatures.
To determine whether the on-going adsorption process
was endothermic or exothermic in nature, adsorption
studies over activated carbon and rice husk were carried
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R. Jain et al. / Journal of Environmental Management 85 (2007) 956–964 961

7 6
R2 = 0.9963
6.5 5.5
Amount Adsorbed × 10-4 (g)

5
6 R2 = 0.9943

1/qe × 104 (Mol.g-1)

4.5
5.5
4 R2 = 0.9961
5
3.5
4.5
3
4
2.5
40 Degree C
3.5
2 50 Degree C
60 Degree C
3
1.5
0 1 2 3 4 5 6
0 0.1 0.2 0.3 0.4 0.5
Contact Time (Hours)
1/Ce × 105 (L. Mol-1)
Fig. 9. Effect of contact time on adsorption of 7.0  105 mol/L
Rhodamine B over rice husk at 60 1C. Fig. 10. Langmuir adsorption isotherms for the Rhodamine B-activated
carbon system.

out at 40, 50 and 60 1C temperatures. In general for both 5

the adsorbents the adsorption of dye increased with an
4.5 R2 = 0.9885
increase in temperature, which indicates that the process
was endothermic in both cases. 4
The results obtained from the adsorption of Rhodamine-
1/qe × 104 (Mol.g-1)

B over rice husk and activated carbon have also been 3.5 R2 = 0.9972
correlated with the following well known forms of the
3
Langmuir (Eq. (1)) and Freundlich (Eq. (2)) models:
2.5 R2 = 0.9771
1 1 1 1
¼ þ , (1)
qe Qo bQo C 2

40 Degree C
1.5
1 50 Degree C
log qe ¼ log K f þ log C, (2) 60 Degree C
n 1
0.03 0.06 0.09 0.12 0.15
where C is the measured molar concentration in solution at 1/Ce × 105 (L. Mol-1)
equilibrium, Qo the number of moles of solute adsorbed per
unit weight of adsorbent, qe the number of moles of solute Fig. 11. Langmuir adsorption isotherms for the Rhodamine B-rice husk
adsorbed per unit weight at concentration C and b, Kf and system.
n are constants.
It was observed that the adsorption of Rhodamine-B
over both the adsorbents fully satisfied the Langmuir The feasibility of the on-going adsorption processes was
(Figs. 10 and 11) and Freundlich (Figs. 12 and 13) models also evaluated by the method suggested by Weber and
and straight lines were obtained in each case. This indicates Chakraborti (1974). Hall et al. (1966) gave a dimensionless
uniform adsorption and strong dye—adsorbent interac- constant, the separation factor ‘r’, which can be calculated
tions over the surfaces of both the adsorbents. The by the following equation:
Langmuir and Freundlich constants obtained from these
1
plots are listed in Table 1. In both cases, the value of Qo r¼ , (3)
1 þ bC o
obtained from the Langmuir plots (i.e. maximum uptake)
increased with an increase in temperature. This also where values of b and Co are obtained from the Langmuir
confirms that the processes were to be endothermic in isotherm. The linear, favorable or irreversible nature of the
nature. However, the Qo values appear to be slightly higher isotherm is dependent on the obtained value of r being
for the Rhodamine-B—rice husk system, indicating thereby unity, between 0 and 1, or zero, respectively. Table 2 clearly
better adsorption ability of rice husk. The data also show shows that in all the cases the values of r were positive and
that the value of Kf is almost unity for both the systems at less than unity, indicating thereby a highly favorable
all temperatures. adsorption in both the cases.
 ARTICLE IN PRESS
962 R. Jain et al. / Journal of Environmental Management 85 (2007) 956–964

-0.3 The Langmuir isotherm data were used for calculating

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 the thermodynamic parameters of each adsorption system
-0.35
using the following equations:
-0.4
DG o ¼ R T ln b, (4)
R2 = 0.954
-0.45
   
T 2T 1 b2
log qe × 10-4

-0.5 o
DH ¼ R ln , (5)
ðT 2  T 1 Þ b1
-0.55
R2 = 0.9994
-0.6 DH o  DG o
DS o ¼ , (6)
-0.65
T
R2 = 0.9931 where b, b1 and b2 are the equilibrium constants at different
-0.7
40 Degree C temperatures, obtained from the slopes of the adsorption
-0.75 50 Degree C isotherms at different concentrations.
60 Degree C The obtained values of the thermodynamic parameters
-0.8
log Ce × 10-5 Gibbs free energy (DGo), enthalpy (DHo) and entropy (DSo)
of the processes are given in Table 3. The negative values of
Fig. 12. Freundlich adsorption isotherms for the Rhodamine B-activated DGo obtained in each case indicate the feasibility and
carbon system. spontaneous nature of the adsorption processes under
standard conditions. It is also observed that in each case,
DGo decreases with increasing temperature, indicating
0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5
-0.2 thereby greater adsorption at higher temperatures. The
R2 = 0.9589
positive values of enthalpy change (DHo) confirm the
endothermic nature of the adsorption in both the cases,
-0.3
while the positive DSo values reflect a good affinity of rice
R2 = 0.9974
husk and activated carbon towards Rhodamine-B.
log qe × 10-4

-0.4
3.3. COD measurements
R2 = 0.9654
-0.5
In order to measure the pollution strength of the dye,
chemical oxygen demand (COD) of the dye solutions was
-0.6 40 Degree C assessed before and after its removal during photo-catalytic
50 Degree C degradation and adsorption over both the adsorbents.
60 Degree C
A significant decrease in the COD values of the Rhodamine
-0.7
log Ce × 10-5
B solution (from 1608 to 232 mg/L in the case of the photo-
catalyzed process and 267 and 276 mg/L when adsorbed
Fig. 13. Freundlich adsorption isotherms for the Rhodamine B-rice husk over activated carbon and rice husk, respectively) was
system. observed. The significant decrease in the COD values

Table 1
Freundlich and Langmuir constants of Rhodamine-B adsorption over different adsorbents at different temperatures

Adsorbent Langmuir constants

Qo  105 mol/g b  104 L/mol

40 1C 50 1C 60 1C 40 1C 50 1C 60 1C

Activated carbon 5.3384 5.8169 6.1109 1.6363 1.8721 3.0567

Rice husk 5.8733 6.8752 8.7796 0.8140 1.0454 1.2941

Adsorbent Freundlich constants

n Kf

40 1C 50 1C 60 1C 40 1C 50 1C 60 1C

Activated carbon 0.1797 0.1902 0.2472 0.9999 0.9999 0.9999

Rice husk 0.2222 0.2449 0.2884 0.9998 0.9998 0.9998
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R. Jain et al. / Journal of Environmental Management 85 (2007) 956–964 963

Table 2 Chen, J.P., Lin, M., 2001. Equilibrium and kinetics of metal ion
Parameters indicating the shape of isotherms adsorption onto a commercial H-type granular activated carbon:
experimental and modeling studies. Water Research 35, 2385–2394.
Adsorbent r-Value Chiang, H.L., Tsai, J.H., Chang, G.H., Jeng, F.T., 2000. Diffusion of
hydrogen sulfide and methyl mercaptan onto microporous alkaline
40 1C 50 1C 60 1C activated carbon. Chemosphere 41, 1227–1232.
Dominguez, C., Garcia, J., Pedraz, M.A., Torres, A., Galan, M.A., 1998.
Activated carbon 0.3802 0.3484 0.2463
Photocatalytic oxidation of organic pollutants in water. Catalysis
Rice husk 0.1816 0.1968 0.2231
Today 40, 85–101.
Gerixhac, A.H., 1993. Photoelectrochemical catalysis of the oxidation of
organic molecules by oxygen on small semiconductor particles with
TiO2 as an example. Electrochimica Acta 38, 39–45.
Table 3 Goncalves, M.S.T., Oliveira-Campos, A.M.F., Pinto, E.M.M.S., Plasen-
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Activated carbon 25.249 26.417 28.592 27.412 167.693
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